CN106011696A - High-strength high-elasticity high-plasticity block nano metallic glass material and preparation method thereof - Google Patents

Abstract

The invention belongs to the design and preparation technology of metallic glass materials, in particular to a high-strength, high-elasticity and high-plasticity in-situ endogenous block nano-metallic glass material and a preparation method thereof. The material includes phase-separated alloying elements Fe and Cu, and alloying elements Zr and Al. The alloy melt undergoes nanoscale phase separation before the glass transition occurs. A bulk metallic glass material containing spherical nano metallic glass particles with a high number density and a matrix metallic glass is prepared by adopting a rapid solidification technology. The number density and volume fraction of spherical nano metallic glass particles are 10 ²⁰ ~ 10 ²⁴ m ^–3 and 45 ~ 49.5%, respectively, and the sizes of metallic glass particles are mainly distributed in the range of 2 ~ 10nm. The in-situ endogenous block nano-metallic glass material of the present invention has high strength, high elasticity and high plasticity, and the block nano-metallic glass material is compressed and deformed at room temperature, the yield strength is 1.6-1.7 GPa, and the elastic limit is not less than 2%. From the height: The columnar sample with diameter=2:1 plastically deforms into a cake shape with height:diameter<1:1 without breaking.

Description

A high-strength, high-elasticity, high-plasticity bulk nano metallic glass material and preparation method thereof

technical field

The invention belongs to the design and preparation technology of metallic glass materials, specifically a high-strength, high-elasticity and high-plasticity block nano-metallic glass material and its preparation method, using phase separation metallurgical characteristics and alloy optimization design theory, adopting rapid solidification technology Obtain in-situ endogenous bulk nano metallic glass materials with high strength, high elasticity and high plasticity.

Background technique

Metallic glass materials (that is, amorphous alloys) have excellent mechanical, physical, and chemical properties, and have broad application prospects in the fields of automobiles, aerospace, electronics, machinery, medical materials, and sporting goods. Since the discovery of Au-Si alloy metallic glass materials in the form of thin ribbons for the first time in 1960, there has been great interest in this new class of metallic materials. In 1982, bulk metallic glasses with critical dimensions larger than 1 mm were reported for the first time. Subsequently, researchers conducted a lot of research on the amorphous forming ability of metallic glasses, and discovered the chemical composition of bulk metallic glasses of various alloy systems. Up to now, there has been rapid development both in the size of bulk metallic glass and in the types of metallic glass alloys. Researchers have successively discovered a variety of metallic glass alloys, such as Cu-based, Fe-based, Ca-based, Al-based, La-based, Zr-based, Pd-based, Co-based, Ti-based, Ni-based, Y-based, Nd-based, Laki and so on. The alloy systems whose critical diameter can reach 10mm include Cu-based, Fe-based, La-based, Zr-based, Pd-based, Ti-based, Pt-based, Y-based, Mg-based, Ca-based, etc. Among them, the Pd-based and Zr-based alloys have the ability to form glass For the strongest, the critical diameter exceeds 70mm. Although the amorphous formation ability of some alloys has been greatly improved, there is generally a bottleneck problem in amorphous alloys-poor room temperature plasticity. This severely limits the practical application of metallic glasses as key materials.

In recent years, Germany's Gleiter has proposed the concept of nanoglass (nanoglasses) material. The structural characteristics of nano-metallic glass materials are that each metallic glass constituent unit is amorphous and its size is at the nanometer scale, and there are a large number of metallic glass/metallic glass interfaces. The techniques for preparing this material mainly use evaporation and magnetron sputtering, so that the production efficiency and sample size of this material are limited. In 2011, Chen used magnetron sputtering technology to deposit AuAgPdCuSiAl nano-metallic glass thin film materials on silicon substrates. In addition, in 2012, Fang of the Gleiter research group prepared Sc ₇₅ Fe ₂₅ nanometer glass powder by evaporation + inert gas condensation method, and then used similar traditional powder metallurgy technology to press the powder into thin sheet Sc ₇₅ Fe ₂₅ nanometer glass. In 2015, Chen used magnetron sputtering technology to prepare FeCuSc nano-metallic glass materials by using the mutual repulsion between alloying elements Fe and Cu. Studies have shown that nano-metallic glass materials have excellent mechanical, magnetic, electrochemical, biocompatibility, and catalytic properties. However, the preparation of nano-metallic glass by evaporation or magnetron sputtering technology has disadvantages such as complex process, difficult control, high cost, and long cycle, especially it is difficult to achieve the productivity and material size required for industrial applications.

Contents of the invention

The purpose of the present invention is to provide a high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material and its preparation method. Through the optimized design of the alloy, the alloy not only undergoes glass transition during the rapid cooling process, but also forms nano Glass tissue structure. On the one hand, it is to solve the alloy design and preparation technology of bulk nano-metallic glass materials, and on the other hand, it is to solve the bottleneck problem of poor room temperature plasticity of bulk metallic glass materials, and to design a new type of high-strength, large elastic limit and superplasticity. Material.

Technical scheme of the present invention is:

A high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material, which contains a liquid-liquid phase separation alloy Fe-Cu formed by alloying elements Fe and Cu, and other alloying elements Zr and Al added to promote the alloy's amorphous transformation. The alloy melt undergoes glass transition and liquid-liquid phase separation during the rapid cooling process, and the liquid-liquid phase separation temperature is required to be slightly higher than the glass transition temperature, that is, the alloy glass transition occurs at the beginning of the alloy liquid-liquid phase separation, ensuring that the alloy melt Only nanoscale phase separation occurs before the glass transition. Liquid-liquid separation forms two liquid phases with alloying element Zr as the main component, one of which is distributed in the other matrix liquid phase in the form of droplets or interconnections; the content of alloying element Fe in the spherical droplets is higher than that in the matrix The liquid phase is high, but the alloy element Cu content in the droplet is lower than that of the matrix liquid phase, and the alloy element Al is more uniformly distributed in the two liquid phases; in the bulk nano metallic glass material, the diameter of the spherical nano metallic glass particles is mainly between 2 and Within the range of 10nm; the number density of spherical nano metallic glass particles is 10 ²⁰ ~ 10 ²⁴ m ^–3 , and the particle volume fraction is 45 ~ 49.5%; compression deformation at room temperature, the bulk nano metallic glass material can be obtained by height: diameter = 2: 1 columnar plastic deformation into a cake shape with height:diameter<1:1, without catastrophic fracture, with ultra-high plasticity, the yield strength of the bulk nano metallic glass material is 1.6-1.7GPa and the elastic limit is not lower than 2%.

In the high-strength, high-elasticity and high-plasticity bulk nano metallic glass material, the atomic proportion of alloying element Fe is 9-16%, the atomic proportion of alloying element Cu is 16-24%, and the atomic proportion of alloying element Zr is The atomic ratio is 55-65%, and the atomic ratio of the alloy element Al is 2-10%;

In the high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material, the atomic proportion of the alloying element Fe in the spherical nano-metallic glass particles is 12-20%, and the atomic proportion of the alloying element Fe in the matrix metallic glass is 9~15%;

In the high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material, the atomic proportion of the alloying element Cu in the spherical nano-metallic glass particles is 10-17%, and the atomic proportion of the alloying element Cu in the matrix metallic glass is 21-30%;

In the high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material, the atomic proportions of the spherical nano-metallic glass particles and the alloy element Zr in the matrix metallic glass are all 55-65%;

In the high-strength, high-elasticity and high-plastic bulk nano-metallic glass material, the atomic proportion of the alloying element Al in the spherical nano-metallic glass particles and the matrix metallic glass is equivalent, and the alloying element Al is basically evenly distributed in the entire material;

In the high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material, in the bulk nano-metallic glass material, the diameter of spherical nano-metallic glass particles is in the range of 2-10 nm;

The high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material is obtained by changing the atomic ratio n _Fe /n _Cu of the alloying element Fe to Cu (the variation range is: 1/4<n _Fe /n _Cu <1) or adding The alloy element X (X=Nb or Ta) with an atomic ratio of no more than 1% regulates the size of the metallic glass particles;

In the high-strength, high-elasticity and high-plastic bulk nano-metallic glass material, in the bulk nano-metallic glass material, the number density of spherical nano-metallic glass particles is in the range of 10 ²⁰ to 10 ²⁴ m ⁻³ ;

In the high-strength, high-elasticity and high-plastic bulk nano-metallic glass material, in the bulk nano-metallic glass material, the volume fraction of spherical nano-metallic glass particles is within the range of 45% to 49.5%;

The preparation method of the high-strength, high-elasticity and high-plasticity bulk nano metallic glass material comprises the following steps:

(1) Through alloy element selection and chemical composition optimization, the alloy composition is precisely designed, and the mixing heat between the alloy elements Fe and Cu is positive and mutually repulsive, and the liquid-liquid phase separation occurs in the alloy melt during the rapid cooling process, requiring liquid- The liquid phase separation temperature is slightly higher than the glass transition temperature of the alloy, that is, the glass transition of the alloy occurs immediately after the liquid-liquid phase separation of the alloy begins, ensuring that only nanoscale phase separation occurs in the alloy melt before the glass transition.

(2) The purity of the Fe, Cu, Zr, and Al metal raw materials used is not less than 99.9 wt%, and the commercially available metal raw materials with clean surfaces are placed in the water-cooled copper crucible of the electric arc melting furnace, and the vacuum degree of the melting chamber is not lower than 2.5 After ×10 ^-3 Pa, high-purity nitrogen gas with a volume purity of 99.999% is filled before arc smelting until the pressure in the smelting chamber reaches 0.05MPa. Before smelting Fe, Cu, Zr, and Al metal raw materials, first smelt Ti ingots to absorb oxygen and other impurities, and further purify the protective gas. When smelting Fe, Cu, Zr, and Al metal raw materials, use electromagnetic stirring, control the smelting current at 200-300A, and repeatedly smelt 3-4 times to obtain Fe-Cu-Zr-Al Master alloy ingot.

(3) Take a few grams of the master alloy and place it in a quartz crucible, and inductively heat and rapidly melt the alloy in a vacuum environment with a vacuum degree of not less than 2.5×10 ^-3 Pa. The nano-metallic glass material is prepared by single-roll melt-slinging or copper mold casting technology at 10 ³ -10 ⁶ K/s.

Advantage of the present invention and beneficial effect are:

The invention makes use of the metallurgical characteristics of the Fe-Cu liquid-liquid phase separation alloy having a liquid component immiscible region, through alloy type selection and chemical composition optimization design, so that the FeCuZrAl alloy melt first undergoes nanoscale transition before glass transition occurs. Liquid-liquid phase separation forms two liquid phases with Zr as the main component, one of which is distributed in the matrix liquid phase in the form of nano-spherical droplets, and the Fe content in the spherical droplets is higher than that in the matrix liquid phase The content of Cu in the spherical droplet is lower than that in the matrix liquid phase, but the distribution of Al in the two liquid phases is relatively uniform. Under rapid cooling conditions such as single-roll melting or copper mold casting, the glass transition occurs in the two liquid phases, and a bulk nano-metallic glass material is formed in situ. According to needs and alloy design, nano-metallic glass materials can be prepared, which not only simplifies and shortens the preparation process of such materials and reduces costs, but also points out the direction for the development of new high-performance metal materials. In the preparation process of the nano metallic glass material, the most ideal method is that the nano metallic glass unit is formed by in-situ endogenous growth.

On the one hand, this can reduce the influence of the external environment on the thermal stability of the nano-metallic glass unit, and can ensure the uniform distribution of the nano-glass unit energy after the material is formed; on the other hand, the solidified nano-metallic glass unit and the metal glass matrix The interfaces are well integrated. This in-situ endogenous method for preparing nano-metallic glass materials has a simple process and low cost. Compared with traditional preparation methods, it has obvious advantages in material sample size and production efficiency. In particular, the material integrates properties such as high strength, large elastic limit, and superplasticity, and is an excellent new metal material.

Description of drawings

Fig. 1 is a high-resolution transmission electron microstructure diagram of the Cu ₃₃ Zr ₅₉ Al ₈ bulk metallic glass material provided for comparison of the nano-metallic glass structure of the present invention, which shows that there is no structural feature, and no liquid-liquid phase separation occurs. There is no endogenous formation of nanometallic glass units.

Fig. 2 is a high-resolution transmission electron micrograph of the bulk nano-metallic glass material prepared by the copper mold casting method of the alloy of Example 1 of the present invention (Fe ₁₀ Cu ₂₃ Zr ₅₉ Al ₈ —sample 1).

Fig. 3 is a high-resolution transmission electron micrograph of the bulk nano-metallic glass material prepared by the copper mold casting method of the alloy (Fe ₁₂ Cu ₂₁ Zr ₅₉ Al ₈ ) in Example 2 of the present invention.

Fig. 4 is a high-resolution transmission electron micrograph of the bulk nano-metallic glass material prepared by the copper mold casting method of the alloy of Example 3 of the present invention (Fe _14.85 Cu _18.15 Zr ₅₉ Al ₈ —sample 3).

Fig. 5 is a high-resolution transmission electron micrograph of the bulk nano-metallic glass material prepared by the copper mold casting method of the alloy (Fe _14.35 Cu _17.65 Zr ₅₉ Al ₈ Nb ₁ ) in Example 4 of the present invention.

Figure 6(a) shows the compression deformation of the bulk nano-metallic glass material at room temperature prepared by the copper mold casting method of the alloy of Example 3 of the present invention (Fe _14.85 Cu _18.15 Zr ₅₉ Al ₈ - sample 3), from height: diameter = 2: The columnar transformation of 1 into a pie-shaped process diagram of height:diameter<1:1, the material did not break during the compression process; (b) is the alloy Fe ₁₀ Cu ₂₃ Zr ₅₉ Al ₈ in Example 1 of the present invention——Sample 1) And Example 3 alloy Fe _14.85 Cu _18.15 Zr ₅₉ Al ₈ of the present invention——sample 3 nanometer metallic glass material compresses the real stress-strain curve in the range of 0-110% strain at room temperature, and the amount of plastic deformation of each sample is due to the equipment Limit, the artificial control strain reaches 110% to stop compression.

detailed description

In the specific implementation process, the present invention provides the alloy design and preparation technology of nano-metallic glass materials, utilizing the metallurgical characteristics of the immiscible region of liquid components in the Fe-Cu liquid-liquid phase separation alloy, through the selection of alloy types and chemical composition Optimize the design so that the FeCuZrAl alloy melt undergoes nanoscale liquid-liquid phase separation before the glass transition occurs, forming two liquid phases with Zr as the main component, one of which is in the form of nano-spherical droplets or interconnected The form is distributed in another matrix liquid phase, the alloy element Fe in the spherical nano-metallic glass particles accounts for 12-20% of the atoms, and the alloy element Fe in the matrix metallic glass accounts for 9-15% of the atoms. The atomic proportion of alloying element Cu in the nano-metallic glass particles is 10-17%, while the atomic proportion of the alloying element Cu in the matrix metallic glass is 21-30%. The alloy in the spherical nano-metallic glass particles and the matrix metallic glass The atomic proportion of the element Zr is 55-65%. The atomic proportion of the alloying element Al in the spherical nano-metallic glass particles and the matrix metallic glass is equivalent. The alloying element Al is basically evenly distributed in the whole material. The atomic ratio is 2 to 10%. Under rapid cooling conditions such as single-roll melting or copper mold casting, the glass transition occurs in the two liquid phases, and a bulk nano-metallic glass material is formed in situ, and its microstructure is shown in Figure 2-5. In order to make a clear comparison with the general structure of bulk metallic glass materials, Fig. 1 shows the high-resolution transmission electron microstructure of CuZrAl bulk metallic glass materials, which shows that there are no structural characteristics and no liquid-liquid phase separation occurs , without the endogenous formation of any nanometallic glass units.

In terms of alloy selection and design of the high-strength, high-elasticity, and high-plasticity bulk nano-metallic glass material, first, the alloying elements Fe and Cu are selected to form an Fe-Cu liquid phase separation alloy, and other alloying elements Zr are added to promote the amorphous transformation of the alloy. and Al. Utilizing that the mixing heat between alloying elements Fe and Cu is positive and mutually repulsive, liquid-liquid phase separation occurs in the alloy melt during rapid cooling, and the liquid-liquid phase separation temperature is required to be slightly higher than the glass transition temperature of the alloy, that is, the glass transition of the alloy is tight. Occurs with the onset of alloy liquid-liquid phase separation, ensuring that only nanoscale phase separation occurs in the alloy melt prior to the glass transition. For this reason, the atomic proportion of alloying element Fe is 9-16%, the atomic proportion of alloying element Cu is 16-24%, the atomic proportion of alloying element Zr is 55-65%, and the atomic proportion of alloying element Al is The atomic ratio is 2 to 10%. In bulk nano metallic glass materials, the diameter of spherical nano metallic glass particles is mainly in the range of 2-10nm. If the size of spherical nano-metallic glass particles is controlled, ① change the atomic ratio of alloying elements Fe and Cu, the best range of variation of the atomic ratio of Fe and Cu is 1/4<n _Fe /n _Cu <1); ② add atoms Alloying element X (X=Nb or Ta) in a proportion not exceeding 1%. The number density of the spherical nano metallic glass particles is in the order of 10 ²⁰ -10 ²⁴ m ^-3 , and the particle volume fraction is 45-49.5%. Carry out the test and analysis of the compressive mechanical properties of the material at room temperature. The yield strength of the bulk nano-metallic glass material is 1.6-1.7GPa, the elastic limit is not lower than 2%, and it has superplasticity. The bulk nano-metallic glass material can be obtained by height: diameter = 2: The columnar plastic deformation of 1 becomes a pie shape with height:diameter<1:1, and there is no catastrophic fracture similar to the compression of traditional metallic glass materials.

In terms of the preparation method of the high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material, first purchase a number of metal raw materials Fe, Cu, Zr, and Al blocks with a purity of not less than 99.9wt% from the market, and clean the surface of the metal raw materials After treatment, according to the designed alloy composition, the metal Fe, Cu, Zr, Al block raw materials are placed in the water-cooled copper crucible of the electric arc melting furnace. Then, when the vacuum degree of the smelting chamber is not lower than 2.5×10 ^-3 Pa, high-purity nitrogen gas with a volume purity of 99.999% is filled before arc smelting until the air pressure in the smelting chamber reaches 0.05MPa. Before melting Ti ingots to absorb oxygen and other impurities, further purify the protective gas. When smelting Fe, Cu, Zr, and Al metal raw materials, electromagnetic stirring is used at the same time. The melting current is controlled at 200-300A, and the melting is repeated for 3 ~4 times to obtain Fe-Cu-Zr-Al master alloy ingot. After the master alloy ingot is cooled, take a few grams of the master alloy and place it in a quartz crucible, and inductively heat and rapidly melt the alloy in a vacuum environment with a vacuum degree of not less than 2.5×10 ^-3 Pa. When the temperature reaches 1100-1250°C, use Nano-metallic glass materials are prepared by rapid solidification technologies such as single-roll melting and throwing, copper mold suction casting, and copper mold spray casting with a cooling rate of not less than 10 ³ to 10 ⁶ K/s.

The present invention provides a design and preparation method of a high-strength, high-elasticity and high-plasticity bulk nano-metallic glass material. The existing form of the material, such as rod, plate, powder, flake, strip, etc., depends on the copper mold used during rapid solidification . When the copper mold suction casting method is used to prepare bulk nano-metallic glass materials, rods (diameter 1-10mm, length not less than 50mm) or plates (thickness 1-5mm, width 2-12mm) can be produced from gram to kilogram batches , the length is not less than 50mm); when the nano-metallic glass material is prepared by the single-roll melting and throwing method, strips from gram to kilogram batches can be prepared (thickness 10-100μm, width 2-30mm, length several meters); high pressure When prepared by gas atomization rapid solidification technology, nano-metallic glass powder (powder diameter 5-300 μm) can be obtained in gram-level to kilogram-level batches. Although the preparation methods of nano-metallic glass materials are different according to different requirements, they are the same in that the glass transition of the alloy melt occurs immediately after the alloy liquid-liquid phase separation begins, ensuring that the alloy melt only occurs at the nanoscale before the glass transition. The phase separation of nanometer-sized spherical glass particles (nano metallic glass units) is dispersed in the metallic glass matrix. After solidification, the interface between the nano-metallic glass units and the metallic glass matrix is well bonded. This in-situ endogenous method for preparing nano-metallic glass materials is simple and cost-effective. Compared with traditional evaporation or sputtering preparation methods, the present invention has obvious advantages in material sample scale and production efficiency. In particular, the material of the invention integrates high strength, large elastic limit, superplasticity, etc., and is an excellent new metal material.

The present invention will be further described in detail below by way of examples.

Example 1

In this embodiment, the chemical composition of the alloy is firstly designed to form an Fe-Cu liquid phase separation alloy with the alloying elements Fe and Cu, and the mixing heat between the alloying elements Fe and Cu is positive and mutually repulsive, and the alloy melt occurs during the rapid cooling process. Liquid-liquid phase separation. Other alloying elements Zr and Al are added to promote the alloy's amorphous transformation. The glass transition of the alloy occurs immediately after the onset of alloy liquid-liquid phase separation, ensuring that only nanoscale phase separation occurs in the alloy melt before the glass transition. The atomic proportion of alloying element Fe is designed to be 10%, the atomic proportion of alloying element Cu is 23%, the atomic ratio of alloying element _Fe to _Cu is designed to be 10/23, and the atomic proportion of alloying element Zr is The proportion is 59%, and the atomic proportion of the alloy element Al is 8%.

Then, a number of metal raw materials Fe, Cu, Zr, and Al blocks with a purity not lower than 99.9wt% are purchased from the market, and the surface of the metal raw materials is cleaned. According to the designed alloy composition, the weighed metal Fe, Cu, Zr, Al block raw materials are placed in the water-cooled copper crucible of the arc melting furnace. Then use mechanical pump + ^{turbomolecular pump} to evacuate the melting chamber. High-purity argon with a volumetric purity of 99.999% until its pressure reaches 0.05MPa. Then, Ti ingots are first smelted by tungsten arc to absorb oxygen and other impurities, and further purify the protective gas. Subsequently, the metal raw materials Fe, Cu, Zr and Al in the water-cooled copper crucible were smelted by electric arc, the smelting current was controlled at 200-300A (240A in this embodiment), and the electromagnetic stirring device was turned on at the same time, and the smelting was repeated 3-4 times to obtain Fe- Cu-Zr-Al master alloy ingot. After the master alloy ingot is cooled, take a few grams of the master alloy and place it in a quartz crucible, and inductively heat and melt it quickly in a vacuum environment with a vacuum degree of not less than 2.5×10 ^-3 Pa (1.5×10 ^-3 Pa in this embodiment) Alloy, when the temperature reaches 1200 ° C, the bulk nano metallic glass material is prepared by copper mold suction casting rapid solidification technology.

A high-resolution transmission electron microscope (HRTEM) was used to observe the prepared bulk nano-metallic glass material sample, as shown in FIG. 2 . By quantitative metallographic analysis software, the average size of the nano-glass particles is about 2.12nm, the number density of the spherical nano-metallic glass particles is about the order of 8.4×10 ²⁴ m ^–3 , and the particle volume fraction is 49.4%. The compressive mechanical properties test and analysis at room temperature shows that the yield strength of the bulk nano-metallic glass material is ~1.61GPa, and the elastic limit is ~2%, as shown in the illustration in Figure 6(b); at a strain rate of 2.5×10 ^-4 Compression height under s ^-1 : diameter = 2:1 bulk nano-metallic glass columnar sample, plastically deformed into a cake shape, showing superplasticity, as shown in the real stress-strain curve of sample 1 in Fig. 6(b).

Example 2

In this embodiment, the chemical composition of the alloy is firstly designed to form an Fe-Cu liquid phase separation alloy with the alloying elements Fe and Cu, and the mixing heat between the alloying elements Fe and Cu is positive and mutually repulsive, and the alloy melt occurs during the rapid cooling process. Liquid-liquid phase separation. Other alloying elements Zr and Al are added to promote the alloy's amorphous transformation. The glass transition of the alloy occurs immediately after the onset of alloy liquid-liquid phase separation, ensuring that only nanoscale phase separation occurs in the alloy melt before the glass transition. The atomic proportion of alloying element Fe is designed to be 12%, the atomic proportion of alloying element Cu is 21%, the atomic ratio of alloying element _Fe to _Cu is designed to be 4/7, and the atomic proportion of alloying element Zr is The proportion is 59%, and the atomic proportion of the alloy element Al is 8%.

Then, a number of metal raw materials Fe, Cu, Zr, and Al blocks with a purity not lower than 99.9wt% are purchased from the market, and the surface of the metal raw materials is cleaned. According to the designed alloy composition, the weighed metal Fe, Cu, Zr, Al block raw materials are placed in the water-cooled copper crucible of the arc melting furnace. Then use mechanical pump + ^{turbomolecular pump} to evacuate the melting chamber. High-purity argon with a volumetric purity of 99.999% until its pressure reaches 0.05MPa. Then, Ti ingots are first smelted by tungsten arc to absorb oxygen and other impurities, and further purify the protective gas. Subsequently, the metal raw materials Fe, Cu, Zr, and Al in the water-cooled copper crucible were smelted by electric arc, the smelting current was controlled at 200-300A (280A in this embodiment), and the electromagnetic stirring device was turned on at the same time, and the smelting was repeated 3-4 times to obtain Fe- Cu-Zr-Al master alloy ingot. After the master alloy ingot is cooled, take a few grams of the master alloy and place it in a quartz crucible, and inductively heat and melt it quickly in a vacuum environment with a vacuum degree of not less than 2.5×10 ^-3 Pa (1.0×10 ^-3 Pa in this embodiment) Alloy, when the temperature reaches 1200 ° C, the bulk nano metallic glass material is prepared by copper mold suction casting rapid solidification technology.

A high-resolution transmission electron microscope (HRTEM) was used to observe the prepared bulk nano-metallic glass material sample, as shown in FIG. 3 . By quantitative metallographic analysis software, the average size of the nano-glass particles is about 2.87nm, the number density of the spherical nano-metallic glass particles is about 6.5×10 ²⁴ m ^–3 , and the particle volume fraction is 49.3%. The compressive mechanical properties test and analysis were carried out at room temperature. The yield strength of the bulk nano-metallic glass material is ~1.63GPa, the elastic limit is ~2%, and the compression height at a strain rate of 2.5×10 ^-4 s ^-1 : diameter = 2 : 1 bulk nano metallic glass columnar sample, plastically deformed into a cake shape, showing superplasticity.

Example 3

In this embodiment, the chemical composition of the alloy is firstly designed to form an Fe-Cu liquid phase separation alloy with the alloying elements Fe and Cu, and the mixing heat between the alloying elements Fe and Cu is positive and mutually repulsive, and the alloy melt occurs during the rapid cooling process. Liquid-liquid phase separation. Other alloying elements Zr and Al are added to promote the alloy's amorphous transformation. The glass transition of the alloy occurs immediately after the onset of alloy liquid-liquid phase separation, ensuring that only nanoscale phase separation occurs in the alloy melt before the glass transition. The atomic proportion of alloying element Fe is designed to be 14.85%, the atomic proportion of alloying element Cu is 18.15%, the atomic ratio of alloying element _Fe to _Cu is designed to be 9/11, and the atomic proportion of alloying element Zr is The proportion is 59%, and the atomic proportion of the alloy element Al is 8%.

Then, a number of metal raw materials Fe, Cu, Zr, and Al blocks with a purity not lower than 99.9wt% are purchased from the market, and the surface of the metal raw materials is cleaned. According to the designed alloy composition, the weighed metal Fe, Cu, Zr, Al block raw materials are placed in the water-cooled copper crucible of the arc melting furnace. Then use mechanical pump + ^{turbomolecular pump} to evacuate the melting chamber. High-purity argon with a volumetric purity of 99.999% until its pressure reaches 0.05MPa. Then, Ti ingots are first smelted by tungsten arc to absorb oxygen and other impurities, and further purify the protective gas. Subsequently, the metal raw materials Fe, Cu, Zr and Al in the water-cooled copper crucible were smelted by electric arc, the smelting current was controlled at 200-300A (240A in this embodiment), and the electromagnetic stirring device was turned on at the same time, and the smelting was repeated 3-4 times to obtain Fe- Cu-Zr-Al master alloy ingot. After the master alloy ingot is cooled, take a few grams of the master alloy and place it in a quartz crucible, and inductively heat and melt it quickly in a vacuum environment with a vacuum degree of not less than 2.5×10 ^-3 Pa (1.5×10 ^-3 Pa in this embodiment) Alloy, when the temperature reaches 1200 ° C, the bulk nano metallic glass material is prepared by copper mold suction casting rapid solidification technology.

A high-resolution transmission electron microscope (HRTEM) was used to observe the prepared bulk nano-metallic glass material sample, as shown in FIG. 4 . By quantitative metallographic analysis software, the average size of the nano-glass particles is about 3.35nm, the number density of the spherical nano-metal glass particles is about 5.2×10 ²⁴ m ^–3 , and the particle volume fraction is 49.4%. The compressive mechanical properties test and analysis at room temperature shows that the yield strength of the bulk nano-metallic glass material is ~1.62GPa, and the elastic limit is ~2%, as shown in the illustration in Figure 6(b); at a strain rate of 2.5×10 ^-4 Compression height under s ^-1 : diameter = 2:1 bulk nano-metallic glass columnar sample, plastically deformed into a cake shape, as shown in Figure 6(a), showing superplasticity, such as the sample in Figure 6(b) 3 Compression true stress-strain curves.

Example 4

In this embodiment, the chemical composition of the alloy is firstly designed to form an Fe-Cu liquid phase separation alloy with the alloying elements Fe and Cu, and the mixing heat between the alloying elements Fe and Cu is positive and mutually repulsive, and the alloy melt occurs during the rapid cooling process. Liquid-liquid phase separation. Other alloying elements Zr and Al are added to promote the alloy's amorphous transformation. The glass transition of the alloy occurs immediately after the onset of alloy liquid-liquid phase separation, ensuring that only nanoscale phase separation occurs in the alloy melt before the glass transition. The atomic proportion of alloying element Fe is designed to be 14.35%, the atomic proportion of alloying element Cu is 17.65%, the atomic ratio of alloying element _Fe to _Cu is designed to be 187/353, and the atomic proportion of alloying element Zr is The proportion is 59%, the atomic proportion of the alloying element Al is 8%, and the alloying element Nb is added with an atomic proportion of 1%.

Then, purchase a number of metal raw materials Fe, Cu, Zr, Al, Nb blocks with a purity not lower than 99.9wt% from the market, and carry out surface cleaning treatment on the metal raw materials. According to the designed alloy composition, the weighed metal Fe, Cu, Zr, Al, Nb block raw materials are placed in the water-cooled copper crucible of the arc melting furnace. Then use mechanical pump + ^{turbomolecular pump} to evacuate the melting chamber. High-purity argon with a volumetric purity of 99.999% until its pressure reaches 0.05MPa. Then, Ti ingots are first smelted by tungsten arc to absorb oxygen and other impurities, and further purify the protective gas. Subsequently, the Fe, Cu, Zr, Al, Nb metal raw materials in the water-cooled copper crucible were arc smelted, the smelting current was controlled at 200-300A (280A in this embodiment), and the electromagnetic stirring device was turned on at the same time, and the smelting was repeated 3-4 times to obtain Fe-Cu-Zr-Al-Nb master alloy ingot. After the master alloy ingot is cooled, take a few grams of the master alloy and place it in a quartz crucible, and inductively heat and melt it quickly in a vacuum environment with a vacuum degree of not less than 2.5×10 ^-3 Pa (1.0×10 ^-3 Pa in this embodiment) Alloy, when the temperature reaches 1200 ° C, the bulk nano metallic glass material is prepared by copper mold suction casting rapid solidification technology.

A high-resolution transmission electron microscope (HRTEM) was used to observe the prepared bulk nano-metallic glass material sample, as shown in FIG. 4 . Through quantitative metallographic analysis software, the average size of the nano-glass particles is about 4.41nm, the number density of the spherical nano-metallic glass particles is about 5.2×10 ²⁴ m ^–3 , and the particle volume fraction is 48.2%. The compressive mechanical properties test and analysis were carried out at room temperature. The yield strength of the bulk nano-metallic glass material is ~1.63GPa, the elastic limit is ~2%, and the compression height at a strain rate of 2.5×10 ^-4 s ^-1 : diameter = 2 : 1 bulk nano metallic glass columnar sample, plastically deformed into a cake shape, showing superplasticity.

Claims (7)

1. the block nanometer metal glass material of a high strength and high flexibility high-ductility, it is characterised in that: include alloy unit Element Fe and Cu forms liquid phase separation alloy Fe-Cu, and other alloying elements promoting amorphous formation added Zr and Al；Alloy melt is occurring before glass transition, occurs nanoscale to be separated, formed both with Zr is the liquid phase of major components, and one of them liquid phase is distributed in another matrix with drops or Join Shape In liquid phase；Melt at single roller and get rid of or under the condition of fast cooling of copper mold casting, two liquid phase generation glass transitions, in situ Interior raw formation contains high number density ball shaped nano metal glass particle and the block nanometer metal of parent metal glass Glass material；High than in matrix liquid phase of Fe content in drop, and the Cu content in spherical droplets compares matrix Low in liquid phase, Al is distribution uniform in two liquid phases；In block nanometer metal glass material, ball shaped nano gold Belong to the diameter of glass particle mainly in the range of 2～10nm；The number density of ball shaped nano metal glass particle It is 10²⁰～10²⁴m^–3, volume fraction is 45～49.5%；At room temperature compression, block nanometer metal glass Glass material is by height: the column of diameter=2:1 plastically deforms into height: < pie of 1:1, its yield strength exists diameter 1.6～1.7GPa, its elastic limit is the lowest by 2%.

2. according to the block nanometer metal glass material of the high strength and high flexibility high-ductility described in claim 1, its feature Being: in block nanometer metal glass material, the atomic ratio shared by alloying element Fe is 9～16%, alloy Atomic ratio shared by element Cu is 16～24%, and the atomic ratio shared by alloy element Zr is 55～65%, Atomic ratio shared by alloy element Al is 2～10%.

3. according to the block nanometer metal glass material of the high strength and high flexibility high-ductility described in claim 1, its feature It is: the atomic ratio 12～20% shared by alloying element Fe in ball shaped nano metal glass particle, and base The atomic ratio 9～15% shared by alloying element Fe in body metal glass.

4. according to the block nanometer metal glass material of the high strength and high flexibility high-ductility described in claim 1, its feature It is: the atomic ratio 10～17% shared by alloying element cu in ball shaped nano metal glass particle, and base Atomic ratio 21～30% shared by alloying element cu in body metal glass.

5. according to the block nanometer metal glass material of the high strength and high flexibility high-ductility described in claim 1, its feature It is: the atomic ratio shared by alloy element Zr in ball shaped nano metal glass particle and parent metal glass is all 55～65%, alloy element Al is former shared by ball shaped nano metal glass particle and parent metal glass Sub-ratio is suitable.

6. according to the block nanometer metal glass material of the high strength and high flexibility high-ductility described in claim 1, its feature Be: in block nanometer metal glass material, the diameter of ball shaped nano metal glass particle and number density 2～ 10nm and 10²⁰～10²⁴m^–3In the range of, by changing the atomic ratio n of alloying element Fe Yu Cu_Fe/n_CuOr Additional trace alloying element X regulates and controls, X=Nb or Ta.

7. according to the preparation side of block nanometer metal glass material of the high strength and high flexibility high-ductility described in claim 1 Method, it is characterised in that comprise the steps:

(1) based on phenomenon of phase separation, select to design with optimization of Chemical Composition by alloying element, make alloy melt Before there is glass transition, first there is the liquid-liquid phase separation of nanoscale, produce the nanometer chi of high number density The drop of degree, controls alloying component, and the volume fraction making matrix liquid phase and nano-liquid droplet is suitable, and nano-liquid droplet is equal Even it is distributed in matrix liquid phase；

(2) used by, the purity of Fe, Cu, Zr, Al raw metal is not less than 99.9wt%, the city of surface cleaning The raw metal sold is placed in the water jacketed copper crucible of arc-melting furnace, and working chamber's vacuum is being not less than 2.5 × 10^-3 After Pa, before electric arc melting, it is filled with the high-purity argon gas that bulk purity is 99.999%, until the air pressure of working chamber reaches 0.05MPa, before melting Fe, Cu, Zr, Al raw metal, first melting Ti ingot absorption impurity, further Purification protective gas, when melting Fe, Cu, Zr, Al raw metal, uses electromagnetic agitation, melting electric current Control 200～300A, melt back 3～4 times, thus obtain Fe-Cu-Zr-Al master alloy ingot；

(3) take foundry alloy number gram to be placed in silica crucible, be not less than 2.5 × 10 in vacuum^-3The vacuum ring of Pa Sensing heating rapid melting alloy under border, after temperature reaches 1100～1250 DEG C, uses rate of cooling to be not less than 10³～10⁶Single roller of K/s is molten to be got rid of or the flash set technology such as copper mold casting prepares nano metal glass material.