CN112553544B - Be-free equal atomic ratio high-entropy amorphous alloy material and preparation method thereof - Google Patents
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- C22C45/00—Amorphous alloys
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Abstract
The invention discloses a Be-free equal atomic ratio high-entropy amorphous alloy material and a preparation method thereof, relating to the field of metal materials; the catalyst comprises the following elements in atomic percentage: ti: 20%, Zr: 20%, Cu: 20%, Ni: 20% and M: 20 percent; m is any one of Nd, Ag and La. On one hand, the alloy does not contain Be element, so that the highly toxic metal is not needed to Be used as an alloy raw material, the environment requirement is met, and the price is relatively low; meanwhile, Nd, Ag or La is selected to replace Be, so that the whole alloy composition still maintains five components, and the amorphous forming capability of the alloy can Be effectively maintained. In addition, the amorphous alloy strip of the material can be prepared by vacuum arc melting and single-roller vacuum melt-spinning technology, has the defects of flat and smooth surface, no pore crack and the like, and has good toughness.
Description
Technical Field
The invention relates to the field of metal materials, in particular to a Be-free equal atomic ratio high-entropy amorphous alloy material and a preparation method thereof.
Background
The amorphous alloy has structural characteristics of long-range disorder, short-range order and isotropy, shows excellent mechanical, magnetic, electrical and electrochemical properties, has wide application prospect in the fields of aerospace, automobiles, precision manufacturing, electronic communication, computers, biomedicine and the like, and is greatly concerned by broad scholars.
The high entropy alloy comprises 5 or more alloy elements, and the atomic percentages of the various alloy constituents are equal or substantially equal. High entropy alloys exhibit a number of unique properties: structurally, due to the high entropy effect in thermodynamics, a high entropy alloy system composed of elements with good chemical compatibility usually generates a few simple solid solutions, even single phases, such as Body Centered Cubic (BCC) or Face Centered Cubic (FCC); in terms of performance, the high-entropy alloy has excellent performances which cannot be compared with the traditional alloy, such as high strength, high hardness, high wear resistance and corrosion resistance, high heat resistance, high resistance and the like.
The high-entropy amorphous alloy is a cross product of the high-entropy alloy and amorphous alloy, has a compact topological structure and a high chemical disorder state, has the comprehensive characteristics of the high-entropy alloy and the traditional amorphous alloy, and has more excellent performance. In 2011, Wangwawa project group first proposed the concept and prepared bulk Sr20Ca20Yb20(Li0.55Mg0.45)20Zn20The high-entropy amorphous alloy shows extremely low glass transition temperature, and shows high-molecular-like thermoplastic deformation behavior at room temperature.
However, the high-entropy amorphous alloy is different from the traditional amorphous alloy in component design, has differences in some empirical parameter criteria, and still solves many problems, so that a great amount of deep experimental exploration and theoretical research are still needed. At present, the reports on the components of high-entropy amorphous alloy with strict equal proportion are not many at home and abroad, and Ti is mainly used20Zr20Cu20Ni20Be20、Ti20Zr20Hf20Be20Cu20、Ti20Zr20Hf20Be20(Cu7.5Ni12.5)、Ti16.7Zr16.7Hf16.7Cu16.7Ni16.7Be16.7However, the alloys all contain a highly toxic metal Be, which is contrary to the environmental requirements of modern society development, so that it is necessary to develop an isoatomic ratio high-entropy amorphous alloy containing no Be.
The invention patent application with the publication number of CN103334065B entitled "high-entropy amorphous alloy material and preparation method thereof" discloses some blocky high-entropy amorphous alloy materials (such as Ti) still containing Be20Hf20Ni20Cu20Be20、NbzNizZrzTizCuzBez、TizZrzHfzNizCuzBez、Ti20Zr20Hf20(Cu20-xNix)Be20) And some high entropy amorphous alloy strips (e.g. Ti) without Be20Zr20Ni20Co20Cu20、Ti20Zr20Ni20Co20Hf20、Nb20Ni20Zr20Ti20Co20、Nb20Ni20Zr20Ti20Cu20、Nb20Ni20Zr20Co20Cu20、NbzNizTizZrzCozCuz)。
However, reports on new components are limited, many problems are not solved yet, and many problems still need a great deal of intensive theoretical research and experimental exploration, so that the development of some novel high-entropy amorphous alloy materials with equal atomic ratio or near atomic ratio has both theoretical and experimental significance.
Disclosure of Invention
One of the purposes of the invention is to provide an equal atomic ratio high-entropy amorphous alloy material without containing Be, which does not contain Be element, so that the highly toxic metal is not needed to Be adopted as an alloy raw material, the environment requirement is met, and the price is relatively low; meanwhile, Nd element, Ag element or La element is selected to replace Be element, so that the whole alloy composition still maintains five components, and the amorphous forming capability of the alloy can Be effectively maintained.
The second purpose of the invention is to provide a preparation method of the Be-free isoatomic ratio high-entropy amorphous alloy material, which adopts a non-consumable vacuum electric arc furnace to obtain a uniform alloy cast ingot, and then obtains an isoatomic ratio high-entropy amorphous alloy strip after vacuum melt spinning.
The embodiment of the invention is realized by the following steps:
in a first aspect, the invention provides an isoatomic ratio high-entropy amorphous alloy material without Be, which comprises the following elements in atomic percentage:
ti element: 20%, Zr element: 20%, Cu element: 20%, Ni element: 20% and M element: 20 percent;
wherein, the M element is any one of Nd element, Ag element and La element.
In an alternative embodiment, the Ti element, the Zr element, the Cu element, the Ni element, and the M element are all high-purity metals having a purity of at least 3N or more.
In a second aspect, the present invention provides a method for preparing the non-Be-containing isoatomic ratio high-entropy amorphous alloy material, including:
ti element, Zr element, Cu element, Ni element and M element are mixed according to the atomic percentage of 20: 20: 20: 20: 20, batching;
smelting the proportioned raw materials in a non-consumable vacuum arc furnace to obtain uniform and consistent alloy ingots;
and (3) preparing the alloy ingot in a vacuum melt-spun machine to obtain the Be-free isoatomic ratio high-entropy amorphous alloy strip.
In an optional embodiment, the step of smelting the proportioned raw materials in a non-consumable vacuum arc furnace to obtain a uniform alloy ingot specifically comprises:
placing the proportioned raw materials in a smelting pit of a non-consumable vacuum arc furnace;
vacuumizing and filling high-purity argon;
repeatedly smelting under the protection of high-purity argon to obtain an alloy ingot.
In an optional embodiment, the step of performing vacuum pumping treatment and filling high-purity argon gas specifically comprises:
the vacuum degree of the equipment cavity reaches 3 multiplied by 10 by rough pumping of a mechanical pump and fine pumping of a molecular pump-3After Pa, filling high-purity argon;
vacuum pumping is carried out again until the vacuum pressure is 3 multiplied by 10-3And after Pa, introducing high-purity argon again.
In an alternative embodiment, in the step of repeatedly smelting under the protection of high-purity argon for multiple times to obtain the alloy ingot:
the smelting times are 4-7 times.
In an optional embodiment, the step of preparing the equal atomic ratio high-entropy amorphous alloy strip without Be from the alloy ingot in a vacuum melt-spun machine specifically comprises the following steps:
crushing the alloy cast ingot, and placing a part of the crushed alloy cast ingot in a quartz tube of a vacuum melt-spun machine as a master alloy;
adjusting the vacuum degree of the furnace chamber of the vacuum melt-spun machine to 2 multiplied by 10-3After Pa, starting a stepless speed regulating motor, and switching on an induction coil power supply after the copper roller rotates at a preset rotation speed to completely melt the master alloy in the quartz tube to obtain an alloy melt;
and (3) high-purity argon is instantaneously filled into the quartz tube, so that a preset pressure difference is formed between the quartz tube and a furnace chamber of the vacuum melt-throwing machine, the alloy melt is driven to Be sprayed to the surface of the copper roller from a nozzle of the quartz tube under the action of the preset pressure difference, and the alloy melt is rapidly cooled to form the Be-free equal-atomic-ratio high-entropy amorphous alloy strip.
In an optional embodiment, the preset rotating speed of the copper roller is 2000-3500 rpm;
the preset pressure difference formed between the quartz tube and the furnace chamber is 0.03-0.05 MPa.
In an optional embodiment, the equal atomic ratio without Be is 20-40 μm thick and 2-4 mm wide than the high-entropy amorphous alloy strip.
In an alternative embodiment, when the M element is an Nd element, the equal atomic ratio without Be is a completely amorphous structure compared with the microstructure of the high-entropy amorphous alloy ribbon;
when the M element is Ag element or La element, the microstructure of the Be-free isoatomic ratio high-entropy amorphous alloy strip is an amorphous structure comprising a small part of second phase and a large part of second phase.
Embodiments of the invention have at least the following advantages or benefits:
the embodiment of the invention provides an equal atomic ratio high-entropy amorphous alloy material without Be, which comprises the following elements in atomic percentage: ti element: 20%, Zr element: 20%, Cu element: 20%, Ni element: 20% and M element: 20 percent; wherein, the M element is any one of Nd element, Ag element and La element. On one hand, the alloy does not contain Be element, so that the highly toxic metal is not needed to Be used as an alloy raw material, the environment requirement is met, and the price is relatively low; meanwhile, Nd element, Ag element or La element is selected to replace Be element, so that the whole alloy composition still maintains five components, and the amorphous forming capability of the alloy can Be effectively maintained.
The embodiment of the invention also provides a preparation method of the Be-free isoatomic ratio high-entropy amorphous alloy material, which adopts a non-consumable vacuum arc furnace to obtain an alloy ingot with uniform components, and then obtains an isoatomic ratio high-entropy amorphous alloy strip after vacuum melt spinning.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an XRD spectrum of a band of high-entropy amorphous alloy with equal atomic ratio and without Be obtained from examples 1 to 3 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The features and properties of the present invention are described in further detail below with reference to examples.
The scheme adopted by the embodiment of the invention mainly provides an equal atomic ratio high-entropy amorphous alloy material without Be, which comprises the following elements in atomic percentage: ti element: 20%, Zr element: 20%, Cu element: 20%, Ni element: 20% and M element: 20 percent; wherein, the M element is any one of Nd element, Ag element and La element.
Specifically, the Ti element, the Zr element, the Cu element, the Ni element, and the M element are all high-purity metals having a purity of at least 3N. And Nd element, Ag element or La element is used for replacing Be element, so that the use of highly toxic metal as an alloy raw material can Be avoided, the environmental requirement is met, and the price is relatively low; meanwhile, the whole alloy composition still keeps five components, and the amorphous forming capability of the alloy can be effectively kept.
In more detail, with a view to improving the amorphous forming ability of the alloy, researchers have proposed a series of principles and methods, the most important of which are three empirical criteria of Inoue: first, a multicomponent alloy system composed of 3 or more components; secondly, the difference of the atomic radii of the main components is more than 12 percent; and thirdly, negative mixing heat exists among main components.
For one, increasing the number of constituent elements can lead to compositional complexity, and long-range diffusion of atoms of different constituent elements, which is essential for the formation of a crystalline phase that competes with the amorphous phase, is suppressed. One of Nd element, Ag element and La element is selected to replace Ti20Zr20Cu20Ni20Be20Be element in the alloy, the whole alloy components still maintain five components, which is beneficial to maintaining the amorphous forming capability of the alloy.
Secondly, the large atomic radius difference makes the long-range diffusion of the constituent atoms more difficult, so that the alloy has larger viscosity in a supercooled liquid phase region, the nucleation and growth of a crystalline phase are hindered, and the disordered structure of a melt is easily kept to the room temperature, thereby being beneficial to forming the amorphous alloy. As is clear from the data shown in Table 1, the Nd atom and the La atom selected in the examples of the present inventionThe largest radius of the atom used, which replaces Ti20Zr20Cu20Ni20Be20The Be in the alloy still keeps large atomic radius difference (maximum can exceed 40%) with other atoms, so that the Nd atom or the La atom also makes long-range diffusion of constituent atoms more difficult, thereby being beneficial to forming amorphous alloy. Similarly, when the Be element is replaced by the Ag element used in the embodiments of the present invention, the atomic radius difference between the atoms of Zr, Cu, and Ni is still 10% or more, although the atomic radius difference between the atoms of Zr, Cu, and Ni is reduced as a whole, thereby being also advantageous for forming amorphous alloys.
TABLE 1 Be, Nd, Ag, La atomic radii and their differences in radii with other atoms (%)
Third, the more negative heat of mixing means that there is a greater bonding force between the constituent atoms, which increases the driving force for the alloy to form amorphous. According to the thermodynamics of alloy formation, the smaller the Gibbs free energy change Δ G ═ Δ H-T Δ S (Δ H and Δ S are the enthalpy and entropy of phase formation, respectively) in the phase transition from melt to crystalline, the more easily amorphous is formed. Obviously, an increase in the number of elements favors an increase in Δ S, and both a greater negative heat of mixing between atoms and a difference in atomic radius increase the atomic stacking density, decreasing Δ H, and consequently Δ G; according to the kinetics of alloy formation, the value of the parameter β ═ Δ S/R (R is the avigado constant), which is inversely proportional to the nucleation rate I and the growth rate U, increases with increasing Δ S, lowering I and U, and thus increasing GFA.
As can be seen from the data in Table 2, the Nd, Ag and La atoms selected by the present invention replace Ti20Zr20Cu20Ni20Be20After Be in the alloy, relatively negative heat of mixing is still kept between Be and other two atoms. Thereby making the groupThe elements have larger bonding force among atoms, and can increase the driving force for forming the amorphous alloy, thereby fully ensuring the amorphous forming capability of the alloy.
TABLE 2 Heat of mixing of Be, Nd, Ag, La atoms with other atoms (kJ/mol)
| Element(s) | Ti | Zr | Cu | Ni |
| Heat of mixing Be atom with other atoms | -30 | -43 | 0 | -4 |
| Heat of mixing Nd atom with other atoms | 17 | 10 | -22 | -30 |
| Heat of mixing Ag atom with other atoms | -2 | -20 | 2 | -15 |
| Heat of mixing La atom with |
20 | 13 | -21 | -27 |
In summary, in the embodiments of the present invention, one of Nd, Ag and La elements is selected to replace Ti20Zr20Cu20Ni20Be20After Be in the alloy, the alloy is still helped to maintain good amorphous forming capability.
Meanwhile, the embodiment of the invention also provides a preparation method of the Be-free isoatomic ratio high-entropy amorphous alloy material, which comprises the following steps:
s1: ti element, Zr element, Cu element, Ni element and M element are mixed according to the atomic percentage of 20: 20: 20: 20: 20, batching;
s2: smelting the proportioned raw materials in a non-consumable vacuum arc furnace to obtain uniform and consistent alloy ingots;
wherein the step S2 includes:
s21: placing the proportioned raw materials in a smelting pit of a non-consumable vacuum arc furnace;
in detail, since the non-consumable vacuum arc furnace is provided with a plurality of smelting pits, and the quantity of the smelting pits is more than one, the raw materials with a plurality of components can be conveniently placed in the smelting pits at corresponding positions respectively, so that the alloy materials with a plurality of components can be obtained uniformly through smelting in the non-consumable vacuum arc furnace, and the time is saved.
S22: vacuumizing and filling high-purity argon;
in detail, the vacuum degree of the equipment cavity reaches 3 multiplied by 10 through rough pumping of a mechanical pump and fine pumping of a molecular pump-3After Pa, filling high-purity argon; vacuum pumping is carried out again until the vacuum pressure is 3 multiplied by 10-3And after Pa, introducing high-purity argon again. Wherein the multiple evacuation is aimed atThe oxygen content in the cell is extracted as much as possible in order to avoid as much reaction of the alloy melt with oxygen as possible during the melting process. Of course, in other embodiments of the present invention, the number of times of vacuum pumping is determined according to the habit of the operator and the working environment, and it is only necessary to ensure that the vacuum pumping is in a proper vacuum state.
S23: repeatedly smelting under the protection of high-purity argon to obtain an alloy ingot.
In detail, the alloy ingot is repeatedly smelted for 4-7 times, so that the uniform alloy ingot can be obtained. Meanwhile, the purpose of repeated melting is to obtain uniform and consistent alloy ingots, so the number of times of melting can be improved and adjusted according to specific situations, and the embodiment is not limited.
S3: and (3) preparing the alloy ingot in a vacuum melt-spun machine to obtain the Be-free isoatomic ratio high-entropy amorphous alloy strip.
In detail, the step S3 specifically includes:
s31: crushing the alloy cast ingot, and placing a part of the crushed alloy cast ingot in a quartz tube of a vacuum melt-spun machine as a master alloy;
in detail, since the alloy ingot obtained by melting the alloy ingot in the non-consumable vacuum arc furnace has a substantially button-like shape and a size generally slightly larger than the inner diameter of the quartz tube, the alloy ingot needs to be crushed before being put into the quartz tube. Meanwhile, the alloy ingot is not required to be completely put into the quartz tube after being crushed, so that the strip can be spun in batches to form a plurality of strips.
S32: adjusting the vacuum degree of the furnace chamber of the vacuum melt-spun machine to 2 multiplied by 10-3After Pa, starting a stepless speed regulating motor, and switching on an induction coil power supply after the copper roller rotates at a preset rotation speed to completely melt the master alloy in the quartz tube to obtain an alloy melt;
in detail, when the vacuum degree of the vacuum flail machine furnace chamber reaches 2 multiplied by 10-3The stepless speed regulating motor is started by Pa, and the power supply of the induction coil is switched on after the rotating speed of the copper roller reaches 2000-3500 rpm (the surface linear velocity is about 20-35 m/s), so that the stone is made to be stoneThe master alloy rod in the quartz tube was completely melted.
S33: high-purity argon is instantaneously filled into the quartz tube, so that a preset pressure difference is formed between the quartz tube and a furnace chamber of the vacuum melt spinning machine, and the alloy melt is driven to flow from a nozzle (the cross section of which is 0.2 multiplied by 3 mm) of the quartz tube under the action of the preset pressure difference2) Spraying the mixture on the surface of a copper roller, and rapidly cooling to form an isoatomic ratio high-entropy amorphous alloy strip without Be.
In detail, the preset pressure difference formed between the quartz tube and the furnace chamber is 0.03-0.05 MPa. The reasonable selection of the strip throwing technological parameters (such as the rotating speed of a copper roller is 2000-3500 rpm, namely the surface linear velocity is about 20-35 m/s, and the pressure difference between a quartz tube and a furnace chamber is 0.03-0.05 MPa) in the steps of the method is to ensure the surface quality and the toughness of the obtained strip. The prepared stripe structure has the advantages of thickness of 20-40 mu m, width of 2-4 mm, flat and smooth surface, no defects such as hole cracks and the like, and good toughness.
In more detail, when the M element is Nd element, the microstructure of the high-entropy amorphous alloy strip without Be is completely amorphous structure compared with the microstructure of the high-entropy amorphous alloy strip; when the M element is Ag element or La element, the microstructure of the Be-free isoatomic ratio high-entropy amorphous alloy strip is an amorphous structure comprising a small part of second phase and a large part of second phase.
The specific implementation process is described in detail below by specific examples:
example 1
As shown in FIG. 1, this example provides a Be-free equiatomic ratio high entropy amorphous alloy material Ti20Zr20Cu20Ni20Nd20The preparation method comprises the following steps:
s1: high-purity Ti, Zr, Cu, Ni and Nd metals (the purity is at least more than 3N) are mixed according to the atomic percentage of 20: 20: 20: 20: 20, preparing materials;
s2: smelting the high-purity metal subjected to ultrasonic treatment in a non-consumable vacuum arc furnace;
wherein, step S2 specifically includes:
s21: placing the proportioned raw materials in a smelting pit of a non-consumable vacuum arc furnace;
s22: the vacuum degree of the equipment cavity reaches 3 multiplied by 10 by rough pumping of a mechanical pump and fine pumping of a molecular pump-3After Pa, filling high-purity argon (5N); then, vacuum was again applied to 3X 10-3Introducing high-purity argon after Pa;
s23: and repeatedly smelting the alloy ingot for 4-7 times under the protection of high-purity argon, thereby obtaining uniform alloy ingots.
S3: and (3) preparing the alloy ingot in a vacuum melt-spun machine to obtain the Be-free isoatomic ratio high-entropy amorphous alloy strip.
Wherein, step S3 specifically includes:
s31: crushing the alloy cast ingot, and placing a part of the crushed alloy cast ingot as a master alloy in a quartz tube (the nozzle section is 0.2 multiplied by 3 mm)2) Performing the following steps;
s32: when the vacuum degree of the furnace chamber of the vacuum melt-spun machine reaches 2 multiplied by 10-3After Pa, starting the stepless speed regulating motor, and switching on an induction coil power supply after the rotating speed of the copper roller reaches 2000rpm (the surface linear velocity is about 20m/s) so as to completely melt the mother alloy rod in the quartz tube;
s33: then high-purity argon is instantaneously filled into the quartz tube, a pressure difference (0.03MPa) is built between the quartz tube and the furnace chamber, the alloy melt is driven to be directly sprayed onto a copper roller rotating at a high speed, and the strip is rapidly cooled to form the strip. The obtained strip has the thickness of 40 mu m and the width of 2mm, has flat and smooth surface, no defects such as hole cracks and the like, and has good toughness.
The stripe structure of the embodiment is detected to be a complete amorphous structure.
Example 2
As shown in FIG. 1, this example provides a Be-free equiatomic ratio high entropy amorphous alloy material Ti20Zr20Cu20Ni20Ag20The preparation method comprises the following steps:
s1: high-purity Ti, Zr, Cu, Ni and Ag (the purity is at least more than 3N) are added according to the atomic percentage of 20: 20: 20: 20: 20, preparing materials;
s2: smelting the high-purity metal subjected to ultrasonic treatment in a non-consumable vacuum arc furnace;
wherein, step S2 specifically includes:
s21: placing the proportioned raw materials in a smelting pit of a non-consumable vacuum arc furnace;
s22: the vacuum degree of the equipment cavity reaches 3 multiplied by 10 by rough pumping of a mechanical pump and fine pumping of a molecular pump-3After Pa, filling high-purity argon (5N); then, vacuum was again applied to 4X 10-3Introducing high-purity argon after Pa;
s23: and repeatedly smelting the alloy ingot for 4-7 times under the protection of high-purity argon, thereby obtaining uniform alloy ingots.
S3: and (3) preparing the alloy ingot in a vacuum melt-spun machine to obtain the Be-free isoatomic ratio high-entropy amorphous alloy strip.
Wherein, step S3 specifically includes:
s31: crushing the alloy cast ingot, and placing a part of the crushed alloy cast ingot as a master alloy in a quartz tube (the nozzle section is 0.2 multiplied by 3 mm)2) Performing the following steps;
s32: when the vacuum degree of the furnace chamber of the vacuum melt-spun machine reaches 2 multiplied by 10-3After Pa, starting the stepless speed regulating motor, and switching on an induction coil power supply after the rotating speed of the copper roller reaches 3000rpm (the surface linear velocity is about 30m/s) so as to completely melt the mother alloy rod in the quartz tube;
s33: then high-purity argon is instantaneously filled into the quartz tube, a pressure difference (0.04MPa) is built between the quartz tube and the furnace chamber, the alloy melt is driven to be directly sprayed onto a copper roller rotating at a high speed, and the strip is rapidly cooled to form the strip. The obtained strip has the thickness of 30 mu m and the width of 3mm, has flat and smooth surface, no defects such as hole cracks and the like, and has good toughness.
The band structure of this example was examined to be an amorphous composite structure containing very little second phase.
Example 3
As shown in FIG. 1, this example provides a Be-free equiatomic ratio high entropy amorphous alloy material Ti20Zr20Cu20Ni20La20Which is prepared byThe method comprises the following steps:
s1: high-purity Ti, Zr, Cu, Ni and La metals (the purity is at least more than 3N) are mixed according to the atomic percentage of 20: 20: 20: 20: 20, preparing materials;
s2: smelting the high-purity metal subjected to ultrasonic treatment in a non-consumable vacuum arc furnace;
wherein, step S2 specifically includes:
s21: placing the proportioned raw materials in a smelting pit of a non-consumable vacuum arc furnace;
s22: the vacuum degree of the equipment cavity reaches 3 multiplied by 10 by rough pumping of a mechanical pump and fine pumping of a molecular pump-3After Pa, filling high-purity argon (5N); then, vacuum was again applied to 3X 10-3Introducing high-purity argon after Pa;
s23: and repeatedly smelting the alloy ingot for 4-7 times under the protection of high-purity argon, thereby obtaining the alloy ingot with uniform components.
S3: and (3) preparing the alloy ingot in a vacuum melt-spun machine to obtain the Be-free isoatomic ratio high-entropy amorphous alloy strip.
Wherein, step S3 specifically includes:
s31: crushing the alloy cast ingot, and placing a part of the crushed alloy cast ingot as a master alloy in a quartz tube (the nozzle section is 0.2 multiplied by 3 mm)2) Performing the following steps;
s32: when the vacuum degree of the furnace chamber of the vacuum melt-spun machine reaches 2 multiplied by 10-3After Pa, starting a stepless speed regulating motor, and switching on an induction coil power supply after the rotating speed of the copper roller reaches 3500rpm (the surface linear velocity is about 35m/s) so as to completely melt the mother alloy rod in the quartz tube;
s33: then high-purity argon is instantaneously filled into the quartz tube, a pressure difference (0.05MPa) is built between the quartz tube and the furnace chamber, the alloy melt is driven to be directly sprayed onto a copper roller rotating at a high speed, and the strip is rapidly cooled to form the strip. The obtained strip has the thickness of 20 mu m and the width of 4mm, has flat and smooth surface, no defects such as hole cracks and the like, and has good toughness.
The band structure of this example was examined to be an amorphous composite structure containing a small amount of the second phase.
As can Be seen from fig. 1, tables 1 and 2 and the schemes described in the above embodiments, the embodiment of the present invention provides an isoatomic ratio high-entropy amorphous alloy material without Be, which does not contain Be element, so that it is unnecessary to use the highly toxic metal as an alloy raw material, which meets the environmental requirements and is relatively cheap; meanwhile, Nd element, Ag element or La element is selected to replace Be element, so that the whole alloy composition still maintains five components, and the amorphous forming capability of the alloy can Be effectively maintained. Meanwhile, the preparation method of the Be-free isoatomic ratio high-entropy amorphous alloy material provided by the embodiment of the invention adopts a non-consumable vacuum arc furnace to obtain uniform alloy ingots, and then obtains isoatomic ratio high-entropy amorphous alloy strips after vacuum melt spinning.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An isoatomic ratio high-entropy amorphous alloy material without Be is characterized by comprising the following elements in atomic percentage:
ti element: 20%, Zr element: 20%, Cu element: 20%, Ni element: 20% and M element: 20 percent;
wherein the M element is any one of Nd element, Ag element and La element.
2. The Be-free isoatomic ratio high-entropy amorphous alloy material as claimed in claim 1, wherein:
the Ti element, the Zr element, the Cu element, the Ni element, and the M element are all high-purity metals having a purity of at least 3N.
3. A preparation method of Be-free equiatomic ratio high-entropy amorphous alloy material as claimed in claim 1 or 2, characterized by comprising:
and (2) mixing the Ti element, the Zr element, the Cu element, the Ni element and the M element according to the atomic percentage of 20: 20: 20: 20: 20, batching;
smelting the proportioned raw materials in a non-consumable vacuum arc furnace to obtain uniform and consistent alloy ingots;
and preparing the alloy ingot in a vacuum melt-spun machine to obtain the Be-free equal-atomic-ratio high-entropy amorphous alloy strip.
4. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material according to claim 3, wherein the step of smelting the proportioned raw materials in the non-consumable vacuum arc furnace to obtain the uniform and consistent alloy ingot casting specifically comprises the following steps:
placing the proportioned raw materials in a smelting pit of the non-consumable vacuum arc furnace;
vacuumizing and filling high-purity argon;
repeatedly smelting under the protection of high-purity argon to obtain the alloy ingot.
5. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material according to claim 4, wherein the steps of vacuumizing and filling the high-purity argon gas specifically comprise:
the vacuum degree of the equipment cavity reaches 3 multiplied by 10 by rough pumping of a mechanical pump and fine pumping of a molecular pump-3After Pa, filling high-purity argon;
vacuum pumping is carried out again until the vacuum pressure is 3 multiplied by 10-3And after Pa, introducing high-purity argon again.
6. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material according to claim 4, wherein in the step of repeatedly smelting under the protection of the high-purity argon gas for multiple times to obtain the alloy ingot:
the smelting times are 4-7 times.
7. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material is characterized in that the step of preparing the Be-free isoatomic ratio high-entropy amorphous alloy strip in the vacuum melt-spun machine from the alloy ingot specifically comprises the following steps:
crushing the alloy cast ingot, and placing a part of the crushed alloy cast ingot in a quartz tube of the vacuum melt-spun machine as a mother alloy;
adjusting the vacuum degree of the furnace chamber of the vacuum melt-spun machine to 2 multiplied by 10-3After Pa, starting a stepless speed regulating motor, and switching on an induction coil power supply after the copper roller rotates at a preset rotation speed to completely melt the master alloy in the quartz tube to obtain an alloy melt;
and high-purity argon is instantaneously filled into the quartz tube, so that a preset pressure difference is formed between the quartz tube and a furnace chamber of the vacuum melt-throwing machine, the alloy melt is driven to Be sprayed to the surface of the copper roller from a nozzle of the quartz tube under the action of the preset pressure difference, and the alloy melt is rapidly cooled to form the Be-free equal atomic ratio high-entropy amorphous alloy strip.
8. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material according to claim 7, is characterized in that:
the preset rotating speed of the copper roller is 2000-3500 rpm;
the preset pressure difference formed between the quartz tube and the furnace chamber is 0.03-0.05 MPa.
9. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material according to claim 7, is characterized in that:
the equal atomic ratio high-entropy amorphous alloy strip without Be is 20-40 mu m in thickness and 2-4 mm in width.
10. The method for preparing the Be-free isoatomic ratio high-entropy amorphous alloy material according to claim 3, wherein the Be-free isoatomic ratio high-entropy amorphous alloy material is characterized in that:
when the M element is an Nd element, the microstructure of the Be-free isoatomic ratio high-entropy amorphous alloy strip is a complete amorphous structure;
when the M element is Ag element or La element, the microstructure of the Be-free isoatomic ratio high-entropy amorphous alloy strip is an amorphous structure comprising a small part of second phase and a large part of second phase.
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| CN106086712A (en) * | 2016-05-31 | 2016-11-09 | 深圳大学 | TiZrHf system high entropy amorphous alloy material and preparation method thereof |
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| CN106086712A (en) * | 2016-05-31 | 2016-11-09 | 深圳大学 | TiZrHf system high entropy amorphous alloy material and preparation method thereof |
| CN107699822A (en) * | 2017-09-20 | 2018-02-16 | 华中科技大学 | A kind of high entropy block amorphous alloy and preparation method thereof |
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