CN111778457A - Al-based amorphous alloy block material and preparation method thereof - Google Patents
Al-based amorphous alloy block material and preparation method thereof Download PDFInfo
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- CN111778457A CN111778457A CN202010620791.3A CN202010620791A CN111778457A CN 111778457 A CN111778457 A CN 111778457A CN 202010620791 A CN202010620791 A CN 202010620791A CN 111778457 A CN111778457 A CN 111778457A
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Abstract
The invention belongs to the technical field of bulk amorphous alloys, and particularly relates to an Al-based amorphous alloy bulk material and a preparation method thereof, wherein the method comprises the steps of weighing aluminum, vanadium, iron and copper, mixing to form a raw material mixture, performing high-energy ball milling mechanical alloying to form amorphous alloy powder, and performing sintering treatment under the conditions of vacuum, high temperature and high pressure to obtain the Al-based amorphous alloy bulk material; wherein the crystallization starting temperature of the amorphous alloy powder is more than or equal to 749K, and the width of a supercooled liquid phase region is more than or equal to 169K; the Al-based amorphous alloy powder material designed and prepared by the invention utilizes the larger atomic mismatching degree and the mixed heat absolute value among elements to obtain a stable amorphous structure, the crystallization starting temperature and the width of a supercooled liquid region respectively reach above 749K and 169K, and the Al-based amorphous alloy powder material is one of the Al-based amorphous alloys with the best thermal stability reported at present; the large-size and high-strength Al-based amorphous block material is obtained by a vacuum high-temperature high-pressure sintering technology, and the microhardness of the Al-based amorphous block material reaches 821-927 Hv.
Description
Technical Field
The invention belongs to the technical field of bulk amorphous alloys, and particularly relates to an Al-based amorphous alloy bulk material and a preparation method thereof.
Background
The Al-based amorphous bulk material has a unique microstructure, shows a plurality of excellent performances such as high specific strength, high specific stiffness and high corrosion resistance, and has wide application prospects in the fields of aerospace, transportation, weaponry and the like. However, since the glass forming ability of the Al-based amorphous material is low, it is difficult to prepare a bulk material having an all-amorphous structure by a conventional liquid rapid cooling process, or a very fast cooling rate is required to obtain a bulk material having an all-amorphous structure. The intrinsic characteristic of the Al-based amorphous alloy provides great challenges for the preparation of large-size amorphous block materials, and also severely restricts the practical application of the Al-based amorphous block materials. Therefore, a large-size Al-based amorphous bulk material with practical application value is obtained, and one of the targets pursued in the fields of amorphous physics and material science is always achieved.
In order to break through the limitation of the liquid fast cooling method for preparing the Al-based amorphous bulk material due to low glass forming capability, a series of solid phase preparation methods are developed at present, wherein amorphous alloy powder is obtained by mechanical alloying and other processes, and then the amorphous alloy powder is subjected to hot pressing or warm extrusion in a supercooled liquid region to form the full amorphous bulk material through metallurgical bonding. Compared with a liquid rapid cooling process, the solid phase approach does not need to consider the problem of controlling heterogeneous nucleation, is suitable for a wider alloy system, can break through the limitation of glass forming capacity or critical cooling speed to the maximum extent, and is beneficial to obtaining a block material with larger geometric dimension.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of an Al-based amorphous alloy block material. Compared with the traditional liquid rapid cooling process, the method does not need to consider the problem of controlling heterogeneous nucleation, can be suitable for a wider alloy system, and can break through the limitation of glass forming capacity or critical cooling speed to the maximum extent so as to obtain a block material with larger geometric dimension.
In order to achieve the above objects, in one aspect, the present invention provides a method for preparing an Al-based amorphous alloy bulk material, the method comprising weighing aluminum, mixing at least two metal raw materials except for aluminum to form a raw material mixture,
mechanically alloying by high-energy ball milling to form amorphous alloy powder,
sintering under high temperature and high pressure to obtain the Al-based amorphous alloy block material;
wherein the crystallization starting temperature of the amorphous alloy powder is more than or equal to 749K, and the width of a supercooled liquid phase region is more than or equal to 169K.
Under the preferable conditions, the raw material mixture contains the following elements in atomic percentage based on the total amount of the raw material mixture: v11.5-12.5%, Fe 11.0-13.0%, Cu 0-3.0%, and the balance of Al and inevitable impurities.
Under the preferable conditions, the raw material mixture contains the following elements in atomic percentage based on the total amount of the raw material mixture: 12.5% of V, 12.5% of Fe, 0.15% of Cu, and the balance of Al and inevitable impurities.
Preferably, each metal material in the material mixture is in the form of powder particles, and the powder particles have an average particle diameter of 50 μm.
Preferably, the conditions of the high-energy ball-milling mechanized alloy comprise: adding stearic acid accounting for 2 percent of the total weight of the raw material mixture and bearing steel balls with the diameter of 10mm, wherein the ball-to-material ratio is 20: 1; high-purity argon is adopted for protection in the ball milling process, and the autorotation speed of the ball milling tank is 350 rpm.
Preferably, the high temperature and high pressure conditions include: the pressure is 3.5-4.5GPa, the sintering temperature is 720-730K, and the holding time is 180-220 s.
The invention also provides the Al-based amorphous alloy block material prepared by the method. The microstructure of the Al-based amorphous alloy block material is a full amorphous phase, and the microhardness is 821-927 Hv.
Compared with the prior art, the invention has the following technical effects:
in the preparation method provided by the invention, the raw material mixture has strong amorphous forming capability through the synergistic cooperation of all component elements, and the amorphous alloy powder with high stability is obtained through mechanical alloying, and then the bulk material with the full amorphous structure is prepared through high-temperature high-pressure sintering, and the hardness of the bulk material is far higher than that of the Al alloy with a crystal structure.
The Al-based amorphous alloy powder material designed and prepared by the invention utilizes the larger atomic mismatching degree and the mixed heat absolute value among elements to obtain a stable amorphous structure, the crystallization starting temperature and the width of a supercooled liquid region respectively reach above 749K and 169K, and the Al-based amorphous alloy powder material is one of the Al-based amorphous alloys with the best thermal stability reported at present; the large-size and high-strength Al-based amorphous block material is obtained by a vacuum high-temperature high-pressure sintering technology, and the microhardness of the Al-based amorphous block material reaches 821-927 Hv.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is an XRD pattern of the alloy powder obtained after ball milling the raw material mixture of example 1 for various periods of time;
FIG. 2 is the particle morphology and selected area electron diffraction pattern of the raw material mixture of example 1 after ball milling for 70 h;
FIG. 3 is the XRD pattern of the bulk alloy material of example 1 and the associated powder and bulk materials;
FIG. 4 is a microstructure of the bulk material prepared in example 1;
FIG. 5 is a graph of microhardness versus load for the bulk material prepared in example 1.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified below by combining the specific drawings and the embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Research shows that the Al-based amorphous alloy (Al-TM-RE) composed of transition group elements and rare earth elements has higher amorphous forming capability and good mechanical property, and is considered to be the Al-based amorphous alloy material with the most application prospect. At present, most Al-based amorphous alloys are mainly Al-Co-M, Al-Cu-M and Al-Fe-M (M: Ti, Zr, Hf, V, Nb, Ta, Cr, W, Mo and the like) systems, and millimeter-scale amorphous thin strips are prepared by utilizing the alloys and a rapid solidification technology, and the hardness of the amorphous thin strips reaches 821-927 Hv. The inventors of the present application found that it is possible to produce bulk materials with more complex geometries and larger dimensions using the above-described solid state sintering method if based on these Al-based amorphous alloy systems. Based on this analysis, the inventors of the present application first obtained a wide supercooled liquid region from an amorphous alloy, and the basic conditions that strong glass-forming ability should satisfy, namely 1) consisting of three or more elements; 2) the atomic radius ratio of the components is more than 13 percent; 3) the mixing heat among the elements is negative, the composition of the Al-based amorphous alloy is designed, and the composition (at.%) Al is obtained75V12.5Fe12.5CuxAnd (x is 0-3.0), alloying and non-crystallizing the element powder by using a mechanical alloying process, and finally preparing the block material with the full amorphous structure by using a high-temperature high-pressure sintering process. According to XRD and DSC analysis, the alloy can be completely amorphized after ball milling for 70 hours, the glass transition temperature of the alloy reaches more than 680K, the width of a supercooled liquid phase region reaches more than 169K, the crystallization starting temperature reaches more than 749K, and the alloy has high thermal stability. The microhardness test shows that the hardness of the amorphous alloy block material is up to 821-927 Hv.
The preparation method comprises the steps of weighing aluminum, vanadium, iron and copper, mixing to form a raw material mixture, performing high-energy ball milling mechanical alloying to form amorphous alloy powder, and performing sintering treatment under the conditions of high temperature and high pressure to obtain the Al-based amorphous alloy block material; wherein the crystallization starting temperature of the amorphous alloy powder is more than or equal to 749K, and the width of a supercooled liquid phase region is more than or equal to 169K.
The preparation method of the Al-based amorphous alloy bulk material provided by the present invention is further illustrated by the following specific examples.
A preparation method of an Al-based amorphous alloy block material comprises the following steps:
(1) the preparation method comprises the following steps of proportioning according to target components, specifically, weighing V, Fe, Cu and Al, and mixing to form a raw material mixture, wherein the raw material mixture contains the following elements in atomic percentage based on the total amount of the raw material mixture: 12.5% of V, 12.5% of Fe, 0.15% of Cu, and the balance of Al and inevitable impurities.
(2) Putting the raw material mixture into a high-energy planetary ball mill, adding stearic acid accounting for 2 percent of the total weight of the raw material mixture and bearing steel balls with the diameter of 10mm, wherein the ball-material ratio is 20: 1; in the ball milling process, high-purity argon is used for protection, and the autorotation speed of the ball milling tank is 350 rpm;
after ball milling for 70 hours, taking out the powder from the ball milling tank in a vacuum glove box under the protection of argon gas and filling the powder into a sealed sample bag;
(3) characterizing the phase structure, the characteristic temperature and the like of the powder by adopting an X-ray diffractometer, a transmission electron microscope and a differential scanning calorimeter, confirming that the obtained powder is a full amorphous structure, and simultaneously obtaining the crystallization starting temperature and the width of a supercooled liquid phase region of the powder; when the temperature rise rate is measured to be 20K/min, the crystallization starting temperature is 749K, and the width of the supercooled liquid phase region is 169K;
(4) putting the powder into a circular film pressing cavity of a press, sealing, and vacuumizing to a vacuum degree of 10-4After Pa, pressing the powder by using a press head of a press until the pressure reaches 4GPa, simultaneously heating the mould, preserving heat when the temperature reaches 723K, releasing pressure after preserving heat for 200s, and taking out the block material from the mould to obtain the block material with the size of
The bulk material of (a);
(5) and grinding and polishing the block material, and testing the hardness of the block material on a microhardness tester to obtain the Vickers hardness values of the block material under different loads.
The results show that: the microhardness of the bulk material prepared in the example 1 decreases with increasing applied load, and when the load is 100-1000g, the microhardness of the bulk material is 821-927 Hv.
Please refer to fig. 1, which is an XRD pattern of the alloy powder obtained after the raw material mixture of example 1 is ball milled for different time; FIG. 2 is the particle morphology and selected area electron diffraction pattern of the raw material mixture of example 1 after ball milling for 70 h; FIG. 3 is the XRD pattern of the bulk alloy material of example 1 and the associated powder and bulk materials; FIG. 4 is a microstructure of the bulk material prepared in example 1; FIG. 5 is a graph of microhardness versus load for the bulk material prepared in example 1.
The foregoing shows and describes the general principles, essential features, and inventive features of this invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation method of an Al-based amorphous alloy block material is characterized by comprising the steps of weighing and mixing aluminum, vanadium, iron and copper to form a raw material mixture, performing high-energy ball milling mechanical alloying to form amorphous alloy powder,
sintering under vacuum, high temperature and high pressure conditions to obtain the Al-based amorphous alloy block material;
wherein the crystallization starting temperature of the amorphous alloy powder is more than or equal to 749K, and the width of a supercooled liquid phase region is more than or equal to 169K.
2. The method according to claim 1, wherein the raw material mixture contains the following elements in atomic percent based on the total amount of the raw material mixture: v11.5-12.5%, Fe 11.0-13.0%, Cu 0-3.0%, and the balance of Al and inevitable impurities.
3. The method according to claim 2, wherein the raw material mixture contains the following elements in atomic percent based on the total amount of the raw material mixture: 12.5% of V, 12.5% of Fe, 0.15% of Cu, and the balance of Al and inevitable impurities.
4. The method of claim 1, wherein each metal starting material in the starting material mixture is in the form of powder particles, and wherein the powder particles have an average particle size of 50 μm.
5. The method of claim 1, wherein the conditions for high energy ball milling the mechanized alloy comprise: adding stearic acid accounting for 2 percent of the total weight of the raw material mixture and bearing steel balls with the diameter of 10mm, wherein the ball-to-material ratio is 20: 1; high-purity argon is adopted for protection in the ball milling process, and the autorotation speed of the ball milling tank is 350 rpm.
6. The method of claim 1, wherein the vacuum, high temperature and high pressure conditions comprise: vacuum degree of 10-4Pa, pressure of 3.5-4.5GPa, sintering temperature of 720-730K and holding time of 180-220 s.
7. The Al-based amorphous alloy bulk material prepared by the method according to any one of claims 1 to 6.
8. The Al-based amorphous alloy bulk material as claimed in claim 7, wherein the microstructure of the Al-based amorphous alloy bulk material is fully amorphous phase, and the microhardness is 821-927 Hv.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114346237A (en) * | 2021-12-11 | 2022-04-15 | 深圳大学 | Application of amorphous alloy, composite material and preparation method thereof |
| CN114985721A (en) * | 2022-04-22 | 2022-09-02 | 福建农林大学 | Fe-Nb-Al series Fe-based amorphous alloy powder with all metal components and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114346237A (en) * | 2021-12-11 | 2022-04-15 | 深圳大学 | Application of amorphous alloy, composite material and preparation method thereof |
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| CN114985721A (en) * | 2022-04-22 | 2022-09-02 | 福建农林大学 | Fe-Nb-Al series Fe-based amorphous alloy powder with all metal components and preparation method thereof |
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Application publication date: 20201016 |