A method for preparing large-area parallel-oriented decadic quasicrystal-like microtubes

Abstract

A method for preparing a large area parallel oriented ten-order quasicrystal approximate phase micron tube belongs to the field of metal materials. The invention adopts vacuum induction melting method to prepare equiatomic ratio Al 20 Si 20 Mn 20 Fe 20 Ga 20 The alloy ingot is then induction heated and melted in a vacuum single-roll copper wheel strip-spinning device to prepare an alloy strip, and a large area of ​​parallel oriented Al is obtained on the free surface of the strip. 18.8 Si 20.6 Mn 22.7 Fe 26.6 Ga 11.3 Quasicrystal-like microtubes. Furthermore, nanoindentation measurements revealed that the microtubes possessed an optimal hardness-Young's modulus combination, reaching 10.9 GPa and 189.3 GPa, respectively, demonstrating superior mechanical properties. The present invention is advantageous in that large-scale, parallel-oriented, decadic quasicrystal-like microtubes were prepared for the first time. The preparation method is simple, easy, and readily mass-produced, providing an effective path for the large-scale preparation of quasicrystal-related tubular materials. The microtubes combine the characteristics of quasicrystals, high-entropy alloys, and micro- and nano-scale materials, and are therefore of significant value in developing their potential applications.

Description

Technical Field

[0001] The present invention relates to the technical field of high entropy alloys, quasicrystal-like phases and micron tube preparation, and in particular to a method for preparing large-area parallel-oriented decadic quasicrystal-like phase micron tubes. Technical Background

[0002] Since Iijima reported carbon nanotubes (CNTs) in 1991, these hollow, one-dimensional tubular materials have been extensively studied due to their unique structure, excellent strength and specific surface area, and impressive optical, electrical, and transport properties. They have important applications in biomedical delivery, energy storage, sensor materials, field emission materials, hydrogen storage, and catalysis. However, due to their small inner diameter, CNTs are easily clogged by other substances during growth, resulting in inefficient utilization of the inner wall and internal cavity, which reduces their practical application value. Consequently, microtubes with diameters between 1 and 10 μm, characterized by monodispersity, chemical stability, and large cavities, have attracted considerable research attention.

[0003] In recent years, researchers have successfully prepared a variety of microtube types using direct vapor deposition, metal-assisted catalysis, hot solution, layered structure curling, and template-assisted methods: carbon, metals (α-Fe, Pd, Se, Te, etc.), oxides (ZnO, Al2O3, Co3O4, SiO2, CeO, etc.), nitrides (SiN x etc.), sulfides (WS2, MoS2, etc.), polymers (polyaniline microtubes, polypyridine microtubes, etc.) and various composite microtubes (carbon / Fe3O4@Fe, catkins / MoS2, metal nanoparticles Pt / carbon fiber, etc.).

[0004] Intermetallic compounds, which exhibit high hardness, wear resistance, oxidation resistance, and unique physical and chemical properties (such as optical, electrical, magnetic, acoustic, thermal, and functional conversion), are used in semiconductor materials, shape memory materials, hydrogen storage catalysts, and magnetic materials. However, few studies have successfully prepared intermetallic compound microtubes. Puente et al. fabricated TiNi intermetallic compound microtubes using titanium-coated nickel wire interdiffusion, demonstrating shape memory and superelastic behavior. However, the preparation process is complex and time-consuming.

[0005] Quasicrystals and quasicrystal-like phases are special types of complex intermetallic compounds. Their tubular structures are rarely observed, especially those formed directly during alloy solidification. Therefore, it would be of great significance to prepare large-scale parallel-oriented microtubes of complex intermetallic compounds and exploit their metallic properties, small size, and parallel orientation to develop their potential applications. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing large-area parallel oriented ten-order quasicrystal approximate phase microtubes. 20 Si 20 Mn 20 Fe 20 Ga 20 Large-scale parallel-oriented microtubes of a decadic quasicrystal-like phase (complex intermetallic compound) have been fabricated from high-entropy alloy ribbons. This provides an important theoretical basis for developing potential applications by leveraging the metallic properties, small size, and parallel orientation of microtubes.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] A large area parallel oriented ten-order quasicrystal approximate phase micron tube is made by melting Al in a vacuum induction resistance furnace. 20 Si 20 Mn 20 Fe 20 Ga 20 The ingots were then induction-heated and melted using a vacuum single-roll copper wheel spinning machine at a spinning speed of 10 m / s. The average length, inner diameter, and outer diameter of the microtubes were approximately 6.99 μm, 0.38 μm, and 1.61 μm, respectively. Their structure is primarily composed of alternating perfect (1 / 0, 2 / 1) domains (lattice constants a = 0.73 nm, b = 1.23 nm, c = 2.24 nm) and defective (1 / 0, 2 / 1) domains.

[0009] The method for preparing a large-area parallel-oriented decadic quasicrystal-like microtube is characterized by the following specific steps:

[0010] 1) The surface of the raw materials of high purity 99.99% Al, 99.3% Si, 99.9% Mn, 99.9% Fe and 99.9% Ga is polished to remove the oxide layer and impurities, and the ingredients are mixed according to the atomic ratio. Then, they are melted in a vacuum induction resistance furnace under argon protection; after melting, they are cooled at room temperature to obtain Al 20 Si 20 Mn 20 Fe 20 Ga 20 ingot;

[0011] 2) The melted ingot was cut into small pieces with a diameter of approximately 1 cm and placed in a quartz tube. The ingot was then induction-heated and melted using a vacuum single-roll copper wheel spinning device to produce a spinning alloy ribbon, the free surface of which was distributed with a large area of ​​parallel-oriented decadic quasicrystal-like micron tubes.

[0012] Furthermore, in step 2), the quartz tube used for the belt spinning has a length of 15 cm, an inner diameter of 1.2 cm, a flat mouth, a length of 3 mm, and a width of 0.3 mm.

[0013] Furthermore, in step 2), the process parameters of the vacuum single-roll copper wheel belt throwing are: belt throwing speed: 10m / s; protective gas: argon; furnace pressure: 0.2Pa; spray bag pressure: 0.02MPa.

[0014] Furthermore, in step 2), the alloy strip has an average width of 5 mm and an average thickness of 70 μm.

[0015] Furthermore, in step 2), the strip-spinning alloy thin strip is divided into a roller-attached surface and a free surface, the roller-attached surface and the free surface have different cooling rates, and a large area of ​​parallel-oriented tenth-order quasicrystal-like micron tubes are distributed on one side of the free surface.

[0016] Furthermore, in step 2), the tenth-order quasicrystal approximates a microtube, and the average length, inner diameter, and outer diameter of the microtube are 6.99 μm, 0.38 μm, and 1.61 μm, respectively.

[0017] The advantages of the present invention are:

[0018] 1) The prepared ten-fold quasicrystal-like phase (complex intermetallic compound) microtubes have large area and parallel orientation.

[0019] 2) The preparation method is simple and easy, with a short cycle, which is conducive to mass production.

[0020] 3) The prepared microtubes have excellent micro-nanoscale mechanical properties.

[0021] 4) The prepared microtubes combine the thermal stability of quasicrystals, the unique atomic arrangement on the surface; the cocktail effect of high-entropy alloys with multiple elements; the four major effects of small size, quantum, surface and interface at the micro-nano scale; and the ability to form large three-dimensional arrays due to controllable shape and parallel orientation, which is of great value for the development of its potential applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Al in Example 1 20 Si 20 Mn 20 Fe 20 Ga 20 Scanning electron microscope image of the free surface microtubes of high entropy alloy thin ribbon.

[0023] Figure 2 Al in Example 1 20 Si 20 Mn 20 Fe 20Ga 20 Scanning electron microscope image of microtubes in a cross-section of a high-entropy alloy ribbon.

[0024] Figure 3 Al in Example 1 20 Si 20 Mn 20 Fe 20 Ga 20 Cross-sectional scanning electron micrograph of a single microtube in a high-entropy alloy ribbon.

[0025] Figure 4 Al in Example 1 20 Si 20 Mn 20 Fe 20 Ga 20 Diagram of the morphological types of microtubes in high-entropy alloy ribbons.

[0026] Figure 5 Al in Example 1 20 Si 20 Mn 20 Fe 20 Ga 20 Statistical distribution of (a) length, (b) inner diameter, and (c) outer diameter of microtubes in high-entropy alloy ribbons.

[0027] Figure 6 Al in Example 1 20 Si 20 Mn 20 Fe 20 Ga 20 Transmission electron microscopy (TEM) bright-field images and selected-area electron diffraction (SAD) patterns of microtubes in high-entropy alloy ribbons. (a) Hollow microtube (Type 2). (b) and (c) SAD patterns of regions b and c in (a). (d) Helical microtube with two ends (Type 3). (e) and (f) SAD patterns of regions e and f in (d). (g) Helical microtube with one end (Type 4). (h) and (i) SAD patterns of regions h and i in (g).

[0028] Figure 7 These are the micro- and nano-scale mechanical properties of the microtubes in the alloy ribbon spun at 10 m / s in Example 1.

[0029] Figure 8 XRD results of alloy ribbons prepared at different spinning speeds: 5m / s, 10m / s, 25m / s.

[0030] Figure 9 This is the scanning electron microscope morphology of the microtubes in the alloy ribbon spun at 5 m / s in Example 2.

[0031] Figure 10 This is the scanning electron microscope morphology of the microtubes in the alloy ribbon spun at 25 m / s in Example 3. DETAILED DESCRIPTION

[0032] Example 1

[0033] 1) The surface of the raw materials of high purity 99.99% Al, 99.3% Si, 99.9% Mn, 99.9% Fe and 99.9% Ga is polished to remove the oxide layer and impurities, and the ingredients are mixed according to the atomic ratio. Then, they are melted in a vacuum induction resistance furnace under argon protection; after melting, they are cooled at room temperature to obtain Al 20 Si 20 Mn 20 Fe 20 Ga 20 ingot;

[0034] 2) The melted ingot was cut into small pieces with a diameter of 1 cm and placed in a quartz tube. The ingot was then induction-heated and melted using a vacuum single-roll copper wheel spinning device at a spinning speed of 10 m / s to produce a spinning alloy ribbon with a large area of ​​parallel-oriented decadic quasicrystal-like micron tubes distributed on its free surface.

[0035] The scanning electron microscope morphology of the tenth order quasicrystal-like microtube prepared on the free surface of the alloy ribbon according to the above method is as follows: Figure 1 shown. Figure 2 This is a cross-sectional SEM image of a microtube in an alloy ribbon. The results show that a large area of ​​uniformly parallel micron-sized tubular structures are distributed on the free surface of the high entropy alloy ribbon. The pores of the microtubes run through the center of the entire microtube, as shown in Figure 2. Figure 3 In addition, Figure 4 As shown in Figure 1, the shapes of microtubes can be roughly divided into four types: semi-arc microtubes (Type 1); hollow microtubes (Type 2); microtubes with spirals at both ends (Type 3); and microtubes with spirals at one end (Type 4). These four types of microtubes are randomly distributed and together form a large area of ​​parallel oriented microtubes. The lengths and inner and outer diameters of 1000 microtubes in the SEM images were counted using image J software. The statistical results are shown in Figure 1. Figure 5 The results show that the average length, inner diameter and outer diameter of the prepared microtubes are 6.99±2.56μm, 0.38±0.13μm and 1.61±0.42μm, respectively.

[0036] Figure 6 Al 20 Si 20 Mn 20 Fe 20 Ga 20Bright field and selected area electron diffraction patterns of three different types of microtubes in high entropy alloy ribbons along the

[010] direction. The results show that, except for the hollow microtubes, which are composed of relatively perfect (1 / 0, 2 / 1) quasicrystal-like phases (lattice constants are a = 0.73nm, b = 1.23nm, c = 2.24nm) domain structures, the structures of the remaining microtubes are composed of perfect (1 / 0, 2 / 1) domains and defective (1 / 0, 2 / 1) domains in different directions rotating and growing alternately around the hollow part. In addition, the composition of the microtubes measured by EDS is Al 18.8 Si 20.6 Mn 22.7 Fe 26.6 Ga 11.3 .

[0037] Nanoindentation tests were performed on the microtubes using a Nano Indenter II, with an indentation depth of 200 nm and a Poisson's ratio of 0.28. Six indentation tests were performed on each sample, and the average value was calculated. Figure 7 A graph showing the micro- and nanoscale mechanical properties of microtubes in a spinning alloy ribbon. The upper left corner of the image shows a nanoindentation on the microtube. Calculated from the nanomechanical load-displacement curve, the hardness and Young's modulus of the quasicrystal-like microtubes reach 10.9 GPa and 189.3 GPa, respectively, demonstrating excellent micro- and nanoscale mechanical properties.

[0038] Example 2

[0039] The method for preparing large-area parallel-oriented decadic quasicrystal-like microtubes in Example 2 is different from that in Example 1 only in that the belt spinning speed in step 2) of Example 2 is 5 m / s.

[0040] The scanning electron microscope morphology of the ten-order quasicrystal-like micron tube prepared according to the method described in Example 2 is as follows: Figure 9 The results show that the free surface of the alloy ribbon is distributed with micron-scale tubular structures, which are the same as the ten-order quasicrystal-like microtubes found in Specific Example 1. However, unlike Specific Example 1, the tubular morphology prepared in Specific Example 2 is poor. Moreover, the area of ​​the prepared microtubes is small, which is consistent with the Figure 8 The tenth quasicrystal / approximate phase diffraction peak intensity of the alloy ribbon with a medium roller speed of 5m / s is weakly matched.

[0041] Example 3

[0042] The method for preparing large-area parallel-oriented decadic quasicrystal-like microtubes in Example 3 is different from that in Example 1 only in that the belt spinning speed in step 2) of Example 3 is 25 m / s.

[0043] The scanning electron microscope morphology of the ten-order quasicrystal-like micron tube prepared according to the method described in Example 3 is as follows: Figure 10As shown in the figure, it can be seen that the microtubes prepared at a roller speed of 25 m / s have a good morphology and consistent orientation. This is the same as the ten-order quasicrystal-like microtubes found in specific example 1. Figure 8 The peak intensity of the tenth quasicrystal / approximate phase diffraction peak of the alloy ribbon with a medium roller speed of 25m / s is weakened compared with that of 10m / s, indicating that the total amount of microtubes prepared at a spinning speed of 25m / s is reduced.

[0044] Figure 8 The XRD comparison diagrams of the alloy ribbons prepared in Examples 1, 2, and 3 show that the phase composition of the alloy ribbons prepared at roller speeds of 5 m / s and 25 m / s is the same as that of the alloy ribbon prepared at a roller speed of 10 m / s, both containing decadic quasicrystal-like microtubes.

Claims

1. A method for preparing large-area parallel-oriented ten-order quasicrystal-like microtubes, characterized in that: The following steps are involved: 1) The surface of the raw materials of high purity 99.99% Al, 99.3% Si, 99.9% Mn, 99.9% Fe and 99.9% Ga is polished to remove the oxide layer and impurities, and the ingredients are mixed according to the atomic ratio; then, they are melted in a vacuum induction resistance furnace under argon protection; after melting, they are cooled at room temperature to obtain Al 20 Si 20 Mn 20 Fe 20 Ga 20 ingot; 2) Take the melted ingot, cut it into small pieces with a diameter of 1 cm, and place it in a quartz tube. Then use a vacuum single-roll copper wheel spinning device for induction heating and melting. The process parameters of the vacuum single-roll copper wheel spinning device are: spinning speed: 10 m / s; Protective gas: argon; furnace pressure: 0.2 Pa; spray bag pressure: 0.02 MPa, the strip alloy thin strip is prepared, and its free surface is distributed with a large area of ​​parallel oriented Al 18.8 Si 20.6 Mn 22.7 Fe 26.6 Ga 11.3 The tenth-order quasicrystal approximates the micron tube; the quartz tube used in the spinning belt has a length of 15 cm, an inner diameter of 1.2 cm, a flat mouth, a length of 3 mm, and a width of 0.3 mm.

2. The method for preparing a large-area parallel-oriented decadic quasicrystal-like microtube according to claim 1, characterized in that: In step 2), the average width of the spun alloy strip is 5 mm and the average thickness is 70 μm.

3. The method for preparing a large-area parallel-oriented decadic quasicrystal-like microtube according to claim 1, characterized in that: In step 2), the strip-spinning alloy thin strip is divided into a roller-attached surface and a free surface. The roller-attached surface and the free surface have different cooling rates, and a large area of ​​parallel-oriented tenth-order quasicrystal-like micron tubes are distributed on one side of the free surface.

4. The method for preparing a large-area parallel-oriented decadic quasicrystal-like microtube according to claim 1, characterized in that: In step 2), the tenth-order quasicrystal approximates a microtube, and the average length, inner diameter, and outer diameter of the microtube are 6.99 μm, 0.38 μm, and 1.61 μm, respectively.

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