CN113523270B - Preparation method of metal nanowire array based on interface reaction and solid-state phase change - Google Patents

Preparation method of metal nanowire array based on interface reaction and solid-state phase change Download PDF

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CN113523270B
CN113523270B CN202110774171.XA CN202110774171A CN113523270B CN 113523270 B CN113523270 B CN 113523270B CN 202110774171 A CN202110774171 A CN 202110774171A CN 113523270 B CN113523270 B CN 113523270B
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CN113523270A (en
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王敬泽
翁冠军
常晶
苏云龙
尹佳庆
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Harbin University of Science and Technology
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    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate

Abstract

The invention belongs to the technical field of preparation of one-dimensional nano materials, and particularly relates to a preparation method of a metal nanowire array based on interface reaction and solid-state phase transition, wherein the preparation method of the metal nanowire array comprises the following steps: firstly, cleaning a substrate; secondly, enabling the low-melting-point alloy as a cladding material to be in close contact with the substrate; thirdly, growing the metal nanowire array in the substrate by a reaction diffusion method; and finally, removing the bulge on the surface of the substrate to obtain the metal nanowire array embedded in the substrate. The invention has the advantages that: (1) The method has the advantages of low cost, short reaction time, and simple and effective operation. (2) The metal nanowire prepared by the method has high orientation, orderliness and uniform length. (3) The method has universality, can select and change the preferred orientation of the substrate crystal grains, control the growth direction and the growth area of the nanowire, and is hopeful to realize the large-scale attachment of the metal nanowire array in the substrate.

Description

Preparation method of metal nanowire array based on interface reaction and solid-state phase change
Technical Field
The invention belongs to the technical field of preparation of one-dimensional nano materials, and particularly relates to a method for preparing a metal nanowire array based on interface reaction and solid-state phase change.
Background
Nano materials are the hot research direction in the field of materials, and one-dimensional nano materials such as nano wires, nano rods and the like can play an important role in the fields of sensors, catalysis, energy sources and the like. The metal nano-wire has unique electricity, magnetism and transmission performance, and has wide application prospect in the fields of photoelectronic devices and the like. Common methods for preparing metal nanowires mainly include chemical vapor deposition, templating, solvothermal methods, and the like. Chemical vapor deposition is a process of regulating and controlling the nucleation and growth of nano materials by controlling parameters such as pressure, airflow rate, substrate temperature and the like under the conditions of high temperature, plasma or laser assistance and the like by utilizing vapor phase chemical reaction. CN 112981530A adopts silicon dioxide auxiliary CVD (chemical vapor deposition reaction) to prepare vanadium dioxide single crystal micro-nano wire, the method has simple preparation process, low cost, high purity and controllable nano wire appearance, but the chemical vapor deposition method has lower deposition rate, and in many occasions, the reaction source participating in deposition and the residual gas after reaction are inflammable, explosive and even toxic, and the tail gas needs to be treated, thus being not beneficial to environmental protection.
The template method is to use the holes with nano-structures to control the growth of nano-materials, thereby preparing nano-wires. The template method can accurately regulate and control the shape, structure and size of the nano wire, can improve the dispersity of the nano wire, and is an important means for preparing the metal nano wire at present. Among them, the porous anodized aluminum film template is the most common, and patent CN 112481660A uses this method to grow metal nanowire arrays in the porous anodized aluminum template, thereby obtaining ordered and regular metal nanowire arrays. According to the method, the appearance of the metal nanowire is more uniform due to the special structure of the template, but the size of the metal nanowire is greatly limited due to the size of the template. In addition, the alumina template has larger brittleness, and is easy to break in the preparation process, so that the difficulty in preparing the nanowire is greatly improved. These problems therefore limit the practical production applications of the template method to a large extent.
The solvothermal method is a method for realizing crystallization and growth of a material from a solution of a soluble metal or a metal organic salt under the conditions of high temperature and high pressure. In a typical synthesis process, a metal source, a solvent, a reducing agent and a reagent which plays a role in guiding crystal growth are added into a hydrothermal kettle according to a certain proportion and react in a subcritical or supercritical environment to form the metal nanowires. Patent CN 108746662A is an Ag nanowire precursor solution prepared by using soluble metal salt. Firstly, the precursor solution and glycol are mixed and heated in an oil bath, and then the product is cooled to room temperature, and a precipitate is obtained by adopting a centrifugal technology, so that the nanowire can be obtained. The method has wide applicability, simple operation and mild reaction conditions. However, the nanowires synthesized by the method usually contain impurities such as particles and nanorods, and further processing and impurity removal are needed. Meanwhile, the method has high requirements on the reliability of equipment and very strict production process. The invention prepares the nanowire array by utilizing an interfacial reaction and a solid-state phase change process. Compared with a template method, the method does not need to use a template to control the growth of the nanowires, and the cost is greatly reduced. Compared with a vapor deposition method, the method has the advantages of wide requirements on equipment and process, no generation of harmful substances, higher purity of the prepared nanowire and less impurities. Therefore, the method is simple to operate, green and nontoxic, the cost is reasonably controlled, the quality of the prepared product is high, and the method is suitable for mass production in actual production and life.
Disclosure of Invention
The invention provides a preparation method of a metal nanowire array based on interface reaction and solid-state phase transition, aiming at solving the problems of complex preparation process, low efficiency and high cost of the existing metal nanowire array
The technical scheme of the invention is as follows:
the preparation method of the metal nanowire array based on the interfacial reaction and the solid-state phase change comprises the following steps:
1. cleaning the surface of the metal substrate;
2. preparing low-melting-point alloy;
3. taking the low-melting-point alloy obtained in the step two as a cladding material, and taking the alloy and a metal substrate after being in close contact as a diffusion couple so as to establish a reaction diffusion system;
4. heating at constant temperature by adopting a covering agent protection method, carrying out growth and solid phase change processes of the intermetallic compound in the reaction diffusion system established in the step two, and regulating and controlling the growth direction of the intermetallic compound according to the preferred orientation of crystal grains in the substrate;
5. and after the heat preservation is finished, machining the metal substrate containing the cladding layer in a polishing mode, removing bulges on the surface of the metal substrate, and obtaining the metal nanowire array embedded in the metal substrate.
In the first step, the substrate is a load matrix of the nanowire, the substrate is selected from a metal Al rolling plate, and the substrate is cleaned by ethanol in an ultrasonic cleaning machine for 5min respectively.
In the second step of the preparation method of the metal nanowire array, the low-melting-point alloy is Mg 46 Zn 54 The alloy is prepared by smelting Mg (with the purity of 99.995%) and Zn (with the purity of 99.995%), wherein the smelting temperature is 700-750 ℃, and the heat preservation time is 30-60 min; wherein Mg is used as a main diffusion element, and Zn is used for reducing the melting point of the alloy.
In the third step, the close contact is realized by a hot cladding mode, the cladding temperature is 450-470 ℃, and the cladding time is 30-60 s.
In the fourth step, a covering agent is added for protection so as to achieve the purpose of preventing the metal nanowire array from being oxidized.
In the fourth step, the constant temperature heating is carried out at the temperature of 450-470 ℃ for 5-10 min.
In the fourth step, the metal Al substrate has preferred orientation on the (111) crystal face.
In the fifth step, 1000-mesh sand paper is used for polishing, the rotation speed of a polishing machine is 200r/min, and the specific polishing time depends on the thickness of the bulge on the Al substrate.
The principle of the invention is as follows:
firstly, carrying out thermodynamic analysis on the formation process of the metal nanowires:
classical nucleation theory teaches that when a new phase nucleates from the parent phase, the total free energy changes to:
ΔG＝ΔG V V+ΔγA
wherein Δ G V Is the change in free energy per volume, V is the core volume of the new phase, a is the surface area of the new phase, and γ is the surface free energy.
The classical theory is developed to the growth process of the metal nanowire, and the total free energy of a single unit cell in the growth process of the metal nanowire under a constant temperature state is changed into:
ΔG＝ΔG V +Δγ hkl
wherein Δ G V Change in free energy per unit cell volume, Δ γ hkl Is the change in the surface free energy of the crystal (hkl).
Gibbs free energy expression equation:
G＝U+pV-TS
wherein U is the system internal energy, p is the ambient pressure, V is the system volume, T is the ambient temperature, and S is the system entropy.
Experiments and researches show that Al is contained under the conditions of constant temperature and constant pressure 3 Mg 2 Conversion to Al 12 Mg 17 The process of (a) involves drastic changes in cell volume, so changes in the internal energy of the system are ignored during the phase change. Therefore,. DELTA.G V Al3Mg2→Al12Mg17 The change of the volume free energy of the single cell is as follows:
Figure BDA0003153790140000021
wherein V 1 Al3Mg2，Al12Mg17 Are respectively Al 3 Mg 2 And Al 12 Mg 17 Cell volume of (1), Δ S Al3Mg2→Al12Mg17 Is the difference in entropy (0.05J/mol/K).
Al 12 Mg 17 Has a unit cell volume of about Al 3 Mg 2 1/20, the total free energy change of the unit cell volume during the growth process of the metal nanowire can be expressed as:
Figure BDA0003153790140000022
crystal surface free energy expression:
Figure BDA0003153790140000023
wherein gamma is hkl Surface energy on the (hkl) face of the crystal,f (hkl) is a reflection parameter of the symmetry of the crystal structure, E b Is a bond energy of d 0 Is the bond length.
Experiments and researches show that the metal nanowire preferentially grows on a (411) crystal face, wherein Al is 3 Mg 2 Is of fcc structure, and has a crystal lattice constant of
Figure BDA0003153790140000031
Key length->
Figure BDA0003153790140000032
Al 12 Mg 17 Is in bcc structure, the crystal lattice constant a is->
Figure BDA0003153790140000033
Figure BDA0003153790140000034
Key length->
Figure BDA0003153790140000035
Therefore, the surface free energy of the single cell changes in the (411) crystal plane 411 Al3Mg2→Al12Mg17 Comprises the following steps:
Δγ 411 ＝0.015E Mg-Al
wherein E Mg-Al Is the bond energy of magnesium-aluminum bond.
Therefore, the total free energy change of the growth process of the metal nanowire can be expressed as:
ΔG＝-19pV 1 Al12Mg17 -0.05T+0.015E Mg-Al
experiments and researches show that in the growth process of the metal nanowire, the volume free energy change is the main driving force, and the surface free energy change is the main resistance. Because the change of the volume free energy is far larger than the change of the surface free energy in the growth process of the metal nanowire, the change delta G of the total free energy is less than 0, namely the growth process of the nanowire is spontaneous.
The invention discloses a preparation method of a metal nanowire array, wherein the growth process of the metal nanowire array can be divided into two stages. In the first stage, the mixture is kept at 450-500 DEG CIn the molten state, mg atoms in MgZn diffuse into the aluminum substrate to react with Al to generate columnar coarse-grained Al 3 Mg 2 . The reaction activation energy required for atoms on the (111) dense planes in the Al cell is greater due to the smallest atomic distance between the dense planes, while Al is 3 Mg 2 Preferentially growing on crystal planes with larger atomic distance and vertical to the close-packed plane to form columnar coarse crystals. In addition, al 3 Mg 2 The cell volume of the aluminum substrate is far larger than that of Al, so that the growth of columnar coarse crystals is further promoted, and the back of the aluminum substrate bulges. In the second stage, mg is further diffused along with the increase of the holding time, and Al generated in the first stage 3 Mg 2 Transformation occurs to form Al with more stable structure 12 Mg 17 . Wherein, al 12 Mg 17 Has a unit cell volume of about Al 3 Mg 2 1/20 of (1), thus Al in stage one 3 Mg 2 Transformation of columnar coarse grains into Al 12 Mg 17 The cell volume is continuously reduced in the process of (1), and finally Al 3 Mg 2 Shrinkage of columnar coarse grains into Al 12 Mg 17 A nanowire.
The invention has the beneficial effects that:
the invention provides a preparation method of a metal nanowire array, which utilizes the characteristic that the atomic distance of a close-packed surface of a crystal structure is small, and the reaction activation energy is high, so that Al in the preparation process 12 Mg 17 The nanowires will avoid growing on the (111) dense plane of the Al unit cell, and will tend to grow in the direction perpendicular to the dense plane, thereby realizing the directional control of the nanowires. Meanwhile, as the metal nanowires grow in the Al substrate, a stable environment is provided, so that the metal nanowires can be stably crystallized and directionally grown. Therefore, the preparation method of the metal nanowire array has good application prospect, and has the following specific advantages:
1. the preparation method provided by the invention firstly obtains the coarse crystal columns of the intermediate phase in the metal substrate, carries out heat treatment on the intermediate phase, finally obtains the metal nanowire array, can realize the adjustable growth direction in the array according to the adjustment of the preferred orientation of the metal substrate, and has the characteristic of controllable growth direction.
2. The preparation method provided by the invention combines the interface reaction and solid phase change modes to prepare the metal nanowire array, compared with vapor deposition, the method does not need to process reaction substances to be in a gas state, avoids the possibility that reaction gas reacts with a substrate or equipment, and products are generally generated in a matrix and are easier to collect; compared with a template method, the growth direction of the nanowires is controlled by utilizing the preferred orientation of the metal substrate, the template with the ordered arrangement rule does not need to be prepared, and the template is removed by a chemical or physical means after the preparation is finished, so that the damage to the metal nanowires is reduced, and the production efficiency is improved; compared with a hydrothermal method, the method has the advantages that a high-pressure closed container is not needed, and the metal nanowire array with good crystallization, less aggregation, high purity, narrow particle size distribution and controllable morphology under most conditions can be obtained only under a high-temperature condition.
3. According to the preparation method provided by the invention, in the preparation process, the cladding area of the cladding material can be adjusted, the temperature and time of heat treatment can be changed, the growth effect of the metal nanowire can be adjusted, the uniform distribution and the complete structure of the obtained metal nanowire array can be ensured, and the technical parameters of the prepared metal nanowire array structure can be controlled more easily.
4. The preparation method provided by the invention has universality, can be popularized to the preparation of various metal nanowire arrays, and has good application in the fields of electrocatalysis, electrodes, capacitors, nanomaterial synthesis and the like.
Drawings
FIGS. 1 (a) to 1 (d) show Al based on solid state phase transition in example 1 of the present invention 12 Mg 17 The nanowire array growth schematic diagram is the preparation method of the nanowire array;
FIG. 2 shows Al prepared in example 1 of the present invention 12 Mg 17 XRD pattern of nanowire array;
FIG. 3 shows Al prepared in example 1 of the present invention 12 Mg 17 Scanning electron microscopy of nanowire arrays.
Detailed Description
In the specific implementation process, the Al of the invention 12 Mg 17 Firstly, cleaning an aluminum alloy substrate; secondly, taking the MgZn-based alloy as a cladding material to be in close contact with the substrate; thirdly, growing the metal nanowire array in the aluminum alloy substrate by a reaction diffusion method; and finally, removing the bulges on the surface of the substrate. The method specifically comprises the following steps:
1. cleaning the surface of the substrate;
2. taking MgZn-based alloy as a cladding material, and taking the MgZn-based alloy and a substrate after being in close contact as a diffusion couple so as to establish a reaction diffusion system; (ii) a
3. Adopting a constant-temperature heating method, carrying out growth and solid phase change processes of the intermetallic compound in the reaction diffusion system established in the step two, and regulating and controlling the growth direction of the intermetallic compound according to the preferred orientation of crystal grains in the substrate;
4. after the heat preservation is finished, machining a diffusion couple containing the MgZn-based alloy cladding layer in a polishing mode, removing bulges on the surface of the metal aluminum plate, and obtaining Al embedded in the aluminum substrate 12 Mg 17 And (4) nanowire arrays.
The present invention will be described in further detail with reference to the following examples and drawings, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way.
Example 1:
in this example, al was prepared 12 Mg 17 Nanowire arrays: and cleaning the aluminum substrate by adopting ethanol in an ultrasonic cleaning machine for 5min. Smelting MgZn alloy as a cladding material, enabling the MgZn alloy to be in close contact with a metal Al plate by a hot cladding method, integrating the MgZn cladding layer and the metal Al plate after the contact to be used as a diffusion couple, taking a covering agent as a protective measure, and carrying out a solid phase change process at the temperature of 450 ℃ for 5min. Taking out the diffusion couple after the reaction is finished, and then mechanically processing the diffusion couple by using a sand paper polishing method, and obtaining the Al with directional growth after the surface bulge of the metal Al plate is removed 12 Mg 17 The technical parameters and performance indexes of the nanowire array are as follows: wire diameter of150-200 nm, 200-300 nm of spacing and 4-6 μm of length.
As shown in fig. 1, the nanowire array growth diagram, it can be seen from fig. 1 that the growth of the metal nanowires is divided into 4 steps, which are (a) Mg atom diffusion; (b) Columnar coarse-grained Al 3 Mg 2 Growing to form a bulge; (c) Near cladding layer end Al 3 Mg 2 Starting solid phase change, and enabling a crystal column to shrink; (d) Al (Al) 3 Mg 2 Complete conversion to Al 12 Mg 17 The pillars become nanowires.
Al prepared as shown in FIG. 2 12 Mg 17 The XRD pattern of the nanowire array can be seen from FIG. 2 that the metal Al plate has preferred orientation on the (111) plane, and Al 12 Mg 17 Preferentially growing on the (411) crystal face.
Al prepared as shown in FIG. 3 12 Mg 17 SEM image of nanowire array, as can be seen in FIG. 3, al 12 Mg 17 The growth directions of the nanowires are consistent, the wire diameter is 150-200 nm, the spacing is 200-300 nm, the length is 4-6 μm, and the nanowires are uniformly distributed.
Example 2:
in this example, al was prepared 12 Mg 17 Nanowire arrays: and cleaning the aluminum substrate by adopting ethanol in an ultrasonic cleaning machine for 5min. Smelting a highly-cocrystallized MgZn alloy as a cladding material, enabling the MgZn alloy to be in close contact with a metal Al plate by a hot cladding method, integrating the MgZn cladding layer and the metal Al plate after the contact to be used as a diffusion couple, taking a covering agent as a protective measure, and carrying out a solid phase change process at 460 ℃ for 5min. Taking out the diffusion couple after the reaction is finished, and then mechanically processing the diffusion couple by adopting an abrasive paper polishing method, and obtaining the Al with directional growth after the surface bulge of the metal Al plate is removed 12 Mg 17 The technical parameters and performance indexes of the nanowire array are as follows: the wire diameter is 150-200 nm, the spacing is 200-300 nm, and the length is 4-6 μm.
Example 3:
in this example, al was prepared 12 Mg 17 Nanowire arrays: cleaning aluminum base by ethanol in ultrasonic cleaning machinePlate washing time 5min. Smelting MgZn alloy as a cladding material, enabling the MgZn alloy to be in close contact with a metal Al plate by a hot cladding method, integrating the MgZn cladding layer and the metal Al plate after the contact as a diffusion couple, taking a covering agent as a protective measure, and carrying out a solid phase change process at the temperature of 470 ℃ for 5min. Taking out the diffusion couple after the reaction is finished, and then mechanically processing the diffusion couple by using a sand paper polishing method, and obtaining the Al with directional growth after the surface bulge of the metal Al plate is removed 12 Mg 17 The technical parameters and performance indexes of the nanowire array are as follows: the wire diameter is 150-200 nm, the distance is 200-300 nm, and the length is 4-6 μm.
Example 4:
in this example, al was prepared 12 Mg 17 Nanowire arrays: and cleaning the aluminum substrate by adopting ethanol in an ultrasonic cleaning machine for 5min. Smelting MgZn alloy as a cladding material, closely contacting the MgZn alloy with a metal Al plate by a hot cladding method, taking the MgZn cladding layer and the metal Al plate as a whole as a diffusion couple after the contact, taking a covering agent as a protective measure, and carrying out a solid phase change process at the temperature of 450 ℃ for 10min. Taking out the diffusion couple after the reaction is finished, and then mechanically processing the diffusion couple by using a sand paper polishing method, and obtaining the Al with directional growth after the surface bulge of the metal Al plate is removed 12 Mg 17 The technical parameters and performance indexes of the nanowire array are as follows: the wire diameter is 150-200 nm, the distance is 200-300 nm, and the length is 4-6 μm.
Example 5:
in this example, al was prepared 12 Mg 17 Nanowire arrays: and cleaning the aluminum substrate by adopting ethanol in an ultrasonic cleaning machine for 5min. The smelted MgZn alloy is used as a cladding material and is in close contact with a metal Al plate by a hot cladding method, after the contact, the MgZn cladding layer and the metal Al plate are integrated to be used as a diffusion couple, a covering agent is used as a protective measure, and a solid phase transition process is carried out at the temperature of 460 ℃ for 10min. Taking out the diffusion couple after the reaction is finished, and then mechanically processing the diffusion couple by using a sand paper polishing method, and obtaining the Al with directional growth after the surface bulge of the metal Al plate is removed 12 Mg 17 Nano linear arrayThe technical parameters and performance indexes are as follows: the wire diameter is 150-200 nm, the distance is 200-300 nm, and the length is 4-6 μm.
Example 6:
in this example, al was prepared 12 Mg 17 Nanowire arrays: and cleaning the aluminum substrate by adopting ethanol in an ultrasonic cleaning machine for 5min. Smelting MgZn alloy as a cladding material, closely contacting the MgZn alloy with a metal Al plate by a hot cladding method, taking the MgZn cladding layer and the metal Al plate as a whole as a diffusion couple after the contact, taking a covering agent as a protective measure, and carrying out a solid phase change process at 470 ℃ for 10min. Taking out the diffusion couple after the reaction is finished, and then mechanically processing the diffusion couple by adopting an abrasive paper polishing method, and obtaining the Al with directional growth after the surface bulge of the metal Al plate is removed 12 Mg 17 The technical parameters and performance indexes of the nanowire array are as follows: the wire diameter is 150-200 nm, the distance is 200-300 nm, and the length is 4-6 μm.

Claims (9)

1. A preparation method of a metal nanowire array based on interface reaction and solid-state phase change is characterized by comprising the following steps: the method comprises the steps of placing an Al substrate in a resistance furnace, taking Mg46Zn54 low-melting-point alloy as a diffusion source, diffusing elements in the Al substrate at the temperature of 450-500 ℃, preferentially growing metal nanowires by means of preferred orientation in the substrate, and finally obtaining Al with consistent orientation 12 Mg 17 The metal nanowire array is characterized in that the Mg46Zn54 low-melting-point alloy is prepared by smelting Mg and Zn, the smelting temperature is 700-750 ℃, and the heat preservation time is 30-60 min.
2. The method for preparing the metal nanowire array based on the interfacial reaction and the solid-state phase transition as claimed in claim 1, wherein the second phase Al is generated in the substrate by the interfacial reaction 3 Mg 2 。
3. The method as claimed in claim 2, wherein the method employs interfacial reaction diffusion to convert the second phase in the substrate into the metal nanowire array structure by using the solid phase transformation to bring the change of the unit cell volume.
4. The method of claim 1, wherein the method utilizes preferred orientation existing in the metal substrate, controls the growth direction of the nanowires, and prepares the metal nanowire array with uniform orientation.
5. The method for preparing a metal nanowire array based on an interfacial reaction and a solid state phase transition as recited in claim 1, comprising the steps of:
1. cleaning the surface of the metal substrate;
2. preparing low-melting-point alloy;
3. taking the low-melting-point alloy obtained in the step two as a cladding material, and taking the alloy and a metal substrate after being in close contact as a diffusion couple so as to establish a reaction diffusion system;
4. heating at constant temperature by adopting a covering agent protection method, performing a metal nanowire growth process in a reaction diffusion system established in the third step, and regulating and controlling the growth direction of the metal nanowire according to the preferred orientation of crystal grains in the substrate;
5. and after the heat preservation is finished, machining the metal substrate containing the cladding layer in a polishing mode, removing bulges on the surface of the metal substrate, and obtaining the metal nanowire array embedded in the metal substrate.
6. The method for preparing a metal nanowire array based on interfacial reaction and solid-state phase transition as claimed in claim 5, wherein in the step one, the metal substrate is a supporting substrate of nanowires, the substrate is selected from a metal Al rolled plate, and the metal Al rolled plate is cleaned by an ultrasonic cleaning machine with ethanol, wherein the specific cleaning time depends on the degree of cleanness of the surface of the metal substrate.
7. The method as claimed in claim 5, wherein in the second step, the low melting point alloy is Mg46Zn54, wherein Mg is used as a raw material for preparing the metal nanowire array, and Zn is used to lower the melting point of the alloy.
8. The method for preparing a metal nanowire array based on interfacial reaction and solid-state phase transition as claimed in claim 5, wherein in step three, the close contact is achieved by thermal cladding, and the specific cladding temperature and time depend on the melting point of the substrate and the cladding material.
9. The method for preparing a metal nanowire array based on interfacial reaction and solid-state phase transition as claimed in claim 5, wherein in step four, the growth of the metal nanowires is achieved by the volume change of unit cells caused by the solid-state phase transition, and the specific growth process depends on the volume change rate of the unit cells before and after the phase transition.
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