Preparation device and preparation method of amorphous nano-alloy particles for brazing coating

Abstract

The invention provides a preparation device and a preparation method of amorphous nano-alloy particles for brazing coating. The preparation device comprises a first gas source module, an electric spark generation system, a second gas source module, a gas heating module, a cooling module and a deposition module, the first gas source module is communicated with the gas inlet end of the electric spark generating system, the second gas source module is communicated with the gas inlet end of the gas heating module, and the gas outlet end of the gas heating module is communicated with the gas outlet end of the electric spark generating system. The air outlet end of the electric spark generation system communicates with the deposition module through the cooling module. The nano-particles prepared by the method are spheres with smooth surfaces, have good dispersibility, can accurately control amorphous nano-particle parameters, are high in stability, low in cost and high in universality, and are suitable for batch preparation of amorphous nano-alloy particles with high stability and controllable size and morphology.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nanomaterial preparation technology and brazing coating, in particular to a preparation device and method of amorphous nanometer alloy particles for brazing coating. BACKGROUND

[0002] Amorphous nanometer alloy particles have the advantages of high strength, high hardness, high wear resistance and high corrosion resistance due to their long-range disorder and short-range order structure characteristics, and are ideal welding materials, which have wide application prospects in the fields of brazing coating and additive manufacturing. However, how to stabilize an amorphous structure which is thermodynamically unstable at the nanometer scale where structural and morphological changes are prone to occur is still a great challenge, and faces difficulties in thermodynamics, dynamics and structure control.

[0003] The existing preparation technology has the following key problems: (1) poor controllability: chemical reduction method is prone to particle agglomeration and crystallization due to local overheating, and it is difficult to accurately control the size and morphology; (2) insufficient stability: the nanometer particles prepared by traditional laser ablation method and electric spark ablation method are prone to crystallization at room temperature, and it is difficult to stably produce single amorphous nanometer particles; (3) weak universality: most methods are only suitable for specific alloy systems, and it is difficult to realize amorphization of other single elements / alloys.

[0004] Therefore, it is an urgent problem to be solved in the field to develop a preparation technology of amorphous nanometer alloy particles for brazing coating, which can accurately control particle parameters, has high stability, low cost and strong universality.

[0005] Therefore, the present application is proposed. SUMMARY

[0006] The present application aims to overcome the shortcomings of the prior art, and provides a preparation device and method of amorphous nanometer alloy particles for brazing coating. The prepared nanometer particles have a smooth spherical surface and good dispersibility, and can accurately control the parameters of amorphous nanometer particles, have high stability, low cost and strong universality, and are suitable for batch preparation of amorphous nanometer alloy particles with high stability and controllable size and morphology.

[0007] In order to achieve the above-mentioned purpose of the present application, the following technical scheme is adopted: A preparation device of amorphous nanometer alloy particles for brazing coating comprises a first gas source module, an electric spark generation system, a second gas source module, a gas heating module, a cooling module and a deposition module. The first gas source module is connected to the gas inlet end of the electric spark generation system, the second gas source module is connected to the gas inlet end of the gas heating module, the gas outlet end of the gas heating module is connected to the gas outlet end of the electric spark generation system, and the gas outlet end of the electric spark generation system is connected to the deposition module through the cooling module.

[0008] Further, the first gas source module outputs gas into the electric spark generation system, the second gas source module outputs gas into the gas heating module, the original carrier gas flowing out of the electric spark generation system mixes with the heated gas flowing out of the gas heating module to obtain mixed carrier gas, atoms and atomic clusters in the mixed carrier gas fuse and grow into nanoparticles after being heated, and the mixed carrier gas enters the cooling module to be cooled to form amorphous nanoparticles and continue to be deposited in the deposition module with the mixed carrier gas.

[0009] Further, the electric spark growth cavity of the electric spark generation system is loaded with a target material, and the target material is at least one of Pb, Bi, Ag, Cu, Al, Fe, Au, Mg, Zn single metal or alloy.

[0010] Further, the gas heating module comprises a gas heating cavity and a heater, and the heater is an induction heater, a resistance heater or a methane burner.

[0011] Further, the cooling module comprises a cooling pipe and a cooling medium, and the mixed carrier gas flowing through the cooling pipe is rapidly cooled by the cooling medium.

[0012] Further, the cooling module is a liquid nitrogen rapid cooling pipe P2, and the liquid nitrogen rapid cooling pipe P2 comprises the cooling pipe and liquid nitrogen, and the cooling pipe is a double-layer pipe, and the cavity between the inner layer pipe and the outer layer pipe is connected to the liquid nitrogen.

[0013] Further, the gas outlet end of the electric spark generation system is connected to the gas inlet end of the carrier gas delivery pipe P1; the gas outlet end of the gas heating cavity is connected to the gas inlet end of the heated gas delivery pipe P3, and the gas outlet end of the heated gas delivery pipe P3 is connected to the gas inlet end of the carrier gas delivery pipe P1.

[0014] Further, the electric spark generation system is connected to the deposition module through the carrier gas delivery pipe P1 and the liquid nitrogen rapid cooling pipe P2.

[0015] Further, the length of the carrier gas delivery pipe P1 is 120-200 cm.

[0016] Further, the preparation device of the amorphous nano-alloy particle for brazing and coating further comprises a central control module; the first gas source module, the electric spark generation system, the second gas source module and the gas heating module are in communication connection with the central control module. The first gas source module comprises a first gas source G1 and a first flow meter F1 connected thereto, and the second gas source module comprises a second gas source G2 and a second flow meter F2 connected thereto; the electric spark generation system is provided with a power control assembly.

[0017] Further, the preparation device of the brazing coating amorphous nano-alloy particles further comprises a characterization module, which is in communication connection with the central control module; the characterization module monitors the product, and the central control module performs feedback adjustment on the process parameters according to the monitoring result.

[0018] Further, the preparation device of the brazing coating amorphous nano-alloy particles further comprises a gas loop pipeline, the gas inlet end of the gas loop pipeline is connected with the deposition chamber, and the gas outlet end of the gas loop pipeline is connected with the gas inlet end of the electric spark generation system.

[0019] A preparation method of amorphous nano-alloy particles, which adopts the preparation device of the brazing coating amorphous nano-alloy particles, comprises the following steps: Step S1, preheat the gas heating cavity; introduce the liquid nitrogen rapid cooling pipe P2 into the circulating liquid nitrogen; load the target material into the electric spark growth cavity; Step S2, after the gas heating cavity is fully preheated, open the first gas source G1, the first flow meter F1, and the electric spark generation system; Step S3, open the second gas source G2 and the second flow meter F2, and after the heated gas reaches a specific temperature, the heated gas flows through the heated gas delivery pipe P3, mixes with the original carrier gas from the first gas source G1 of the electric spark generation system, and then enters the carrier gas delivery pipe P1; Step S4, the heated gas in the carrier gas delivery pipe P1 mixes with the original carrier gas flowing out of the electric spark generation system, so that the temperature of the mixed carrier gas in the carrier gas delivery pipe P1 rises, and at this time, the atoms and atomic clusters in the mixed carrier gas are fused and grown into nano-particles after being heated; Step S5, the nano-particles in step S4 enter the liquid nitrogen rapid cooling pipe P2 under the action of the mixed carrier gas, are rapidly cooled in the liquid nitrogen rapid cooling pipe P2 to form amorphous nano-particles, and continue to be deposited on the substrate in the deposition chamber with the mixed carrier gas.

[0020] Further, the preparation method further comprises: step S6, using a spectrometer to perform real-time in-situ characterization on the obtained amorphous nano-particles, monitoring the size, morphology, and other properties of the product, and performing feedback adjustment on the previously set process parameters according to the monitoring result, so as to obtain the target amorphous nano-alloy particle product; Step S7, the tail gas of the cooled mixed carrier gas enters the electric spark generation system through the gas loop pipeline, and participates in the preparation again to realize recycling.

[0021] Further, in step S1, the gas heating cavity is preheated to 300-700℃.

[0022] Further, in step S2, the flow rate of the first flow meter F1 is set to 1.5L / min-8L / min.

[0023] Further, the voltage of the electric spark generating system in step S2 is set to 0.5kV~2.5kV.

[0024] Further, the flow rate of the second flow meter F2 in step S3 is set to 1.5L / min~8L / min.

[0025] Further, the heating gas reaches a temperature of 300~700℃ in step S3.

[0026] Compared with the prior art, the present application has the following advantages: 1. The preparation device and method of the amorphous nano-alloy particles for brazing and coating, the prepared nano-particles have a spherical surface and good dispersibility, and solve the problems of agglomeration and irregular shape of the product prepared by conventional commercial electric spark equipment.

[0027] 2. The preparation device and method of the amorphous nano-alloy particles for brazing and coating can accurately control the parameters of the amorphous nano-particles, have high stability, low cost and strong universality, and are suitable for batch preparation of amorphous nano-alloy particles with high stability and controllable size and morphology, while conventional commercial equipment is difficult to stably prepare amorphous nano-particles.

[0028] 3. The preparation device of the amorphous nano-alloy particles for brazing and coating can realize real-time in-situ monitoring of the product by introducing a spectrometer, timely regulation of the product, and controllable preparation of different size samples.

[0029] 4. The preparation device of the amorphous nano-alloy particles for brazing and coating can realize recycling of the carrier gas by recycling the tail gas of the mixed carrier gas, save the amount of gas, and reduce the cost. BRIEF DESCRIPTION OF DRAWINGS

[0030] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the description of the specific embodiments or the prior art. Obviously, the drawings described below are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0031] Figure 1 The structure diagram of the preparation device of the amorphous nano-alloy particles for brazing and coating of the present application; Figure 2 The morphology diagram of the agglomerated and irregular morphology Pb-Bi alloy nano-particles prepared by the conventional commercial electric spark equipment; Figure 3 The morphology diagram of the amorphous Pb-Bi nano-alloy particles prepared in Example 1 of the present application; Figure 4 The image shows the morphology of the amorphous Pb-Bi nanoalloy particles prepared in Example 2 of this invention. Figure 5 The image shows the morphology of the amorphous Pb-Bi nanoalloy particles prepared in Example 3 of this invention. Figure 6 The image shows the morphology of the spherical amorphous Ag-Cu alloy nanoparticles prepared in Example 4 of this invention. Figure 7 This is a morphology image of the smooth-surfaced spherical amorphous nanoalloy particles prepared in Example 5 of the present invention; Figure 8 The elemental distribution diagram of the spherical amorphous Pb-Bi alloy nanoparticles prepared in Example 5 of this invention in TEM; Figure 9 The EDS energy dispersive spectroscopy results are shown for the amorphous Pb-Bi alloy nanoparticles prepared in Example 5 of this invention. Detailed Implementation

[0032] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0033] An apparatus for preparing amorphous nano-alloy particles for brazing includes a first gas source module, an electric spark generating system, a second gas source module, a gas heating module, a cooling module, and a deposition module. The first gas source module is connected to the gas inlet of the electric spark generating system, the second gas source module is connected to the gas inlet of the gas heating module, the gas outlet of the gas heating module is connected to the gas outlet of the electric spark generating system, and the gas outlet of the electric spark generating system is connected to the deposition module through the cooling module.

[0034] like Figure 1 As shown, this invention adds [a feature] to the existing commercial EDM equipment. Figure 1 The device is shown in the orange dashed box. The core idea of ​​the modified device is to heat the original carrier gas at the outlet of the electric spark growth chamber, so that the atoms or atomic clusters in the original carrier gas are heated and fused to grow into nanoparticles, and deposited on the substrate before the nanoparticles further merge and grow, in order to avoid product agglomeration.

[0035] Preferably, the first gas source module outputs gas into the electric spark generation system, the second gas source module outputs gas into the gas heating module, the room temperature original carrier gas flowing out of the electric spark generation system is mixed with the high temperature gas flowing out of the gas heating module to obtain mixed carrier gas, atoms and atomic clusters in the mixed carrier gas are fused and grown into nanoparticles after being heated, the mixed carrier gas enters the cooling module to be cooled to form amorphous nanoparticles, and the amorphous nanoparticles continue to be deposited on the substrate in the deposition module with the mixed carrier gas.

[0036] Preferably, the target material is loaded in the electric spark growth cavity of the electric spark generation system, and the target material is a conductive material such as a metal element or an alloy. The present application can be applied to the preparation of amorphous nano-alloy particles of various metals / alloys, and has strong universality.

[0037] Preferably, the target material is at least one of elemental metals such as Pb, Bi, Ag, Cu, Al, Fe, Au, Mg, and Zn or an alloy.

[0038] Preferably, the gas heating module comprises a gas heating cavity and a heater, and the heater is an induction heater, an electric resistance heater, or a methane burner.

[0039] To heat the original carrier gas, the wall of the carrier gas delivery pipe was heated in the early stage to heat the original carrier gas through heat radiation of the pipe wall. However, both experimental and simulation results show that this method is not feasible. Through a large number of experiments and simulations, the present application finally selects the method of mixing high temperature gas with normal (low) temperature carrier gas to achieve the purpose of heating.

[0040] Preferably, the cooling module comprises a cooling pipe and a cooling medium, and the mixed carrier gas flowing through the cooling pipe is rapidly cooled by the cooling medium.

[0041] Preferably, the cooling module is a liquid nitrogen quenching pipe P2, the liquid nitrogen quenching pipe P2 comprises a cooling pipe and liquid nitrogen, the cooling pipe is a double-layer pipe, and the cavity between the inner layer pipe and the outer layer pipe is filled with liquid nitrogen.

[0042] The deposition chamber of the deposition module is a deposition chamber commonly used in the prior art of nanoparticle preparation devices, and will not be described here. The amorphous nanoparticles are deposited on the substrate in the deposition chamber with the mixed carrier gas.

[0043] The application adds a gas path near the carrier gas outlet of the electric spark generation system, introduces the gas into the gas heating cavity to rapidly heat the gas flowing therethrough, the heated gas is mixed with the original carrier gas, the temperature of the mixed carrier gas rapidly rises, the atoms and atomic clusters therein are heated and gathered to grow into nanoparticles, then the mixed carrier gas enters the cooling pipe, liquid nitrogen is introduced between the inner pipe and the outer pipe of the cooling pipe, the mixed carrier gas flowing therethrough is rapidly cooled to generate amorphous nanoparticles, and the amorphous nanoparticles are rapidly deposited on the substrate in the deposition chamber to obtain uniformly distributed amorphous nano-alloy particles. Compared with the existing commercial electric spark equipment, the modified equipment can effectively avoid the occurrence of agglomeration and the generation of irregular products, and the size of the nanoparticles can be adjusted by controlling the flow rate of the carrier gas.

[0044] Preferably, the gas outlet end of the electric spark generation system is connected to the gas inlet end of the carrier gas delivery pipe P1; the gas outlet end of the gas heating cavity is connected to the gas inlet end of the heated gas delivery pipe P3, the gas outlet end of the heated gas delivery pipe P3 is connected to the gas inlet end of the carrier gas delivery pipe P1, the room temperature original carrier gas flowing out of the electric spark generation system is mixed with the heated gas flowing out of the gas heating cavity to obtain mixed carrier gas, and the atoms and atomic clusters in the mixed carrier gas are fused and grown into nanoparticles after being heated.

[0045] Preferably, the electric spark generation system is connected to the deposition module through the carrier gas delivery pipe P1 and the liquid nitrogen rapid cooling pipe P2, the gas outlet end of the carrier gas delivery pipe P1 is connected to the inner pipe of the liquid nitrogen rapid cooling pipe P2, and the mixed carrier gas flowing through the inner pipe is rapidly cooled by liquid nitrogen to form amorphous nanoparticles.

[0046] Preferably, the length of the carrier gas delivery pipe P1 is 120-200 cm, including but not limited to 120 cm, 140 cm, 160 cm, 180 cm and 200 cm. The length of the carrier gas delivery pipe P1 affects the transportation distance and time of the atoms and atomic clusters in the mixed carrier gas, and further affects the size of the nanoparticles fused and grown after being heated. The flight time of the nanoparticles in the pipe is controlled by controlling the flow rate of the mixed carrier gas, and the size of the nanoparticles is adjusted.

[0047] Preferably, the preparation device of the brazing and coating amorphous nano-alloy particles further comprises a central control module; the first gas source module, the electric spark generation system, the second gas source module and the gas heating module are in communication connection with the central control module for gas source flow control, electric spark control and gas heating temperature control.

[0048] Among the many emerging methods for preparing nanoparticles, spark ablation technology has become a very promising preparation method due to its advantages such as normal pressure operation, high product purity, suitability for complex alloy preparation, and strong scalability (can be used for nano-printing deposition, nano-3D printing). Figure 2 As shown in FIG. 1, the Pb-Bi alloy nanoparticles prepared by the conventional commercial spark device are prone to agglomeration and have irregular morphology, which seriously restricts the application of the technology. In view of these problems, the present application provides a preparation device and a preparation method for preparing non-agglomerated spherical amorphous nano-alloy particles for brazing, which can control the size of the amorphous nanoparticles and has strong stability, and can improve the defects of the existing device.

[0049] Preferably, the first gas source module comprises a first gas source G1 and a first flow meter F1 connected thereto, and the gas of the first gas source G1 reaches the spark generation system after passing through the first flow meter F1; the second gas source module comprises a second gas source G2 and a second flow meter F2 connected thereto, and the gas of the second gas source G2 reaches the gas heating cavity after passing through the second flow meter F2.

[0050] Preferably, the spark generation system is provided with a power control component to control the spark current intensity and the voltage of the spark generation system.

[0051] Preferably, the preparation device of the amorphous nano-alloy particles for brazing further comprises a characterization module, which is in communication connection with the central control module. The characterization module uses a spectrometer to perform real-time detection and in-situ characterization on the amorphous nanoparticles of the deposited sample, and monitors the size, morphology, and physical state of the product. The central control module adjusts the process parameters according to the monitoring results, so as to timely adjust the process parameters, controls the product by controlling the gas flow, spark, or gas heating temperature, and prepares amorphous nano-alloy particles of different sizes. The present application can control the size of the nano-alloy particles by controlling the process parameters of the control system, such as controlling the gas flow, spark voltage and current intensity, and gas heating temperature.

[0052] Preferably, the central control module further comprises a user interface for gas flow control, gas heating temperature control, spark control, and display of characterization property monitoring results, etc., and the user interface can control the above process parameters.

[0053] Preferably, the device for preparing the amorphous nano-alloy particles for brazing further comprises a gas loop pipeline, the gas inlet end of the gas loop pipeline is connected to the deposition chamber, and the gas outlet end of the gas loop pipeline is connected to the gas inlet end of the spark generation system. The tail gas of the mixed carrier gas flows through the gas loop pipeline after passing through the deposition chamber, reenters the spark generation system, participates in the preparation again, and realizes recycling.

[0054] A method for preparing amorphous nano-alloy particles, comprising the following steps: Step S1, preheat the gas heating cavity; introduce the liquid nitrogen rapid cooling pipe P2 into the circulating liquid nitrogen; load the metal target material into the spark growth cavity; Step S2, after the gas heating cavity is sufficiently preheated, open the first gas source G1, the first flow meter F1, and the spark generation system; Step S3, after the spark generation system is stable for 5-10 minutes, open the second gas source G2 and the second flow meter F2, and stabilize for 5-10 minutes; after the heated gas flowing out of the gas heating cavity reaches a specific temperature, the heated gas flows through the heated gas delivery pipe P3, mixes with the original carrier gas of the first gas source G1 passing through the spark generation system, and then enters the carrier gas delivery pipe P1; Step S4, the heated gas in the carrier gas delivery pipe P1 mixes with the room temperature original carrier gas of the first gas source G1 flowing out of the spark generation system, so that the temperature of the mixed carrier gas in the carrier gas delivery pipe P1 rises; at this time, the atoms and atomic clusters in the mixed carrier gas fuse and grow into nano-particles after being heated; Step S5, the nano-particles in step S4 enter the liquid nitrogen rapid cooling pipe P2 under the action of the mixed carrier gas, are rapidly cooled in the liquid nitrogen rapid cooling pipe P2 to form amorphous nano-particles, and continue to be deposited on the substrate in the deposition chamber along with the mixed carrier gas; Step S6, the obtained amorphous nano-particles are characterized in real time in situ by using a spectrometer, the size, morphology, and state of the product are monitored, and the process parameters set in the previous steps are adjusted according to the monitoring results, so as to obtain the target amorphous nano-alloy particle product; Step S7, the tail gas of the cooled mixed carrier gas enters the spark generation system through the gas loop pipeline, participates in the preparation again, and realizes recycling.

[0055] Preferably, in step S1, the gas heating cavity is preheated to 300-700°C, including but not limited to 300°C, 400°C, 500°C, 600°C, and 700°C.

[0056] Preferably, in step S2, the flow rate of the first flow meter F1 is set to 1.5-8 L / min, including but not limited to 1.5 L / min, 2 L / min, 3 L / min, 4 L / min, 5 L / min, 6 L / min, 7 L / min, and 8 L / min.

[0057] Preferably, the voltage of the spark generation system in step S2 is set to 0.5kV~2.5kV, including but not limited to 0.5kV, 1kV, 1.5kV, 2kV, 2.5kV, and the current is set to 1mA~10mA, including but not limited to 1mA, 2mA, 3mA, 4mA, 5mA, 6mA, 7mA, 8mA, 9mA, 10mA.

[0058] Preferably, the flow rate of the second flow meter F2 in step S3 is set to 1.5L / min~8L / min, including but not limited to 1.5L / min, 2L / min, 3L / min, 4L / min, 5L / min, 6L / min, 7L / min, 8L / min.

[0059] Preferably, the heating gas in step S3 reaches a temperature of 300~700℃, including but not limited to 300℃, 400℃, 500℃, 600℃, 700℃.

[0060] Example 1 The method for preparing amorphous Pb-Bi binary alloy nanoparticles with an average particle size of 5nm comprises the following steps: a. Preheat the gas heating cavity; circulate liquid nitrogen in the cavities of the inner and outer layers of the liquid nitrogen quenching tube P2; load the Pb-Bi alloy target material into the spark growth cavity; b. After the gas heating cavity is fully preheated, open the first gas source G1 and the first flow meter F1, adjust the flow rate of the first flow meter F1 to 5L / min, and turn on the spark generation system, adjust the voltage to 0.9kV and the current to 2mA; c. After the spark generation system is stable for 5 minutes, open the second gas source G2 and the second flow meter F2, adjust the flow rate of the second flow meter F2 to 5L / min, and after being stable for 10 minutes, set the heating gas flowing out of the gas heating cavity to about 450℃, the heating gas flows through the heating gas delivery pipe P3, then mixes with the original carrier gas of the first gas source G1 passing through the spark generation module, and enters the carrier gas delivery pipe P1; d. The heating gas entering the carrier gas delivery pipe P1 mixes with the room temperature carrier gas of the first gas source G1 flowing out of the spark generation system, so that the temperature of the mixed carrier gas in the carrier gas delivery pipe P1 rises, at this time the atoms and atomic clusters in the mixed carrier gas are fused and grown into nanoparticles after being heated; e. The nanoparticles enter the liquid nitrogen quenching tube P2 under the action of the mixed carrier gas, are rapidly cooled in the liquid nitrogen quenching tube P2 to form amorphous nanoparticles, and continue to be deposited on the substrate in the deposition chamber with the mixed carrier gas; f. The obtained amorphous nanoparticles can be characterized in real time in situ by a spectrometer, and the size and state of the product can be monitored. The process parameters set in advance can be adjusted according to the monitoring results, so as to obtain the target amorphous nano-alloy particle product.

[0061] g. The tail gas of the mixed carrier gas after being cooled enters the electric spark generation system through the gas loop pipeline to participate in the preparation again and realize recycling.

[0062] The alloy nanoparticles prepared above are subjected to electron diffraction and energy spectrum test in a transmission electron microscope. The test results show that the nanoparticles are amorphous Pb-Bi binary alloy nanoparticles.

[0063] Example 2 The difference between this example and Example 1 is that the average particle size of the amorphous Pb-Bi binary alloy nanoparticles prepared is 20 nm; the flow of the first flow meter F1 is adjusted to 4 L / min, and the voltage of the electric spark generation system is adjusted to 0.8 kV and the current is adjusted to 3 mA in step b; the flow of the second flow meter F2 is adjusted to 4 L / min in step c. The rest is the same as Example 1.

[0064] Example 3 The difference between this example and Example 1 is that the average particle size of the amorphous Pb-Bi binary alloy nanoparticles prepared is 85 nm; the flow of the first flow meter F1 is adjusted to 2.5 L / min, and the voltage of the electric spark generation system is adjusted to 0.8 kV and the current is adjusted to 4 mA in step b; the flow of the second flow meter F2 is adjusted to 3 L / min in step c. The rest is the same as Example 1.

[0065] Example 4 The difference between this example and Example 1 is that spherical amorphous Ag-Cu alloy nanoparticles are prepared; the Ag-Cu alloy target is loaded into the electric spark growth cavity in step a; the flow of the first flow meter F1 is adjusted to 4 L / min, and the voltage of the electric spark generation system is adjusted to 1.2 kV and the current is adjusted to 5 mA in step b; the flow of the second flow meter F2 is adjusted to 5 L / min, and the heated gas flowing out of the gas heating cavity is set to about 700℃ in step c.

[0066] Example 5 The difference between this example and Example 1 is that the average particle size of the amorphous Pb-Bi binary alloy nanoparticles prepared is 40 nm; the flow of the first flow meter F1 is adjusted to 4 L / min, and the voltage of the electric spark generation system is adjusted to 0.8 kV and the current is adjusted to 4.3 mA in step b; the flow of the second flow meter F2 is adjusted to 3.5 L / min in step c. The rest is the same as Example 1.

[0067] Test Example The nanometer alloy particles prepared in Examples 1-4 were subjected to electron diffraction and energy spectrum test in a transmission electron microscope, and the test results are shown in Figures 3~9 .

[0068] As shown in Figures 3~5 , by adjusting the process parameters, amorphous Pb-Bi nanometer alloy particles with controllable size were prepared in Examples 1-3, and amorphous Pb-Bi nanometer alloy particles with different particle sizes (average particle sizes of a-5 nm, b-20 nm, and c-85 nm) were obtained.

[0069] As shown in Figure 6 , spherical amorphous Ag-Cu alloy nanometer particles were prepared in Example 4.

[0070] As shown in Figure 7 , spherical nanometer alloy particles with smooth surface were prepared in Example 5, and the electron diffraction results showed that they were amorphous.

[0071] Figure 8 The element distribution map of the Pb-Bi binary alloy nanometer particles prepared in Example 5, the morphology and element distribution characterization of the amorphous Pb-Bi alloy nanometer particles in TEM, (a) high-angle annular dark field image shows that the contrast of the nanometer alloy is uniform; (b)-(d) EDS-mapping test results show that the Bi and Pb elements in the nanometer particles are uniformly distributed; indicating that the two elements are uniformly mixed.

[0072] As shown in Figure 9 , the EDS spectrum test of the amorphous Pb-Bi alloy nanometer particles prepared in Example 5, the element type and distribution were detected by X-ray energy dispersive spectroscopy (EDS). The EDS spectrum shows that, in addition to Cu (instrument self-contained), the prepared sample only contains Pb and Bi two elements; the nanometer alloy particles mainly contain Pb and Bi two elements, do not contain impurities, and the distribution of the two metal elements is uniform.

[0073] Those skilled in the art will readily understand that the above description is only the preferred embodiment of the present application, and is not intended to limit the present application, and any modification, equivalent replacement and improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. An apparatus for producing amorphous nanoscale alloy particles for thermal spray coating, characterized by comprising: The device comprises a first gas source module, an electric spark generating system, a second gas source module, a gas heating module, a cooling module and a deposition module; the first gas source module is connected to the gas inlet end of the electric spark generating system, the second gas source module is connected to the gas inlet end of the gas heating module, the gas outlet end of the gas heating module is connected to the gas outlet end of the electric spark generating system, and the gas outlet end of the electric spark generating system is connected to the deposition module through the cooling module.

2. The apparatus for preparing the amorphous nanoscale alloy particles for brazing coating according to claim 1, wherein, The first gas source module outputs gas into the electric spark generating system, the second gas source module outputs gas into the gas heating module, the original carrier gas flowing out of the electric spark generating system is mixed with the heated gas flowing out of the gas heating module to obtain mixed carrier gas, the atoms and atomic clusters in the mixed carrier gas are fused and grown into nanoparticles after being heated, the mixed carrier gas is cooled in the cooling module to form amorphous nanoparticles, and the mixed carrier gas continues to be deposited in the deposition module.

3. The apparatus for preparing the amorphous nanoscale alloy particles for brazing coating according to claim 1, wherein, The device comprises at least one of the following technical features: (1) The electric spark growing cavity of the electric spark generating system is loaded with a target material, and the target material is at least one of Pb, Bi, Ag, Cu, Al, Fe, Au, Mg, Zn single metal or alloy; (2) The gas heating module comprises a gas heating cavity and a heater, and the heater is an induction heater, an electric resistance heater or a methane burner; (3) The cooling module comprises a cooling pipe and a cooling medium, and the mixed carrier gas flowing through the cooling pipe is rapidly cooled by the cooling medium.

4. The apparatus for preparing the amorphous nanometer alloy particles for brazing coating according to claim 3, wherein, The device comprises at least one of the following technical features: (1) The cooling module is a liquid nitrogen rapid cooling pipe P2, which comprises the cooling pipe and liquid nitrogen, and the cooling pipe is a double-layer pipe, and the cavity between the inner layer pipe and the outer layer pipe is connected to the liquid nitrogen; (2) The gas outlet end of the electric spark generating system is connected to the gas inlet end of a carrier gas conveying pipe P1, the gas outlet end of the gas heating cavity is connected to the gas inlet end of a heated gas conveying pipe P3, and the gas outlet end of the heated gas conveying pipe P3 is connected to the gas inlet end of the carrier gas conveying pipe P1; (3) The electric spark generating system is connected to the deposition module through the carrier gas conveying pipe P1 and the liquid nitrogen rapid cooling pipe P2; (4) The length of the carrier gas conveying pipe P1 is 120-200 cm.

5. The apparatus of claim 1, wherein the apparatus is characterized by: The device for preparing amorphous nano-alloy particles for brazing and coating further comprises a central control module; the first gas source module, the electric spark generating system, the second gas source module and the gas heating module are in communication connection with the central control module; The first gas source module comprises a first gas source G1 and a first flow meter F1 connected thereto, and the second gas source module comprises a second gas source G2 and a second flow meter F2 connected thereto; the electric spark generating system is provided with a power control assembly.

6. The apparatus for preparing the amorphous nanoscale alloy particles for brazing coating according to claim 5, wherein the apparatus is characterized by, The device for preparing amorphous nano-alloy particles for brazing and coating further comprises a characterization module, which is in communication connection with the central control module; the characterization module monitors the product, and the central control module adjusts the process parameters according to the monitoring results.

7. The apparatus of claim 1, wherein the apparatus is characterized by: The preparation device of the brazing coating amorphous nano alloy particles also comprises a gas loop pipeline, an inlet end of the gas loop pipeline is connected to the deposition chamber, and an outlet end of the gas loop pipeline is connected to an inlet end of the electric spark generation system.

8. A method for producing amorphous nanometer alloy particles, using the apparatus for producing amorphous nanometer alloy particles for soldering according to any one of claims 1 to 7, characterized by, The method comprises the following steps: Step S1, preheat the gas heating cavity; introduce the circulating liquid nitrogen into the liquid nitrogen quenching pipe P2; load the target material into the electric spark growth cavity; Step S2, after the gas heating cavity is sufficiently preheated, open the first gas source G1, the first flow meter F1, and the electric spark generation system; Step S3, open the second gas source G2 and the second flow meter F2, and after the heating gas reaches a specific temperature, the heating gas flows through the heating gas delivery pipe P3, mixes with the original carrier gas flowing through the first gas source G1 of the electric spark generation system, and then enters the carrier gas delivery pipe P1; Step S4, the heating gas in the carrier gas delivery pipe P1 mixes with the original carrier gas flowing out of the electric spark generation system, so that the temperature of the mixed carrier gas in the carrier gas delivery pipe P1 rises, and at this time, the atoms and atomic clusters in the mixed carrier gas are fused and grown into nano particles after being heated; Step S5, the nano particles in step S4 enter the liquid nitrogen quenching pipe P2 under the action of the mixed carrier gas, are rapidly cooled in the liquid nitrogen quenching pipe P2 to form amorphous nano particles, and continue to be deposited on the substrate in the deposition chamber along with the mixed carrier gas.

9. The method of claim 8, wherein the non-crystalline nanoalloy particles are prepared by a process comprising: The preparation method also comprises the following steps: step S6, using a spectrometer to perform real-time in-situ characterization on the obtained amorphous nano particles, monitoring the size, morphology, and other properties of the product, and feeding back and adjusting the process parameters set in the previous steps according to the monitoring results to obtain the target amorphous nano alloy particle product; Step S7, the tail gas of the cooled mixed carrier gas enters the electric spark generation system through the gas loop pipeline and participates in the preparation again to realize recycling.

10. The method of claim 9, wherein the amorphous alloy nanoparticles are prepared by a process comprising: The method comprises at least one of the following technical features: (1) in step S1, the gas heating cavity is preheated to 300-700°C; (2) in step S2, the flow rate of the first flow meter F1 is set to 1.5-8 L / min; (3) in step S2, the voltage of the electric spark generation system is set to 0.5-2.5 kV; (4) in step S3, the flow rate of the second flow meter F2 is set to 1.5-8 L / min; (5) in step S3, the heating gas reaches a temperature of 300-700°C.

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