CN110967358A - High-flux copper alloy preparation method - Google Patents
High-flux copper alloy preparation method Download PDFInfo
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- CN110967358A CN110967358A CN201811440750.5A CN201811440750A CN110967358A CN 110967358 A CN110967358 A CN 110967358A CN 201811440750 A CN201811440750 A CN 201811440750A CN 110967358 A CN110967358 A CN 110967358A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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Abstract
The invention discloses a method for preparing a copper alloy with high flux. The pulse current is utilized to generate Joule heat between two nano synapses to realize instant melting and solidification so as to simulate the melting and solidification processes of the traditional casting process, and chemical elements of the two nano synapses are diffused and mixed in the process, so that the components of a middle fusion welding area contain the elements of the nano synapses on two sides; the chemical composition of the welding area can be continuously changed and adjusted by breaking and welding with other synapses; meanwhile, the composition determination and the phase characterization can be carried out in situ, so that each fusion welding area can be immediately subjected to characterization test, and the time for alloy analysis and test is greatly shortened. Compared with the traditional smelting test, the method disclosed by the invention has the advantages that the consumption of raw materials, time and energy is reduced by several orders of magnitude.
Description
Technical Field
The invention relates to a development method of a copper alloy, in particular to a method for preparing the copper alloy in a high-flux manner.
Background
High performance copper alloys, particularly those having high strength and high electrical conductivity, have always occupied the high-end product market for copper alloys. The high-strength and high-conductivity copper alloy is widely applied to the fields of electronics, electric power, mechanical manufacturing and the like, and is particularly suitable for manufacturing electrodes with high working current density, IC lead frames, contact net leads, crystallizer inner sleeves and the like. Although the yield of Chinese copper alloy is stable in the world for 17 years, high-end copper alloy such as high-strength high-conductivity copper alloy still needs to be imported in a large quantity, and the development of high-strength high-conductivity copper alloy with own intellectual property rights is urgently needed.
The first challenge in developing high-strength and high-conductivity copper alloys is that the strength and the conductivity of the copper alloys are in conflict. Generally, the increase in strength tends to come at the expense of a decrease in conductivity. How to develop the research on the components of the copper alloy and design a copper alloy material with proper components to greatly improve the alloy strength and slightly reduce the conductivity is the key point of the current research on the high-strength and high-conductivity copper alloy.
At present, the development of new components of the high-strength and high-conductivity copper alloy is still based on the traditional alloy design and trial and error principle. Some alloy components are drawn up through a binary or ternary phase diagram of thermodynamic calculation alloy, and then smelting processing and test verification are carried out. The method is also effective for simple binary or ternary copper alloy systems. However, for a complex system containing more components, such as a complex system containing seven elements of Cr, Be, Ni, Si, Zn, Ag and Cu, the original alloy design and research methods and techniques are ineffective and can only Be verified by experience and experiment. If the sample amount of the test component is small, the influence action and rule of various alloy elements are difficult to reflect. And the test cost and time are obviously improved by enlarging the sample size. Therefore, there is an urgent need to develop a method for high throughput preparation and characterization of copper alloys.
Assumed to be developedThe copper alloy contains 5 alloying elements, the composition of which can be represented as CuABCDE. In order to research the influence rule of D and E elements with different contents on the composition and structure of the CuABCDE copper alloy phase, a series of CuABCD with different contents need to be preparedxEyAnd (3) alloying. Fixing D according to the requirement of the traditional trial-and-error methodx1Element content, then carrying out ingredient melting to prepare a series of CuABCD with different E element contentsx1EyThen, grinding a sample to be used as a transmission electron microscope and other microstructure tests to analyze the phase composition and the structure of the alloy; then changing the content of the D element (x2), and preparing and analyzing a series of CuABCD with different E element contents by proportioning, smelting and preparingx2EyAlloying; this is repeated. The process is extremely complicated, time-consuming and labor-consuming. According to the calculation of 5g of minimum specification ingot casting of an electric arc melting furnace, in order to research the influence rule of D and E elements with different contents on the composition and the structure of a CuABCDE copper alloy phase, the traditional trial and error method needs to smelt at least 25 times (the calculation is carried out according to 5 numerical points of the D element and the E element respectively), and the required material is at least 125 g. The single smelting consumes at least 2kWh of electricity and at least 1 hour; i.e. a total consumption of about 50kWh, which takes 25 hours. In addition, the alloy is required to be subjected to necessary sample treatment such as grinding and polishing and then sent to a transmission electron microscope or energy spectrum test, and the time required is extremely long.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a copper alloy with high flux. The method can carry out measurement and phase characterization on the components of each fusion welding area in situ, so that each fusion welding area can immediately obtain a characterization test, and compared with the traditional fusion test, the method has the advantages that the raw material consumption, the time consumption and the energy consumption are reduced by several orders of magnitude.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a method for preparing a copper alloy in a high-flux manner comprises the following preparation steps:
the prepared copper alloy contains 6 metal elements, wherein A, B, C, D, E respectively represent different metal elements;
(1) taking an alloy wire with the diameter of 0.4mm and the length of 2-5 mm and the component of CuABC, and shearing the alloy wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head of the nano synapse is 20-500 nm; the alloy wire is arranged at the movable end of a transmission electron microscope sample rod, and the fracture faces outwards; wherein the number of finger-like nano synapses is at least 1; the nano synapses can be in other shapes, and the finger-shaped nano synapses are convenient for the contact fusion welding of the two nano synapses and the pulling-off of a fusion welding area.
(2) Taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of D, grinding the metal wire with the circular section into a semicircular section line, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(3) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of E, grinding the metal wire with the circular section into a semicircular section line, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(4) aligning and splicing the two metal wires with the semicircular sections obtained in the steps (2) and (3) into a wire with a quasi-circular section, and placing the wire into the fixed end of the sample rod of the transmission electron microscope with the fracture facing outwards;
(5) enabling the alloy wire obtained in the step (1) to be opposite to the fracture surface of the metal wire obtained in the step (4) at a distance of 0.5-1.5 mm; loading the sample rod into a transmission electron microscope, vacuumizing, and starting the transmission electron microscope; face-to-face refers to the case of pointing to the finger similar to tip-to-tip, for example, a finger on the left arm would point to the finger with a finger on the right arm. So that the experiment can be carried out in a contact way;
(6) moving the CuABC alloy wire in an electron microscope to enable the nano synapse of the CuABC alloy wire to be in contact with the nano synapse of the D metal wire, and applying a certain amount of pulse current between the CuABC alloy wire and the D metal wire, wherein the magnitude of the pulse current can be 1 nA-1 mA, so that the two nano synapses are welded under the action of the pulse current;
(7) testing of fusion welding area component CuABCD by energy spectrometerx1Analyzing the phase composition and structure of the fusion welding area by using a transmission electron microscope so as to obtain the phase composition and structure information under the composition;
(8) moving the CuABC alloy wire, breaking the fusion welding area, then using the nano synapse with the fusion welding area to contact with the nano synapse of the E metal wire, repeating the fusion welding operation in the step (6), and then repeating the component, phase composition and structure testing operation in the step (7) to obtain the component CuABCD of the fusion welding areax1Ey1、CuABCDx1Ey1Phase composition and structural information under composition;
(9) repeating the step (8) for a plurality of times to prepare a series of CuABCD with different E contentsx1EyAlloying and obtaining CuABCDx1EyPhase composition and structural information under composition;
(10) repeating the step (6) for 2 times, and breaking a fusion welding area which comprises CuABCDx2Then, the nano synapse with the welding area is contacted with the nano synapse of the E metal wire, the welding operation in the step (6) is repeated, and then the component, the phase composition and the structure testing operation in the step (7) are repeated, so that the component CuABCD of the welding area is obtainedx2Ey、CuABCDx2EyPhase composition and structural information under composition;
(11) repeating the step (10) for a plurality of times to obtain a series of CuABCD with different D and E contentsxEyPhase composition and structural information under composition.
In some preferred embodiments, the nanosynaptic may have other shapes.
In some preferred modes, the metal wire with the component of the D element can be replaced by an alloy wire containing at least 2 metal elements, and the influence rule of different elements on the phase composition and the structure of the alloy can be researched through the alloy structure obtained in the preparation process.
In other preferable modes, the metal wire having the composition of the E element may be replaced with an alloy wire containing at least 2 metal elements.
In other preferred forms, the alloy wire having the composition CuABC may be replaced with a single-element metal wire such as Cu, Zn, or other metal elements.
In other preferred embodiments, the alloy wire having the composition CuABC may be replaced with a copper alloy wire containing at least 2 metal elements.
The invention also provides a method for preparing the copper alloy with high flux, which comprises the following preparation steps:
(1) taking an alloy wire with the diameter of 0.4mm and the length of 2-5 mm, wherein the alloy wire comprises Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si, and shearing the alloy wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head of the nano synapse is 20-500 nm; the alloy wire is arranged at the movable end of a transmission electron microscope sample rod, and the fracture faces outwards; wherein the number of finger-like nano synapses is at least 1;
(2) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of Fe, grinding the metal wire with the circular cross section into a metal wire with a semicircular cross section, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(3) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of Cr, grinding the metal wire with the circular section into a semicircular section line, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(4) aligning and splicing the two metal wires with the semicircular sections obtained in the steps (2) and (3) into a wire with a quasi-circular section, and placing the wire into the fixed end of the sample rod of the transmission electron microscope with the fracture facing outwards;
(5) enabling the alloy wire obtained in the step (1) to be opposite to the fracture surface of the metal wire obtained in the step (4) at a distance of 0.5-1.5 mm; loading the sample rod into a transmission electron microscope, vacuumizing, and starting the transmission electron microscope; the face-to-face condition refers to the condition of pointing to the finger like tip-to-tip, for example, the finger of the left arm and the finger of the right arm should point to the finger, so that the experiment can be performed by contact;
(6) moving a Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire in a transmission electron microscope to enable a nano synapse of the Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire to be in contact with a nano synapse of an Fe metal wire, and applying a pulse current with a certain magnitude, such as 1 nA-1 mA pulse current, between the Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire and the Fe metal wire to enable the two nano synapses to be welded under the action of the pulse current;
(7) testing the components of the fusion welding area by using an energy spectrometer, and analyzing the phase composition and the structure of the fusion welding area by using a transmission electron microscope, thereby obtaining the phase composition and the structure information under the components;
(8) moving a Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire to break the fusion bonded area, and then repeating the fusion bonding operation in step (6) using the nano-synapses with the fusion bonded area to make contact with the nano-synapses of the Cr metal wire, and then repeating the composition, phase composition and structure testing operations in step (7) to obtain phase composition and structure information for the fusion bonded area having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.15wt.% Cr, Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.15wt.% Cr;
(9) repeating the step (8) for a plurality of times, preparing a series of alloys with different Cr contents and obtaining phase composition and structure information under the composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-ywt.% Cr;
(10) repeating the step (6) for 2 times, breaking the fusion welding zone, wherein the composition of the fusion welding zone is Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe, then contacting the nano synapse with the fusion welding zone with the nano synapse of the Cr metal wire, repeating the fusion welding operation in the step (6), and then repeating the composition, phase composition and structure testing operation in the step (7) to obtain the composition and structure information of the fusion welding zone with the composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe-ywt.% Cr and the composition and structure information of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe-ywt.% Cr;
(11) repeating the step (10) for a plurality of times to obtain a series of CuCoNiSiFe with different Fe and Cr contentsxCryPhase composition and structural information under composition.
A method for preparing a high-entropy alloy in a high flux mode comprises the following steps:
(1) taking an alloy wire with the diameter of 0.4mm and the length of 2-5 mm and the components of ABC, and shearing the alloy wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head of the nano synapse is 20-500 nm; the alloy wire is arranged at the movable end of a transmission electron microscope sample rod, and the fracture faces outwards; wherein the number of finger-like nano synapses is at least 1;
(2) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of D, grinding the metal wire with the circular cross section into a metal wire with a semicircular cross section, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(3) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of E, grinding the metal wire with the circular cross section into a metal wire with a semicircular cross section, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(4) aligning and splicing the two metal wires with the semicircular sections obtained in the steps (2) and (3) into a wire with a quasi-circular section, and placing the wire into the fixed end of the sample rod of the transmission electron microscope with the fracture facing outwards;
(5) enabling the alloy wire obtained in the step (1) to be opposite to the fracture surface of the metal wire obtained in the step (4) at a distance of 0.5-1.5 mm; loading the sample rod into a transmission electron microscope, vacuumizing, and starting the electron microscope; the face-to-face condition refers to the condition of pointing to the finger like tip-to-tip, for example, the finger of the left arm and the finger of the right arm should point to the finger, so that the experiment can be performed by contact;
(6) moving the ABC alloy wire in an electron microscope to enable the nano synapse of the ABC alloy wire to be in contact with the nano synapse of the D metal wire, and applying a certain pulse current, such as 1 nA-1 mA pulse current, between the ABC alloy wire and the D metal wire to enable the two nano synapses to be welded under the action of the pulse current;
(7) testing the components of the fusion welding area into ABCD by an energy spectrometerx1Analyzing the phase composition and structure of the fusion welding area by using a transmission electron microscope so as to obtain the phase composition and structure information under the composition;
(8) moving the ABC alloy wire, breaking the fusion welding area, then using the nano synapse with the fusion welding area to contact with the nano synapse of the E metal wire, repeating the fusion welding operation in the step (6), and then repeating the component, phase composition and structure test operation in the step (7) to obtain the component ABCD of the fusion welding areax1Ey1、ABCDx1Ey1Phase composition and structural information under composition;
(9) repeating the step (8) for a plurality of times to prepare a series of ABCD with different E contentsx1EyAlloying and obtaining ABCDx1EyPhase composition and structural information under composition;
(10) repeating the step (6) for 2 times, and breaking the fusion welding area, wherein the component of the fusion welding area is ABCDx2Then, the nano synapse with the welding area is contacted with the nano synapse of the E metal wire, the welding operation in the step (6) is repeated, and then the component, the phase composition and the structure test operation in the step (7) are repeated, so that the component ABCD of the welding area is obtainedx2Ey、ABCDx2EyPhase composition and structural information under composition;
(11) repeating the step (10) for several times to obtain a series of ABCD with different D and E contentsxEyPhase composition and structural information under composition.
The invention has the beneficial effects that:
(1) the invention utilizes the joule heat generated by the pulse current between two nanometer synapses to realize instant melting and solidification so as to simulate the melting and solidification process of the traditional melting and casting process; in the process, chemical elements of the two nano synapses are diffused and mixed, so that the components of the middle fusion welding area comprise the elements in the nano synapses on the two sides; by pulling off and welding with other nanometer synapses, the chemical composition of the welding area can be changed and adjusted continuously, and the alloy with different chemical compositions can be prepared.
(2) The invention utilizes the phase component testing capability of the transmission electron microscope, and can carry out in-situ determination and phase characterization on the components of each fusion welding area, so that each fusion welding area can immediately obtain a characterization test, the time of alloy analysis and test is greatly shortened, and the influence rule of different elements on the composition and the structure of the alloy phase can be timely researched. The method can effectively avoid the problems that the traditional method carries out synthesis and detection, and the detection of the hysteresis is not beneficial to researching the influence of a certain element on the synthesis of the alloy.
(3) The size of the nano synapse adopted by the invention is extremely small, and the single synapse is only 4.9 multiplied by 10 according to the calculation of phi 40nm multiplied by 50nm-16g (density calculated as Fe) is very little compared with 5g of traditional smelting, thus greatly saving raw materials.
(4) The electric energy consumed during single pulse fusion welding is calculated according to 3V and 1 muA lasting for 1s, the energy consumption is only 15 muJ, and compared with the traditional 2kWh smelting, the electric energy is greatly saved.
(5) In the aspect of time consumption, the time required for fusion welding of a pair of nano synapses only needs 1s, and the time for fusion welding once is about 5 minutes by considering the displacement and alignment time; the in-situ composition and phase analysis takes about 15 minutes, namely only 20 minutes are needed to complete the preparation and analysis of the alloy with one composition, and compared with the traditional smelting, the time is saved.
Drawings
FIG. 1 is a schematic diagram of the preparation of a copper alloy according to the present invention.
FIG. 2(a) is a flow chart of steps taken to obtain fusion-bonded regions of different compositions in the present invention when preparing a copper alloy; (b) transmission electron microscopy images for the fusion welding procedure of example 1; (c) the result of the energy spectrum test of the fusion welding area in (b).
FIG. 3(a) is a transmission electron microscope image of second phase particles in a weld zone having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.87 wt.% Cr when a copper alloy was prepared according to example 1; (b) the results of the energy spectrum test for the second phase particles in the weld zone having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.87 wt.% Cr.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to the accompanying drawings, and it should be noted that the detailed description is only for describing the present invention, and should not be construed as limiting the present invention.
Example 1
The invention provides a method for preparing a copper alloy with high flux, which comprises the following preparation steps:
(1) taking an alloy wire with the diameter of 0.4mm and the length of 2-5 mm, wherein the alloy wire comprises Cu, 0.3wt.% Co, 0.2wt.% Ni and 0.08wt.% Si, and cutting the alloy wire by using pliers to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; the alloy wire is arranged at the movable end of a transmission electron microscope sample rod, and the fracture faces outwards; wherein the number of finger-like nano synapses is at least 1;
(2) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of Fe, grinding the metal wire with the circular cross section into a metal wire with a semicircular cross section by using sand paper, and then cutting off the metal wire by using pliers to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(3) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of Cr, grinding the metal wire with the circular cross section into a metal wire with a semicircular cross section by using sand paper, and then cutting off the metal wire by using pliers to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm; wherein the number of finger-like nano synapses is at least 1;
(4) aligning and splicing the two metal wires with the semicircular sections obtained in the steps (2) and (3) into a wire with a quasi-circular section, and placing the wire into the fixed end of the sample rod of the transmission electron microscope with the fracture facing outwards;
(5) enabling the alloy wire obtained in the step (1) to be opposite to the fracture surface of the metal wire obtained in the step (4) at a distance of 0.5-1.5 mm; loading the sample rod into a transmission electron microscope, vacuumizing, and starting the transmission electron microscope; the face-to-face condition refers to the condition of pointing to the finger like tip-to-tip, for example, the finger of the left arm and the finger of the right arm should point to the finger, so that the experiment can be performed by contact;
(6) moving a Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire in an electron microscope to enable a nano synapse of the Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire to be in contact with a nano synapse of an Fe metal wire, and applying a pulse current with a certain size, such as 1 nA-1 mA, between the Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire and the Fe metal wire, so that the two nano synapses are welded under the action of the pulse current;
(7) testing the components of a fusion welding area by using an energy spectrometer carried by a transmission electron microscope to be Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe, and analyzing the phase composition and the structure of the fusion welding area by using a transmission electron microscope selected area electron diffraction technology, a transmission electron microscope morphology observation technology and a high-resolution observation technology, thereby obtaining the phase composition and structure information under the components;
(8) moving a Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire to break the fusion bonded area, and then repeating the fusion bonding operation in step (6) using the nano-synapses with the fusion bonded area to make contact with the nano-synapses of the Cr metal wire, and then repeating the composition, phase composition and structure testing operations in step (7) to obtain phase composition and structure information for the fusion bonded area having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.15wt.% Cr, Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.15wt.% Cr;
(9) repeating the step (8) for a plurality of times to prepare a series of CuCoNiSiFeCr alloys with different Cr contents and obtain phase composition and structure information under the composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-ywt.% Cr;
(10) repeating the step (6) for 2 times, breaking the fusion welding zone, wherein the composition of the fusion welding zone is Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe, then contacting the nano synapse with the fusion welding zone with the nano synapse of the Cr metal wire, repeating the fusion welding operation in the step (6), and then repeating the composition, phase composition and structure testing operation in the step (7) to obtain the composition and structure information of the fusion welding zone with the composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe-ywt.% Cr and the composition and structure information of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe-ywt.% Cr;
(11) repeating the step (10) for a plurality of times to obtain a series of CuCoNiSiFe with different Fe and Cr contentsxCryPhase composition and structural information under composition.
A series of CuCoNiSiFe with Fe and Cr contentsxCryThe phase composition and structural information under composition are shown in table 1.
TABLE 1 CuCoNiSiFexCryPhase composition and structural information under composition
Example 1 the preparation principle for preparing a copper alloy is shown in fig. 1, wherein CuABC is specifically an alloy wire having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si, D is specifically a metal wire having a composition of Fe, and E is specifically a metal wire having a composition of Cr; the CuABC alloy wire is arranged at the movable end of the transmission electron microscope sample rod, the D and E metal wires are arranged at the fixed end, a fracture contains a nano synapse, the CuABC nano synapse can be contacted with the D or E nano synapse by moving the movable end, and then a pulse current is applied by an external power supply, so that the two contacted nano synapses can be melted and welded. The invention utilizes the joule heat generated by the pulse current between two nanometer synapses to realize instant melting and solidification so as to simulate the melting and solidification process of the traditional melting and casting process. In the process, two nano-synapse chemical elements are subjected to diffusion mixing, so that the middle fusion welding area component contains the elements of the nano-synapses on two sides.
Example 1 when a copper alloy is prepared, the flow steps taken to obtain fusion-bonded regions of different compositions are shown in fig. 2(a), in which CuABC is specifically an alloy wire having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si, D is specifically a metal wire having a composition of Fe, and E is specifically a metal wire having a composition of Cr; i represents that the nano synapse of CuABC is contacted with the nano synapse of D, II represents that the nano synapse of CuABC is contacted with the nano synapse of D and then is subjected to fusion welding, III represents that the fusion welding area is broken by moving the CuABC, and IV represents that the nano synapse of CuABC with the fusion welding area is contacted with the nano synapse of E and then is subjected to fusion welding; by repeating the operation of this process, fusion-welded regions of different compositions can be obtained. The chemical composition of the fusion welding area can be changed and adjusted continuously by breaking and welding with new nanometer synapses.
Example 1 in the case of preparing a copper alloy, a transmission electron microscope image of a fusion welding process is shown in fig. 2 (b); the upper part of the arrow is two nano synapses which are not contacted before being electrified; the lower part of the arrow is welded together after the contact is electrified; the lower left corner of FIG. 2(b) shows the electron diffraction pattern of the welded-together portion, illustrating that the crystal structure is a face-centered cubic structure.
The energy spectrum test result of the fusion welding area in fig. 2(b) is shown in fig. 2(c), and the composition of the fusion welding area can be obtained from fig. 2(c) as follows: cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.43 wt.% Cr.
Example 1 a transmission electron microscope image of second phase particles in a weld zone having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.87 wt.% Cr is shown in fig. 3(a) when a copper alloy is prepared; the results of the spectroscopy test for the second phase particles in the weld zone with a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.87 wt.% Cr are shown in FIG. 3 (b).
Claims (4)
1. A method for preparing a copper alloy in a high flux is characterized by comprising the following preparation steps: the prepared copper alloy contains 6 metal elements, wherein A, B, C, D, E respectively represent different metal elements;
(1) taking an alloy wire with the diameter of 0.4mm and the length of 2-5 mm and the component of CuABC, and shearing the alloy wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head of the nano synapse is 20-500 nm; the alloy wire is arranged at the movable end of a transmission electron microscope sample rod, and the fracture faces outwards;
(2) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of D, grinding the metal wire with the circular section into a semicircular section line, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm;
(3) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of E, grinding the metal wire with the circular section into a semicircular section line, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm;
(4) aligning and splicing the two metal wires with the semicircular sections obtained in the steps (2) and (3) into a wire with a quasi-circular section, and placing the wire into the fixed end of the sample rod of the transmission electron microscope with the fracture facing outwards;
(5) enabling the alloy wire obtained in the step (1) to be opposite to the fracture surface of the metal wire obtained in the step (4) at a distance of 0.5-1.5 mm; loading the sample rod into a transmission electron microscope, vacuumizing, and starting the transmission electron microscope;
(6) moving the CuABC alloy wire in an electron microscope to enable the nano synapse of the CuABC alloy wire to be in contact with the nano synapse of the D metal wire, and applying a certain pulse current between the CuABC alloy wire and the D metal wire to enable the two nano synapses to be welded under the action of the pulse current;
(7) testing of fusion welding area component CuABCD by energy spectrometer x1Analyzing the phase composition and structure of the fusion welding area by using a transmission electron microscope so as to obtain the phase composition and structure information under the composition;
(8) moving the CuABC alloy wire, breaking the fusion welding area, then using the nano synapse with the fusion welding area to contact with the nano synapse of the E metal wire, repeating the fusion welding operation in the step (6), and then repeating the component, phase composition and structure testing operation in the step (7) to obtain the component CuABCD of the fusion welding area x1Ey1、CuABCD x1Ey1Phase composition and structural information under composition;
(9) repeating the step (8) for a plurality of times to prepare a series of CuABCD with different E contents x1EyAlloying and obtaining CuABCD x1EyPhase composition and structural information under composition;
(10) repeating the step (6) for 2 times, and breaking a fusion welding area which comprises CuABCD x2Then, the nano synapse with the welding area is contacted with the nano synapse of the E metal wire, the welding operation in the step (6) is repeated, and then the component, the phase composition and the structure testing operation in the step (7) are repeated, so that the component CuABCD of the welding area is obtained x2Ey、CuABCD x2EyThe ingredients are as followsPhase composition and structural information of;
(11) repeating the step (10) for a plurality of times to obtain a series of CuABCD with different D and E contents x EyPhase composition and structural information under composition.
2. The method for high throughput production of copper alloy according to claim 1, wherein the metal wire having composition D is replaced with an alloy wire.
3. The method for high throughput production of copper alloy according to claim 1, wherein the metal wire having composition E is replaced with an alloy wire.
4. A method for preparing a copper alloy in a high flux is characterized by comprising the following preparation steps:
(1) taking an alloy wire with the diameter of 0.4mm and the length of 2-5 mm, wherein the alloy wire comprises Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si, and shearing the alloy wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head of the nano synapse is 20-500 nm; the alloy wire is arranged at the movable end of a transmission electron microscope sample rod, and the fracture faces outwards;
(2) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of Fe, grinding the metal wire with the circular cross section into a metal wire with a semicircular cross section, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm;
(3) taking a metal wire with the diameter of 0.4mm and the length of 2-5 mm and the component of Cr, grinding the metal wire with the circular section into a semicircular section line, and then cutting off the metal wire to enable a fracture to generate a finger-shaped nano synapse with the length of 50-2000 nm, wherein the diameter of the head part of the nano synapse is 20-500 nm;
(4) aligning and splicing the two metal wires with the semicircular sections obtained in the steps (2) and (3) into a wire with a quasi-circular section, and placing the wire into the fixed end of the sample rod of the transmission electron microscope with the fracture facing outwards;
(5) enabling the alloy wire obtained in the step (1) to be opposite to the fracture surface of the metal wire obtained in the step (4) at a distance of 0.5-1.5 mm; loading the sample rod into a transmission electron microscope, vacuumizing, and starting the transmission electron microscope;
(6) moving a Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire in a transmission electron microscope to enable a nano synapse of the Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire to be in contact with a nano synapse of an Fe metal wire, and applying a pulse current with a certain magnitude between the Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire and the Fe metal wire to enable the two nano synapses to be welded under the action of the pulse current;
(7) testing the components of the fusion welding area by using an energy spectrometer, and analyzing the phase composition and the structure of the fusion welding area by using a transmission electron microscope, thereby obtaining the phase composition and the structure information under the components;
(8) moving a Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si alloy wire to break the fusion bonded area, and then repeating the fusion bonding operation in step (6) using the nano-synapses with the fusion bonded area to make contact with the nano-synapses of the Cr metal wire, and then repeating the composition, phase composition and structure testing operations in step (7) to obtain phase composition and structure information for the fusion bonded area having a composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.15wt.% Cr, Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-0.15wt.% Cr;
(9) repeating the step (8) several times to prepare a series of alloys with different Cr contents and obtain Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.26wt.% Fe-yPhase composition and structural information at wt.% Cr composition;
(10) repeating the step (6) for 2 times, breaking the fusion welding area, wherein the composition of the fusion welding area is Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe, then contacting the nano synapse with the fusion welding area with the nano synapse of the Cr metal wire, repeating the fusion welding operation in the step (6), and then repeating the composition, phase composition and structure testing operation in the step (7) to obtain the fusion welding area with the composition of Cu-0.3wt.% Co-0.2wt.% Ni-0.08wt.% Si-0.54wt.% Fe-yCr and Cu 0.3wt.% Co 0.2wt.% Ni 0.08wt.% Si 0.54wt.% Fe-yPhase composition and structural information at wt.% Cr composition;
(11) repeating the step (10) for a plurality of times to obtain a series of CuCoNiSiFe with different Fe and Cr contents x Cr y Phase composition ofAnd structural information.
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