CN115430948A - In-situ synthesized MAX phase enhanced tin-based lead-free solder and preparation method thereof - Google Patents
In-situ synthesized MAX phase enhanced tin-based lead-free solder and preparation method thereof Download PDFInfo
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- CN115430948A CN115430948A CN202211226386.9A CN202211226386A CN115430948A CN 115430948 A CN115430948 A CN 115430948A CN 202211226386 A CN202211226386 A CN 202211226386A CN 115430948 A CN115430948 A CN 115430948A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
The invention discloses an in-situ synthesized MAX phase enhanced tin-based lead-free solder, which comprises Sn or Sn alloy/MAX composite lead-free solder prepared by taking MAX phase generated in situ in a Sn or Sn alloy matrix as an enhancement phase, wherein Sn or Sn alloy accounts for 90-99.5% of the mass of the whole material; the MAX phase accounts for 0.5% -10% of the mass of the whole material. The invention also discloses an electronic product using the in-situ synthesized MAX phase enhanced tin-based lead-free solder and a preparation method of the in-situ synthesized MAX phase enhanced tin-based lead-free solder. The MAX phase particles synthesized in situ and the matrix have good bonding property, and the interdiffusion between the reinforcing phase and the matrix phase only exists between the MAX phase Sn atomic layer and the matrix phase Sn, so that the reinforcing phase cannot be dissolved or coarsened, and the stability of the lead-free solder is ensured.
Description
Technical Field
The invention relates to an in-situ synthesized MAX phase enhanced tin-based lead-free solder and a preparation method thereof, belonging to the technical field of welding materials.
Background
The traditional tin-lead solder has the characteristics of excellent weldability, ductility, conductivity, corrosion resistance and the like, so that the tin-lead solder is widely applied to the electronic industry. However, lead has high toxicity and accumulation, and seriously harms the ecological environment and human health. Since the last 90 s, various countries in the world have been developing leadless sports, and lead-containing materials are gradually eliminated, so that people are forced to find alternative materials for tin-lead solder. At present, lead-free systems such as pure Sn-Ag, sn-Cu, sn-Zn, sn-Ag-Cu and the like are more concerned, but an ideal substitute of tin-lead solder is not found. The main problems of the current lead-free solder are focused on the aspects of high melting point, poor mechanical property and the like.
The lead-free solder modification method mainly comprises two aspects of alloying and second phase addition. The alloying only can partially improve the performance of the solder, and the second phase particles not only can refine the microstructure, but also can improve the mechanical property, the wettability and the like through dispersion strengthening. The second phase particles can be mainly divided into active particles (such as metal particles of Co, ni, cu, al, etc.) and inactive particles (such as Al 2 O 3 、ZrO 2 And (3) ceramic particles; carbon materials such as graphene and carbon nanotubes). The active particles can react with the matrix, so that the bonding property between the active particles and the matrix is better, but the reinforcing phase can be interdiffused, dissolved or coarsened during the service process, so that the performance of the solder is unstable. The inactive particles have high strength and good stability, have good effect of inhibiting the growth of crystal grains and dislocation movement, but have poor combination with a matrix.
Aiming at the problems in the prior art, the invention provides MAX phase enhanced tin-based lead-free solder and a preparation method thereof. The in-situ synthesized MAX phase particles and the matrix have good bonding property, and the interdiffusion between the reinforcing phase and the matrix phase only exists between the MAX phase Sn atomic layer and the matrix phase Sn, so that the reinforcing phase cannot be dissolved or coarsened, and the stability of the lead-free solder is ensured.
The invention has wide application range, can be applied to tin-based lead-free solders with different components and MAX phases with different elements at M position, can ensure that the reinforcing phase and the matrix have good bonding property and the reinforcing phase can be kept stable in the using process.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides the in-situ synthesized MAX phase enhanced tin-based lead-free solder, wherein the in-situ synthesized MAX phase can improve the hardness, yield strength and shear strength of the lead-free solder, mainly due to the refinement of the in-situ synthesized MAX phase relative to the lead-free solder and the enhancement of the MAX phase; meanwhile, the MAX phase synthesized in situ and the matrix phase have better bonding property, and can form atomic scale bonding, so that the mechanical property is improved more remarkably.
The invention also aims to provide an electronic product using the MAX phase enhanced tin-based lead-free solder synthesized in situ, the lead-free solder of the invention is comparable to the lead solder of tin-lead alloy, and the prepared electronic product has stable performance.
The invention also aims to provide a preparation method of the MAX phase enhanced tin-based lead-free solder synthesized in situ, which is characterized in that the MAX phase synthesized in situ through the reaction of C @ M core-shell powder and a matrix phase has better bonding property with the matrix phase compared with the enhanced phase added directly, and can form atomic scale bonding, thereby improving the mechanical property more obviously.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises Sn or Sn alloy/MAX composite lead-free solder prepared by taking MAX phase generated in situ in a Sn or Sn alloy matrix as an enhancement phase, wherein the Sn or Sn alloy accounts for 90-99.5% of the mass of the whole material; the MAX phase accounts for 0.5-10% of the mass of the whole material.
The Sn alloy includes an Sn-Cu alloy, an Sn-Ag alloy, an Sn-In alloy, an Sn-Zn alloy, an Sn-Bi alloy, or an Sn-Ag-Cu alloy.
The A-site element in the MAX phase is Sn, the X-site element is MAX phase of C, including Ti 2 SnC、Nb 2 SnC、Zr 2 SnC、Lu 2 SnC、Hf 2 SnC or Ti 3 SnC 2 。
In the lead-free solder, the MAX phase is uniformly distributed in the matrix phase, and the particle size of the MAX phase is 1-200 nm.
The circuit board of the MAX phase enhanced tin-based lead-free solder synthesized in situ is used.
The electronic product using the circuit board is characterized by comprising a mobile phone, a computer, a tablet personal computer, a keyboard, a mouse, a television, a refrigerator, an air conditioner, an electric kettle and an automobile.
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps:
s1: placing the simple substance M powder into a plasma ball mill, cleaning the surface through the plasma ball mill, and refining particles;
s2: placing the simple substance M powder subjected to plasma ball milling treatment in a powder atomic layer deposition cavity, and depositing a layer of carbon on the surface of the simple substance M powder to form C @ M core-shell powder;
s3: respectively weighing the C @ M core-shell powder and a ball milling medium, and placing the powder and the ball milling medium in an ultrasonic dispersion instrument to uniformly disperse the C @ M core-shell powder;
s4: weighing matrix phase powder, adding the matrix phase powder into the mixture obtained in the step S3 to obtain mixed powder, and then placing the mixed powder into a ball mill for ball milling;
s5: placing the ball-milled mixture of S4 in a drying box for drying to obtain uniformly mixed raw material powder;
s6: putting the uniformly mixed raw material powder into a mould, and carrying out cold press molding to obtain a blank;
s7: and (3) heating the pressed and formed blank at high temperature in a protective atmosphere or vacuum, and synthesizing the MAX phase enhanced tin-based lead-free solder in situ.
The ball milling medium is deionized water or absolute ethyl alcohol; the material of the grinding balls in the ball mill is agate; the mass ratio of the grinding balls to the ball-milling medium to the mixed powder in the S4 is (1-5): (0.5-2.5): 1, the ball milling speed is 100-400 r/min, and the time is 2-12 hours.
In S1, the rotating speed of a plasma ball mill is 1000-2000 r/min, and the time is 3-12 h; in S2, the atomic ratio of the simple substance M powder to the deposited layer is 2: (0.8-1.2); s4, matrix phase powder is Sn or Sn alloy; in S5, the drying temperature is 40-80 ℃, and the drying time is 2-12 hours; and S6, cold press molding pressure is 100-500 MPa, and the pressure maintaining time is 1-10 minutes.
In S7, the protective atmosphere is vacuum, argon or nitrogen, the high-temperature heating temperature is 1100-1500 ℃, and the high-temperature heating heat preservation time is 1-4 hours.
The invention has the following beneficial effects:
the MAX synthesized in situ has little influence on relative melting point, so the application range of the lead-free solder is not influenced.
The MAX phase synthesized in situ reduces the contact angle between the solder and the copper substrate, and is beneficial to forming good connection between the solder and the substrate, mainly because the MAX phase particles with micro-nano size have high activity and can be adsorbed at the interface in the melting process of the solder, so that the surface tension is reduced.
The MAX phase synthesized in situ can obviously refine grains, and the stable physicochemical property of the MAX phase enables the MAX phase to still exist stably in the melting process of the solder, so that the MAX phase can be used as a heterogeneous phase nucleation site to improve the nucleation rate. Meanwhile, the A site element is MAX phase of Sn, and the mismatch degree between the A atomic layer and beta-Sn is low, so that the nucleation rate is improved more obviously compared with Ti powder, graphite powder and the like, and the outstanding grain refining effect is achieved.
The MAX phase synthesized in situ can improve the hardness, yield strength and shear strength, which are mainly due to the refinement of the MAX phase synthesized in situ relative to the lead-free solder structure and the enhancement effect of the MAX phase. Moreover, compared with a directly added reinforcing phase, the MAX phase synthesized in situ through the phase reaction of the C @ M core-shell powder and the matrix phase has better bonding property with the matrix phase, and can form atomic scale bonding, so that the mechanical property is improved more remarkably.
According to the C @ M core-shell powder, in the powder atomic layer deposition process, the cavity can vibrate and roll, and therefore the outside of particles can be wrapped with a deposition layer. The X atom is a small atom in an octahedron, and the atomic radius of C is smaller than that of M; meanwhile, the M particles and the C layer both contain a plurality of atoms, and the M particles and the C layer are chemically adsorbed to obtain the C @ M core-shell powder.
The invention provides an in-situ synthesized MAX phase enhanced tin-based lead-free solder and a preparation method thereof. The in-situ synthesized MAX phase particles and the matrix have good bonding property, and the interdiffusion between the reinforcing phase and the matrix phase only exists between the MAX phase Sn atomic layer and the matrix phase Sn, so that the reinforcing phase cannot be dissolved or coarsened, and the stability of the lead-free solder is ensured.
The invention has wide application range, can be applied to tin-based lead-free solders with different components and MAX phases with different elements at M position, can ensure that the reinforcing phase and the matrix have good bonding property and the reinforcing phase can be kept stable in the using process.
Drawings
FIG. 1 is a schematic diagram of the MAX phase structure of the present invention;
FIG. 2 is a schematic illustration of the in situ synthesis of MAX phase enhanced tin-based lead-free solder of the present invention;
FIG. 3 is a schematic illustration of the interdiffusion process between the matrix phase and MAX phase of the present invention;
FIG. 4 is a micro-topography of C @ Ti prepared in example 1;
fig. 5 is a microstructure view of the lead-free solder prepared in example 6.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and specific examples. The following examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Example 1
An in-situ synthesized MAX phase enhanced tin-based lead-free solder:
taking MAX phase generated in situ in Sn or Sn alloy matrix as a reinforcing phase to prepare Sn (or Sn alloy)/MAX composite lead-free solder, wherein Sn (or Sn alloy) accounts for 90-99.5% of the mass of the whole material; the MAX phase accounts for 0.5-10% of the mass of the whole material.
MAX phase is a general name of ternary nano lamellar carbide or nitride, wherein M is transition metal element, A is main group IIIA and IVA element, X is carbon or nitrogen, and n =1, 2, 3 \8230. MAX phase by M 6 X octahedral layers are stacked alternately with a atomic layer a, and X atoms are located in octahedra formed by close stacking of M atoms, as shown in fig. 1. The MAX phase family contains a number of members with the A-site element being Sn and the X-site element being C. Therefore, C can be coated on the surface of the M-site element nano-particles, then C @ M core-shell powder is uniformly dispersed in the Sn (or Sn alloy) matrix, and then MAX phase enhanced tin-based lead-free solder is synthesized in situ by high-temperature sintering, as shown in FIG. 2. The reinforcing phase is synthesized in situ by taking Sn in the matrix as a Sn atom source, so that the matrix phase and the reinforcing phase have good bonding property. At the same time, M in MAX phases 6 Strong binding force in the X octahedral layer, M 6 The bonding force between the X octahedral layer and the a atomic layer is weak, and the mobility of the a atoms is strongest among the three atoms, so the interdiffusion between the matrix phase and the MAX phase is mainly the interdiffusion between Sn atoms in the matrix and Sn atoms in the MAX phase Sn atomic layer, as shown in fig. 3. The reinforcing phase can not be dissolved or coarsened, namely, the reinforcing phase can be kept stable in the service process of the lead-free solder.
The MAX phase refers to MAX phase with an A bit element of Sn and an X bit element of C, and comprises Ti 2 SnC、Nb 2 SnC、Zr 2 SnC、Lu 2 SnC、Hf 2 SnC、Ti 3 SnC 2 。
The matrix phase In the composite lead-free solder comprises Sn, sn-Cu alloy, sn-Ag alloy, sn-In alloy, sn-Zn alloy, sn-Bi alloy and Sn-Ag-Cu alloy.
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps: and (3) placing the simple substance Ti powder into a plasma ball mill for ball milling, wherein the ball milling rotation speed is 1500r/min, and the time is 12h. The Ti powder subjected to plasma ball milling is placed in a powder atomic layer deposition cavity, a layer of C is deposited on the surface of the Ti powder to form C @ Ti core-shell powder, and the atomic ratio of the Ti powder to the C deposition layer is 2. Respectively weighing 0.05g of C @ Ti core-shell powder and 10g of absolute ethyl alcohol, adding the C @ Ti core-shell powder into the absolute ethyl alcohol, and placing the mixture in an ultrasonic dispersion instrument to uniformly disperse the C @ Ti core-shell powder in the absolute ethyl alcohol. Respectively weighing 9.95g of Sn powder and 10g of grinding balls, adding the Sn powder and the 10g of grinding balls together with the mixture of C @ Ti core-shell powder and absolute ethyl alcohol into a ball milling tank, and placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 100r/min, and the time is 12 hours.
The ball-milled mixture was dried in a drying oven at 60 ℃ for 12 hours. And (3) placing the dried mixture into a mold, and maintaining the pressure for 5 minutes at 200MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1350 ℃ under the argon protection atmosphere, preserving heat for 1h, and then cooling to room temperature along with the furnace.
Namely, the in-situ synthesized MAX phase enhanced tin-based lead-free solder of the embodiment comprises 99.5% of Sn and 0.5% of Ti by mass of the whole material 2 SnC。
FIG. 4 is a microstructure of the prepared C @ Ti, from which it can be seen that the surface of the titanium particles is coated with a layer of carbon, and the upper right-hand inset is a schematic three-dimensional structure of C @ Ti.
Example 2
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps: and (3) placing the simple substance Ti powder into a plasma ball mill for ball milling, wherein the ball milling rotating speed is 1000r/min, and the time is 12h. The Ti powder subjected to plasma ball milling is placed in a powder atomic layer deposition cavity, a layer of C is deposited on the surface of the Ti powder to form C @ Ti core-shell powder, and the atomic ratio of the Ti powder to the C deposition layer is 2. Respectively weighing 0.5g of C @ Ti core-shell powder and 20g of absolute ethyl alcohol, adding the C @ Ti core-shell powder into the absolute ethyl alcohol, and placing the mixture in an ultrasonic dispersion instrument to uniformly disperse the C @ Ti core-shell powder in the absolute ethyl alcohol. Respectively weighing 9.5g of Sn powder and 10g of grinding balls, adding the Sn powder and the 10g of grinding balls together with the mixture of C @ Ti core-shell powder and absolute ethyl alcohol into a ball milling tank, and placing the mixture into a ball mill for ball milling, wherein the ball milling speed is 100r/min, and the time is 12 hours.
The ball-milled mixture was dried in a drying oven at 80 ℃ for 6 hours. And (4) placing the dried mixture into a mold, and maintaining the pressure for 5 minutes at 200MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1330 ℃ under the argon protection atmosphere, preserving heat for 2 hours, and then cooling to room temperature along with the furnace.
Namely, the in-situ synthesized MAX phase enhanced tin-based lead-free solder of the embodiment comprises 95% of Sn and 5% of Ti by mass of the whole material 2 SnC。
Example 3
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps: and (3) placing the simple substance Ti powder into a plasma ball mill for ball milling, wherein the ball milling speed is 2000r/min, and the time is 3h. The Ti powder subjected to plasma ball milling is placed in a powder atomic layer deposition cavity, a layer of C is deposited on the surface of the Ti powder to form C @ Ti core-shell powder, and the atomic ratio of the Ti powder to the C deposition layer is 2. Weighing 1g of C @ Ti core-shell powder and 25g of deionized water respectively, adding the C @ Ti core-shell powder into the deionized water, and placing the deionized water in an ultrasonic dispersion instrument to uniformly disperse the C @ Ti core-shell powder in the deionized water. Respectively weighing 9g of Sn powder and 50g of grinding balls, adding the Sn powder and the 50g of grinding balls together with the mixture of C @ Ti core-shell powder and deionized water into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling, wherein the ball milling speed is 400r/min, and the time is 2 hours.
The ball-milled mixture was dried in a drying oven at 40 ℃ for 12 hours. And (4) placing the dried mixture into a mold, and maintaining the pressure for 10 minutes at 100MPa to obtain a raw material blank. And (3) placing the blank in a high-temperature furnace, heating to 1300 ℃ under the argon protective atmosphere, preserving heat for 4 hours, and then cooling to room temperature along with the furnace.
Namely, the in-situ synthesized MAX phase enhanced tin-based lead-free solder of the embodiment comprises Sn accounting for 90% of the mass of the whole material and Ti accounting for 10% of the mass of the whole material 2 SnC。
Example 4
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps: and (3) placing the elementary substance Cr powder into a plasma ball mill for ball milling, wherein the ball milling speed is 1800r/min, and the time is 4h. Placing Cr powder subjected to plasma ball milling in a powder atomic layer deposition cavity, and depositing a layer of C on the surface of the Cr powder to form C @ Cr core-shell powder, wherein the atomic ratio of the Cr powder to the C deposition layer is 2. Respectively weighing 0.5g of C @ Zr nuclear shell powder and 20g of deionized water, adding the C @ Cr nuclear shell powder into the deionized water, and placing the mixture into an ultrasonic dispersion instrument to uniformly disperse the C @ Cr nuclear shell powder in the deionized water. Respectively weighing 9.5g of Sn powder and 10g of grinding balls, adding the Sn powder and 10g of grinding balls together with the mixture of C @ Cr core-shell powder and deionized water into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling, wherein the ball milling speed is 250r/min, and the time is 6 hours.
The ball-milled mixture was dried in a drying oven at 80 ℃ for 6 hours. And (3) placing the dried mixture into a mold, and maintaining the pressure for 1 minute at 500MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1100 ℃ under the argon protective atmosphere, preserving heat for 4 hours, and then cooling to room temperature along with the furnace.
Example 5
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps: and (3) placing the simple substance Nb powder into a plasma ball mill for ball milling, wherein the ball milling speed is 1500r/min, and the time is 8h. Placing Nb powder subjected to plasma ball milling in a powder atomic layer deposition cavity, and depositing a layer of C on the surface of the Nb powder to form C @ Nb core-shell powder, wherein the atomic ratio of the Nb powder to the C deposition layer is 2. Respectively weighing 0.5g of C @ Nb nuclear shell powder and 5g of deionized water, adding the C @ Nb nuclear shell powder into the deionized water, and placing the mixture into an ultrasonic dispersion instrument to uniformly disperse the C @ Nb nuclear shell powder in the deionized water. Respectively weighing 9.5g of Sn powder and 10g of grinding balls, adding the Sn powder and the 10g of grinding balls together with the mixture of the C @ Nb core-shell powder and the deionized water into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling, wherein the ball milling speed is 300r/min, and the time is 12 hours.
The ball-milled mixture was dried in a drying oven at 80 ℃ for 2 hours. And (3) placing the dried mixture into a mold, and maintaining the pressure for 1 minute at 500MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1500 ℃ under the nitrogen protection atmosphere, preserving heat for 1h, and then cooling to room temperature along with the furnace.
Example 6
A preparation method of an in-situ synthesized MAX phase enhanced tin-based lead-free solder comprises the following steps: and (3) placing the simple substance Ti powder into a plasma ball mill for ball milling, wherein the ball milling speed is 1000r/min, and the time is 12h. Placing Ti powder subjected to plasma ball milling in a powder atomic layer deposition cavity, and depositing a layer of C on the surface of the Ti powder to form C @ Ti core-shell powder, wherein the atomic ratio of the Ti powder to the C deposition layer is 2. Respectively weighing 0.5g of C @ Ti core-shell powder and 20g of absolute ethyl alcohol, adding the C @ Ti core-shell powder into the absolute ethyl alcohol, and placing the mixture in an ultrasonic dispersion instrument to uniformly disperse the C @ Ti core-shell powder in the absolute ethyl alcohol. Respectively weighing 9.5g of Sn-Cu powder and 10g of grinding balls, adding the Sn-Cu powder and the grinding balls together with the mixture of C @ Ti core-shell powder and absolute ethyl alcohol into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling, wherein the ball milling speed is 100r/min, and the time is 12 hours.
The ball-milled mixture was dried in a drying oven at 80 ℃ for 4 hours. And (3) placing the dried mixture into a mold, and maintaining the pressure for 3 minutes at 300MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1300 ℃ under the argon protection atmosphere, preserving heat for 2 hours, and then cooling to room temperature along with the furnace. The microstructure of the prepared lead-free solder is shown in FIG. 5, from which Ti can be seen 2 The SnC is uniformly distributed in the matrix phase, and the measurement and statistics of the Sn grain size of the matrix phase can show that: the average grain size of the alloy is 2.11 mu m, and the average grain size is opposite to that of the reinforcing phase Ti 2 The SnC particle size is measured and counted to obtain the following result: the particle size is 1-200 nm.
Example 7
A circuit board using the in situ synthesized MAX phase enhanced tin-based lead free solder of any one of examples 1-6.
The product using the circuit board of this embodiment will use tin-based solder, such as electronic products (mobile phone, computer, tablet computer, keyboard, mouse, etc.), household appliances (television, refrigerator, air conditioner, electric kettle, etc.), industrial products (automobile, instrument, etc.), and will not be described herein any more.
Comparative example 1
And (3) putting the pure Sn powder into a mould, and keeping the pressure for 10 minutes at 100MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1300 ℃ under the argon protection atmosphere, preserving heat for 4 hours, and then cooling to room temperature along with the furnace.
Comparative example 2
And placing the Sn-Cu powder into a die, and maintaining the pressure for 3 minutes at 300MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1300 ℃ under the argon protection atmosphere, preserving heat for 2 hours, and then cooling to room temperature along with the furnace.
Comparative example 3
0.4g of Ti powder, 0.1g of graphite powder and 20g of absolute ethyl alcohol are respectively weighed and placed in an ultrasonic dispersion instrument to uniformly disperse the Ti powder and the graphite powder in the absolute ethyl alcohol. Respectively weighing 9.5g of Sn powder and 10g of grinding balls, adding the mixture of Ti powder, graphite powder and absolute ethyl alcohol into a ball milling tank, and placing the ball milling tank into a ball mill for ball milling, wherein the ball milling rotating speed is 100r/min, and the time is 12 hours. The ball-milled mixture was dried in a drying oven at 80 ℃ for 6 hours. And (3) placing the dried mixture into a mold, and maintaining the pressure for 5 minutes at 200MPa to obtain a raw material blank. And (3) placing the blank body in a high-temperature furnace, heating to 1330 ℃ under the argon protection atmosphere, preserving heat for 2 hours, and then cooling to room temperature along with the furnace.
Comparative example 4
Conventional Sn63Pb37 tin-lead eutectic solder.
The following table 1 shows the results of the performance test of the solders of examples 1 to 6 and comparative examples 1 to 4.
Table 1 table for examining the properties of the solders of examples 1 to 6 and comparative examples 1 to 4
It should be appreciated that in the foregoing description of exemplary embodiments of the invention, various features of the invention are sometimes grouped together in a single embodiment, figure, or description thereof for the purpose of streamlining the disclosure and aiding in the understanding of one or more of the various inventive aspects. However, the disclosed method should not be construed to reflect the intent: that the invention as claimed requires more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the claims following the detailed description are hereby expressly incorporated into this detailed description, with each claim standing on its own as a separate embodiment of this invention.
While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this description, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as described herein. Furthermore, it should be noted that the language used in the specification has been principally selected for readability and instructional purposes, and may not have been selected to delineate or circumscribe the inventive subject matter. Accordingly, many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the appended claims. The present invention has been disclosed with respect to the scope of the invention, which is to be considered as illustrative and not restrictive, and the scope of the invention is defined by the appended claims.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention, and such modifications and adaptations are intended to be within the scope of the invention.
Claims (10)
1. The in-situ synthesized MAX phase enhanced tin-based lead-free solder is characterized by comprising the steps of preparing Sn or Sn alloy/MAX composite lead-free solder by taking MAX phase generated in situ in a Sn or Sn alloy matrix as an enhancement phase, wherein Sn or Sn alloy accounts for 90-99.5% of the mass of the whole material; the MAX phase accounts for 0.5-10% of the mass of the whole material.
2. An In-situ synthesized MAX phase enhanced tin-based lead-free solder as claimed In claim 1, wherein the Sn alloy comprises Sn-Cu alloy, sn-Ag alloy, sn-In alloy, sn-Zn alloy, sn-Bi alloy or Sn-Ag-Cu alloy.
3. The in-situ synthesized MAX phase enhanced tin-based lead-free solder of claim 1, wherein the A site element in MAX phase is Sn and the X site element is MAX phase of C, comprising Ti 2 SnC、Nb 2 SnC、Zr 2 SnC、Lu 2 SnC、Hf 2 SnC or Ti 3 SnC 2 。
4. The in-situ synthesized MAX phase enhanced tin-based lead-free solder according to claim 1, wherein in the lead-free solder, MAX phases are uniformly distributed in a matrix phase, and the particle size of the MAX phases is 1 to 200nm.
5. A circuit board using the in-situ synthesized MAX phase enhanced tin-based lead-free solder according to any one of claims 1 to 4.
6. An electronic product using the circuit board of claim 5, comprising a mobile phone, a computer, a tablet computer, a keyboard, a mouse, a television, a refrigerator, an air conditioner, an electric kettle, and an automobile.
7. The method for preparing the MAX phase enhanced tin-based lead-free solder as claimed in any one of claims 1 to 4, wherein the method comprises the following steps:
s1: placing the simple substance M powder into a plasma ball mill, cleaning the surface through the plasma ball mill, and refining particles;
s2: placing the simple substance M powder subjected to plasma ball milling treatment in a powder atomic layer deposition cavity, and depositing a layer of carbon on the surface of the simple substance M powder to form C @ M core-shell powder;
s3: respectively weighing the C @ M nuclear shell powder and a ball milling medium, and putting the C @ M nuclear shell powder and the ball milling medium in an ultrasonic dispersion instrument to uniformly disperse the C @ M nuclear shell powder;
s4: weighing matrix phase powder, adding the matrix phase powder into the mixture obtained in the step S3 to obtain mixed powder, and then placing the mixed powder into a ball mill for ball milling;
s5: placing the ball-milled mixture of S4 in a drying box for drying to obtain uniformly mixed raw material powder;
s6: putting the uniformly mixed raw material powder into a mould, and carrying out cold press molding to obtain a blank;
s7: and (3) heating the pressed and formed blank at high temperature in a protective atmosphere or vacuum, and synthesizing the MAX phase enhanced tin-based lead-free solder in situ.
8. The preparation method according to claim 7, wherein the ball milling medium is deionized water or absolute ethyl alcohol; the grinding balls in the ball mill are made of agate; the mass ratio of the grinding balls to the ball-milling medium to the mixed powder in the S4 is (1 to 5): (0.5 to 2.5): 1, the ball milling speed is 100 to 400r/min, and the time is 2 to 12 hours.
9. The preparation method of claim 7, wherein in S1, the rotation speed of the plasma ball mill is 1000 to 2000r/min, and the time is 3 to 12h; in S2, the atomic ratio of the simple substance M powder to the deposited layer is 2: (0.8 to 1.2); in S4, matrix phase powder is Sn or Sn alloy; s5, drying at the temperature of 40-80 ℃ for 2-12 hours; and S6, cold press molding is carried out at the pressure of 100 to 500MPa, and the pressure maintaining time is 1 to 10 minutes.
10. The preparation method according to claim 7, wherein in S7, the protective atmosphere is vacuum, argon or nitrogen, the temperature of high-temperature heating is 1100 to 1500 ℃, and the holding time of high-temperature heating is 1 to 4 hours.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169996A (en) * | 2011-03-31 | 2011-08-31 | 湖南工业大学 | Micro-sphere compound anode material with core-shell structure and preparation method thereof |
| CN104393266A (en) * | 2014-12-08 | 2015-03-04 | 北京化工大学 | Silicon-carbon composite electrode material of core-shell structure and preparation method thereof |
| US20200230746A1 (en) * | 2019-01-22 | 2020-07-23 | Exxonmobil Research And Engineering Company | Composite components fabricated by in-situ reaction synthesis during additive manufacturing |
| CN112157257A (en) * | 2020-09-17 | 2021-01-01 | 中国科学院电工研究所 | In-situ toughening method for tough and integral Cu/Sn/Ag welding material |
| CN113714680A (en) * | 2021-09-29 | 2021-11-30 | 南京工程学院 | High-potential-concentration MAX phase and preparation method thereof, and lead-free solder capable of effectively inhibiting tin whisker growth and preparation method thereof |
-
2022
- 2022-10-09 CN CN202211226386.9A patent/CN115430948B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102169996A (en) * | 2011-03-31 | 2011-08-31 | 湖南工业大学 | Micro-sphere compound anode material with core-shell structure and preparation method thereof |
| CN104393266A (en) * | 2014-12-08 | 2015-03-04 | 北京化工大学 | Silicon-carbon composite electrode material of core-shell structure and preparation method thereof |
| US20200230746A1 (en) * | 2019-01-22 | 2020-07-23 | Exxonmobil Research And Engineering Company | Composite components fabricated by in-situ reaction synthesis during additive manufacturing |
| CN112157257A (en) * | 2020-09-17 | 2021-01-01 | 中国科学院电工研究所 | In-situ toughening method for tough and integral Cu/Sn/Ag welding material |
| CN113714680A (en) * | 2021-09-29 | 2021-11-30 | 南京工程学院 | High-potential-concentration MAX phase and preparation method thereof, and lead-free solder capable of effectively inhibiting tin whisker growth and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王泽宇等: "纳米材料增强复合钎料的研究进展" * |
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