阅读说明：本技术 一种微纳米颗粒增强的高铟铜基活性钎料及其制备方法 (Micro-nano particle reinforced high-indium copper-based active solder and preparation method thereof ) 是由 杜全斌 张黎燕 龙伟民 王晓侃 王星星 秦磊 陈超 张卫伟 崔冰 徐东 于 2019-09-25 设计创作，主要内容包括：一种微纳米颗粒增强的高铟铜基活性钎料,包括以下重量份数原料：85～95份基础组元、2.5～9份活性组元、0.1～1份微量组元和2～5份微纳米增强颗粒；其制备方法为：称重备料、高频感应熔炼中间合金、真空熔炼钎料、常规加工成丝状或带状活性钎料。本发明配方设计合理,性价比高,所述基础组元按重量份包括5～15份铟、3～8份锡、1～3份锰、1～5份磷、0.5～3份锑、0.5～5份硅、0.5～5份锗和余量铜,通过铟、磷复合代锡的方法,不仅降低了铜基活性钎料的熔化温度,还提高了钎料的塑性、改善钎料加工性能；通过添加微纳米颗粒,提高了钎料和钎焊接头的强度。(A micro-nano particle reinforced high-indium copper-based active solder comprises the following raw materials in parts by weight: 85-95 parts of basic components, 2.5-9 parts of active components, 0.1-1 part of trace components and 2-5 parts of micro-nano reinforcing particles; the preparation method comprises the following steps: weighing, preparing materials, high-frequency induction smelting of intermediate alloy, vacuum smelting of brazing filler metal, and conventional processing into filamentous or banded active brazing filler metal. The copper-based active brazing filler metal has the advantages that the formula design is reasonable, the cost performance is high, the base components comprise 5-15 parts of indium, 3-8 parts of tin, 1-3 parts of manganese, 1-5 parts of phosphorus, 0.5-3 parts of antimony, 0.5-5 parts of silicon, 0.5-5 parts of germanium and the balance of copper in parts by weight, and the melting temperature of the copper-based active brazing filler metal is reduced, the plasticity of the brazing filler metal is improved, and the processing performance of the brazing filler metal is improved by a method of substituting tin by compounding indium and phosphorus; by adding the micro-nano particles, the strength of the brazing filler metal and the brazing joint is improved.)

1. The micro-nano particle reinforced high-indium copper-based active solder is characterized by comprising the following raw materials in parts by weight: 85-95 parts of basic components, 2.5-10 parts of active components, 0.1-1 part of trace components and 2-6 parts of micro-nano reinforced particles;

wherein the base component comprises the following components in parts by weight: 5-15 parts of indium, 3-8 parts of tin, 1-3 parts of manganese, 1-5 parts of phosphorus, 0.5-3 parts of antimony, 0.5-5 parts of silicon, 0.5-5 parts of germanium and the balance of copper; the active component comprises the following components in parts by weight: 66-85 parts of titanium and 15-44 parts of chromium; the trace component is rare earth cerium; the components exist in the forms of copper indium intermediate alloy, copper tin intermediate alloy, copper manganese intermediate alloy, copper phosphorus intermediate alloy, copper antimony intermediate alloy, copper silicon intermediate alloy, copper germanium intermediate alloy, copper titanium intermediate alloy, copper chromium intermediate alloy and copper cerium intermediate alloy respectively;

the micro-nano enhanced particles are cobalt-coated micro-nano diamond particles with the particle size of 10-500 nm.

2. The preparation method of the micro-nano particle reinforced high-indium copper-based active solder according to claim 1, which is characterized by comprising the following steps:

step one, putting raw materials of copper, copper-indium intermediate alloy and copper-tin intermediate alloy into a high-frequency induction smelting furnace, heating to 300-400 ℃, adding charcoal to cover, continuously heating to 1100-1150 ℃, completely melting pure copper, copper-indium intermediate alloy and copper-tin intermediate alloy, sequentially adding the copper-silicon intermediate alloy, copper-germanium intermediate alloy and copper-manganese intermediate alloy in the step one, adding charcoal again to cover, fully stirring the solution for 2-5 min by using high-pressure inert gas after the raw materials are completely melted, cooling the solution to 900-1000 ℃, preserving heat, sequentially adding the copper-antimony intermediate alloy and the copper-phosphorus intermediate alloy in the step one, fully stirring after the raw materials are completely melted, standing and cooling to 700-900 ℃, slagging off and casting into alloy ingots;

step two, placing the alloy ingot in the step one into a magnesium oxide crucible, placing the magnesium oxide crucible containing the alloy ingot into an induction coil arranged in a vacuum glove box, placing the copper-titanium intermediate alloy, the copper-chromium intermediate alloy and the copper-cerium intermediate alloy in the step one into a material containing disc A, placing the cobalt-coated micro-nano diamond particles in the step one into a material containing disc B, and placing the two material containing discs in the vacuum glove box;

step three, vacuumizing the vacuum glove box until the vacuum degree is 1 multiplied by 10^-3～5×10^-3 Pa, filling argon into a vacuum glove box, enabling the working air pressure in the vacuum glove box to be 0.5-1.5 Pa, heating a magnesium oxide crucible to 900-1000 ℃, pouring a copper-titanium intermediate alloy, a copper-chromium intermediate alloy and a copper-cerium intermediate alloy into the magnesium oxide crucible after an alloy cast ingot is completely melted, fully stirring until the materials are completely melted, cooling to 850-900 ℃, pouring cobalt-coated micro-nano diamond particles into the magnesium oxide crucible, fully stirring for 3-6 min, and then casting into a brazing filler metal cast ingot;

and step four, removing oxide skin on the brazing filler metal cast ingot in the step three, and processing the brazing filler metal cast ingot into filamentous or banded micro-nano particle reinforced copper-based composite active brazing filler metal.

3. The micro-nano particle reinforced copper-based composite active solder and the preparation method thereof according to claim 2, characterized in that before the cobalt-coated micro-nano diamond particles are poured into the magnesia crucible, the cobalt-coated micro-nano diamond particles are uniformly mixed with a proper amount of dispersant, wherein the dispersant is a mixture of polyalkylene glycol, polyethylene diamine and ethanol.

4. The preparation method of the micro-nano particle reinforced high-indium copper-based active solder according to claim 2, wherein the preparation method of the cobalt-coated micro-nano diamond particles comprises the following steps:

sequentially carrying out oil removal, rinsing, coarsening, rinsing, hydrophilization, rinsing, sensitization and activation, rinsing, degumming and rinsing on the surfaces of the micro-nano diamond particles, and air-drying for later use;

adding cobalt sulfate heptahydrate, sodium hypophosphite monohydrate, sodium citrate, sodium sulfate and sodium dodecyl sulfate into deionized water to prepare a solution, and adjusting the pH value of the solution to be 8.5-10 to obtain a chemical cobalt plating solution;

and step three, placing the micro-nano diamond particles treated in the step one into a chemical cobalt plating solution, electromagnetically stirring at the temperature of 90-100 ℃, plating for 20-60 min, taking out, cleaning to be neutral by using distilled water, and drying in vacuum at the temperature of 80-150 ℃ to obtain the cobalt-coated micro-nano diamond particles.

5. The micro-nano particle reinforced copper-based composite active solder and the preparation method thereof according to claim 4, wherein the coarsening comprises the following steps:

a. adding ferrous sulfate, ferrous chloride, ammonium nitrate, 50 wt% of hydrogen peroxide and 95 wt% of ethanol into deionized water, and fully mixing to prepare the water-soluble paint;

b. and pouring the coarsening solution into an atomization generator, uniformly placing the diamond on an atomization platform, and carrying out atomization etching on the diamond, wherein the atomization etching temperature is 50-80 ℃, and the atomization etching time is 10-30 min.

6. The micro-nano particle reinforced copper-based composite active solder and the preparation method thereof according to claim 4, wherein the hydrophilization method comprises the following steps: and (3) placing the roughened micro-nano diamond particles into a hydrophilization solution to be soaked for 3-15 hours, adding chromium trioxide, chromate and 98 wt% sulfuric acid into deionized water, and fully mixing to prepare the hydrophilization solution, wherein the chromate is one or more of barium chromate, potassium chromate, sodium chromate and magnesium chromate.

7. The micro-nano particle reinforced copper-based composite active solder and the preparation method thereof according to claim 4, wherein the sensitization activation comprises the following steps:

a. weighing stannic chloride powder and palladium chloride powder in a molar ratio of 2: 1 for later use;

b. completely dissolving the tin chloride powder weighed in the step a in deionized water to form a solution A, wherein the ratio of the deionized water to the tin chloride powder is 20-30: 1, and the deionized water is measured in milliliters and the tin chloride powder is measured in grams;

c. b, dissolving all the palladium chloride powder weighed in the step a into deionized water to form

The volume of the deionized water is 40-60: 1 to the palladium chloride powder, wherein the deionized water is measured in milliliters, and the palladium chloride powder is measured in grams;

d. slowly adding the solution A into the solution B, and fully stirring to obtain a solution C;

e. adding the solution C into chloride, adding a stabilizer, fully stirring, heating to 40-60 ℃, and preserving heat for 1-10 hours to obtain a D-sensitized activating solution;

f. diluting the D-sensitized activating solution with ethanol to obtain an E activating solution, and putting the micro-nano diamond particles subjected to hydrophilization into the E activating solution for activation at the activation temperature of 50-60 ℃ for 2-10 min.

8. The micro-nano particle reinforced copper-based composite active solder and the preparation method thereof according to claim 7, wherein the chloride is one or more of sodium chloride, potassium chloride, calcium chloride, magnesium chloride and lithium chloride;

the stabilizer is one or more of natural polymer protein, agar, gum arabic, tannic acid, polyvinyl pyrimidine, polyvinyl amide, polyvinylpyrrolidone, poly- (4-vinylpyrrolidone) and polyphthalamide.

Technical Field

The invention relates to the technical field of brazing materials and preparation thereof, in particular to a micro-nano particle reinforced high-indium copper-based active brazing filler metal and a preparation method thereof.

Background

Diamond has extremely high hardness and excellent wear resistance, determines that the diamond is an ideal grinding material for manufacturing brittle material processing tools, and is widely applied to the fields of petroleum drilling, geological exploration, stone processing, building decoration and the like. Because the diamond particles are fine, the diamond needs to be manufactured into a single-layer diamond tool or a multi-layer diamond tool before use. The traditional manufacturing method is a plating method and a sintering method, however, the diamond and the metal bond which are combined by covalent bonds have higher interface energy, so that the metal bond is difficult to effectively wet on the surface of the diamond, and the interface bonding force is poorer. Therefore, the plated diamond is only mechanically embedded, and the diamond is easy to fall off, low in sharpness and short in service life when in use; in the sintered diamond tool, because the graphitization temperature of the diamond is limited, reliable atom layer surface connection is difficult to form between the diamond and a bonding agent or the connection strength is low, the holding force on the diamond is small, and when cutting force is applied, the diamond is easy to fall off early, so that the service life of the diamond tool is shortened, and the processing efficiency of the diamond tool is reduced. Therefore, research institutions at home and abroad try to prepare diamond tools by a brazing method, and the diamond tools are expected to realize firm holding of a metal bonding agent layer on diamond abrasive grains by means of chemical metallurgical reaction between active brazing filler metal and diamond and a grinding wheel matrix, so that the requirement of high-efficiency processing of heavy load is met.

The active solder for soldering diamond mainly comprises nickel-based active solder, copper-based active solder and silver-based active solder. The melting temperature of the nickel-based active brazing filler metal is high, the liquidus temperature of the nickel-based active brazing filler metal is generally higher than 900 ℃, and during the brazing process, the diamond is easy to have thermal damage, so that the use performance of the diamond tool is influenced; the silver-based active solder has lower melting temperature, does not damage diamonds in the brazing process, but has lower strength, limits the processing range of diamond tools, increases the brazing cost due to higher silver content, and limits the using amount of the silver-based active solder; compared with nickel-based and silver-based solders, the copper-based active solder has moderate melting temperature and strength, does not contain silver, and has low cost, so the copper-based active solder has good application prospect in soldering diamond tools.

At present, commercially available or intensively researched copper-based active solders are mainly CuSnTi solder, CuMnTi solder, CuFeTi solder and CuZnTi solder, and solders evolved on the basis of the solders. The research of the CuSnTi solder is the most extensive, and the research considers that the CuSnTi solder has moderate melting temperature, good wettability to diamond and good fluidity, but the solder has high tin element content, and a microstructure contains a large amount of strip-shaped, blocky and other SnTi and CuTi brittle phases, so that the solder has poor plasticity, reduced mechanical properties and can not be formed by rolling. In order to overcome the forming problem of the CuSnTi solder, the prior art provides an electroplating method for preparing the copper-tin-titanium solder, but has the problems that firstly, titanium is an active element and is easy to oxidize in the plating process; secondly, the plating time is long, and the solder preparation efficiency is low; thirdly, the plating solution pollutes the environment. When the Mn content in the CuMnTi solder is 34.7 wt%, the CuMnTi solder has lower melting temperature, and can reduce the thermal damage of diamond, but the excessively high Mn content leads to the increase of the brittleness of the solder and the deterioration of the processing performance, and simultaneously, the Mn element has larger thermal expansion coefficient, further enlarges the thermal expansion coefficient difference between the CuMnTi solder and the diamond, and increases the residual stress of an interface. The CuFeTi solder has higher strength, but Fe is a diamond catalyst material, and diamond graphitization is easily promoted during soldering. The CuZnTi solder has low melting point, good plasticity and good processing performance, but Zn in the solder is volatile, the solder has unstable performance and is not suitable for vacuum brazing, and Ti element is easy to oxidize in the conventional brazing process to reduce the brazing performance.

Although the strength, hardness and wear resistance of the copper-based active solder are higher than those of the silver-based active solder, the abrasion ratio of diamond and a solder matrix in a diamond tool brazed by the copper-based solder is still not proper, namely, the abrasion speed of the solder matrix is higher than that of the diamond in the use process of the diamond tool, so that the solder matrix around the diamond is abraded quickly, and the service life is shortened. The particle reinforcing phase is added into the solder matrix, so that the dispersion strengthening effect is realized on the solder matrix, and the strength and the wear resistance of the solder matrix can be improved to a certain extent. However, the method for adding the particle reinforced phase is mainly applied to the silver-based brazing filler metal, and the application of the particle reinforced phase in the copper-based brazing filler metal is not reported, so that the development of the micro-nano particle reinforced high-indium copper-based active brazing filler metal has great significance for the preparation of high-performance diamond tools.

Disclosure of Invention

In order to solve the problems, the invention provides a micro-nano particle reinforced high-indium copper-based active solder and a preparation method thereof, the solder has good wettability to diamond, and can ensure that the diamond and a substrate form firm metallurgical bonding; the melting temperature of the brazing filler metal is low, and the diamond is less in thermal damage; the brazing filler metal has high strength, and the wear resistance of the diamond tool can be improved; the brazing filler metal has good plasticity and can be processed into shapes of bands, sheets, wires, powder and the like; the solder contains no noble metal elements such as silver and the like, and the cost is low.

The invention is realized by the following technical scheme:

the micro-nano particle reinforced high-indium copper-based active solder comprises the following raw materials in parts by weight: 85-95 parts of basic components, 2.5-10 parts of active components, 0.1-1 part of trace components and 2-6 parts of micro-nano reinforced particles;

wherein the base component comprises the following components in parts by weight: 5-15 parts of indium, 3-8 parts of tin, 1-3 parts of manganese, 1-5 parts of phosphorus, 0.5-3 parts of antimony, 0.5-5 parts of silicon, 0.5-5 parts of germanium and the balance of copper; the active component comprises the following components in parts by weight: 66-85 parts of titanium and 15-44 parts of chromium; the trace component is rare earth cerium; the components exist in the forms of copper indium intermediate alloy, copper tin intermediate alloy, copper manganese intermediate alloy, copper phosphorus intermediate alloy, copper antimony intermediate alloy, copper silicon intermediate alloy, copper germanium intermediate alloy, copper titanium intermediate alloy, copper chromium intermediate alloy and copper cerium intermediate alloy respectively;

the micro-nano enhanced particles are cobalt-coated micro-nano diamond particles with the particle size of 10-500 nm.

A preparation method of a micro-nano particle reinforced high-indium copper-based active solder specifically comprises the following steps:

step one, putting raw materials of copper, copper-indium intermediate alloy and copper-tin intermediate alloy into a high-frequency induction smelting furnace, heating to 300-400 ℃, adding charcoal to cover, continuously heating to 1100-1150 ℃, completely melting pure copper, copper-indium intermediate alloy and copper-tin intermediate alloy, sequentially adding the copper-silicon intermediate alloy, copper-germanium intermediate alloy and copper-manganese intermediate alloy in the step one, adding charcoal again to cover, fully stirring the solution for 2-5 min by using high-pressure inert gas after the raw materials are completely melted, cooling the solution to 900-1000 ℃, preserving heat, sequentially adding the copper-antimony intermediate alloy and the copper-phosphorus intermediate alloy in the step one, fully stirring after the raw materials are completely melted, standing and cooling to 700-900 ℃, slagging off and casting into alloy ingots;

step two, placing the alloy ingot in the step one into a magnesium oxide crucible, placing the magnesium oxide crucible containing the alloy ingot into an induction coil arranged in a vacuum glove box, placing the copper-titanium intermediate alloy, the copper-chromium intermediate alloy and the copper-cerium intermediate alloy in the step one into a material containing disc A, placing the cobalt-coated micro-nano diamond particles in the step one into a material containing disc B, and placing the two material containing discs in the vacuum glove box;

step three, vacuumizing the vacuum glove box until the vacuum degree is 1 multiplied by 10^～3～5×10^～3 Pa, filling argon into the vacuum glove box to ensure that the working air pressure in the vacuum glove box is 0.5-1.5 Pa, heating the magnesium oxide crucible to 900-1000 ℃, pouring the copper-titanium intermediate alloy, the copper-chromium intermediate alloy and the copper-cerium intermediate alloy into the magnesium oxide crucible after the alloy cast ingot is completely melted, fully stirring until the materials are completely melted, cooling to ensure that the materials are completely meltedPouring the cobalt-coated micro-nano diamond particles into a magnesium oxide crucible at 850-900 ℃, fully stirring for 3-6 min, and casting into a brazing filler metal cast ingot;

and step four, removing oxide skin on the brazing filler metal cast ingot in the step three, and processing the brazing filler metal cast ingot into filamentous or banded micro-nano particle reinforced copper-based composite active brazing filler metal.

Further optimizing, before the cobalt-coated micro-nano diamond particles are poured into a magnesium oxide crucible, uniformly mixing the cobalt-coated micro-nano diamond particles with a proper amount of a dispersing agent, wherein the dispersing agent is a mixture of polyalkylene glycol, polyethylene diamine and ethanol.

Further preferably, the preparation method of the cobalt-coated micro-nano diamond particles comprises the following steps:

sequentially carrying out oil removal, rinsing, coarsening, rinsing, hydrophilization, rinsing, sensitization and activation, rinsing, degumming and rinsing on the surfaces of the micro-nano diamond particles, and air-drying for later use;

adding cobalt sulfate heptahydrate, sodium hypophosphite monohydrate, sodium citrate, sodium sulfate and sodium dodecyl sulfate into deionized water to prepare a solution, and adjusting the pH value of the solution to be 8.5-10 to obtain a chemical cobalt plating solution;

and step three, placing the micro-nano diamond particles treated in the step one into a chemical cobalt plating solution, electromagnetically stirring at the temperature of 90-100 ℃, plating for 20-60 min, taking out, cleaning to be neutral by using distilled water, and drying in vacuum at the temperature of 80-150 ℃ to obtain the cobalt-coated micro-nano diamond particles.

Further optimized, the coarsening comprises the following steps:

a. adding ferrous sulfate, ferrous chloride, ammonium nitrate, 50 wt% of hydrogen peroxide and 95 wt% of ethanol into deionized water, and fully mixing to prepare the water-soluble paint;

b. and pouring the coarsening solution into an atomization generator, uniformly placing the diamond on an atomization platform, and carrying out atomization etching on the diamond, wherein the atomization etching temperature is 50-80 ℃, and the atomization etching time is 10-30 min.

Further optimized, the hydrophilization method comprises the following steps: and (3) placing the roughened micro-nano diamond particles into a hydrophilization solution to be soaked for 3-15 hours, adding chromium trioxide, chromate and 98 wt% sulfuric acid into deionized water, and fully mixing to prepare the hydrophilization solution, wherein the chromate is one or more of barium chromate, potassium chromate, sodium chromate and magnesium chromate.

Further preferably, the sensitization activation comprises the following steps:

a. weighing stannic chloride powder and palladium chloride powder in a molar ratio of 2: 1 for later use;

b. completely dissolving the tin chloride powder weighed in the step a in deionized water to form a solution A, wherein the ratio of the deionized water to the tin chloride powder is 20-30: 1, and the deionized water is measured in milliliters and the tin chloride powder is measured in grams;

c. completely dissolving the palladium chloride powder weighed in the step a into deionized water to form a solution B, wherein the volume of the added deionized water is 40-60: 1 in proportion to the palladium chloride powder, and the deionized water is measured in milliliters and the palladium chloride powder is measured in grams;

d. slowly adding the solution A into the solution B, and fully stirring to obtain a solution C;

e. adding the solution C into chloride, adding a stabilizer, fully stirring, heating to 40-60 ℃, and preserving heat for 1-10 hours to obtain a D-sensitized activating solution;

f. diluting the D-sensitized activating solution with ethanol to obtain an E activating solution, and putting the micro-nano diamond particles subjected to hydrophilization into the E activating solution for activation at the activation temperature of 50-60 ℃ for 2-10 min.

Further optimizing, the chloride salt is one or more of sodium chloride, potassium chloride, calcium chloride, magnesium chloride and lithium chloride;

the stabilizer is one or more of natural polymer protein, agar, gum arabic, tannic acid, polyvinyl pyrimidine, polyvinyl amide, polyvinylpyrrolidone, poly- (4-vinylpyrrolidone) and polyphthalamide.

The invention has the beneficial effects that:

(1) aiming at the high tin defect of the CuSnTi solder, the invention reduces the tin content by adding indium with high proportion and compositely adding a small amount of phosphorus, manganese, silicon, antimony and germanium to replace partial tin, thereby further reducing the melting temperature of the solder, preventing massive or strip-shaped SnTi compounds from being formed in soldering seams, optimizing the microstructure of the soldering seams, simultaneously, the indium and the antimony have the dispersion strengthening effect and the silicon, the manganese and the germanium have the solid solution strengthening effect at room temperature, and further improving the strength and the wear resistance of the soldering seams;

(2) the invention considers the thermal expansion coefficient of the brazing filler metal for the selection of the brazing filler metal elements, and sets the mass parts of the selected elements according to the mixing theory of the thermal expansion coefficient, thereby ensuring that the thermal expansion coefficient of the brazing filler metal is between diamond and a steel matrix and reducing the brazing residual stress;

(3) according to the invention, the cobalt-coated micro-nano diamond particles are used as a reinforcing phase to prepare the high-indium copper-based active solder, the cobalt-coated micro-nano diamond particles and the high-indium copper-based solder have good compatibility, the reinforcing phase in the solder is well combined with a solder substrate, and interface defects do not exist, so that the strength and the wear resistance of the copper-based solder are improved.

Drawings

FIG. 1 is a microstructure diagram of a micro-nano particle-reinforced high-indium copper-based active solder prepared in example 1;

FIG. 2 is a topography of a micro-nano particle-enhanced high-indium copper-based active solder brazed diamond prepared in example 1;

reference numerals: 1. micro-nano diamond particles.

Detailed Description

The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings of the present invention.