CN111155087A - Method for plating Cu and Ni on dispersion copper vacuum brazing coating film - Google Patents

Method for plating Cu and Ni on dispersion copper vacuum brazing coating film Download PDF

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CN111155087A
CN111155087A CN201911354120.0A CN201911354120A CN111155087A CN 111155087 A CN111155087 A CN 111155087A CN 201911354120 A CN201911354120 A CN 201911354120A CN 111155087 A CN111155087 A CN 111155087A
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dispersed copper
copper
vacuum
film
dispersed
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CN111155087B (en
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刘锦慧
杨平
陈梅
侯蕊
王小明
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Shaanxi Sirui Advanced Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/137—Spraying in vacuum or in an inert atmosphere

Abstract

The invention discloses a method for plating Cu and Ni on a dispersion copper vacuum brazing coating film, which comprises the steps of impurity removal, coarsening and modification of the surface of the dispersion copper, plasma vacuum coating, vacuum brazing and the like. The invention discloses a method for modifying the surface of dispersed copper, which is characterized in that boric acid-containing treatment liquid is sprayed to form a film, the boric acid is converted into boron trioxide at high temperature and then embedded on the surface of the dispersed copper to be used as a connecting point, and the brazing performance of the dispersed copper is improved by increasing the binding force of a metal film layer and the surface of the dispersed copper.

Description

Method for plating Cu and Ni on dispersion copper vacuum brazing coating film
Technical Field
The invention belongs to the technical field of brazing, and particularly relates to a method for plating Cu and Ni on a diffusion copper vacuum brazing coating film.
Background
The rotary anode X-ray tube is a high vacuum electric vacuum device, when the electronic tube works, the anode is grounded, and the cathode is connected with negative high voltage (maximum 150 kV). The contact resistance from the tungsten disk surface to the anode bar causes a certain potential difference. The anode electron flow is from the tungsten disk → the copper bush → the shaft → the steel ball → the upper and lower outer rings. The subsequent electron current path enters the anode bar from the upper and lower outer rings, the gasket and the like to form a loop with the power supply.
With the improvement of medical system, high-grade diagnostic instruments are more and more popular, wherein a whole machine adopting a high-power high-speed rotating anode X-ray tube is adopted, and after a high-power (800-1000 mA) high-speed rotating anode X-ray tube is installed in the whole machine and runs for months, the high-power high-speed rotating anode X-ray tube including a rotor copper sleeve and a bearing assembly are easy to damage and have a much shorter service life than that of a medium-speed rotating anode X-ray tube.
The dispersion copper has the characteristics of high strength, high conductivity, high softening temperature and the like, so that the dispersion copper is more suitable as a rotor copper sleeve of an X-ray tube, the problem of poor joint strength of the dispersion copper and steel after brazing in the welding process can be caused due to the difference of physical properties, the brazing performance of the dispersion copper is improved by mostly adopting a metal film plated on the surface of the dispersion copper in the prior art, but the conventional method cannot meet the market requirement for improving the effect.
Therefore, a vacuum brazing coating method with improved brazing performance of dispersed copper is needed to meet the actual market demand.
Disclosure of Invention
The invention aims to solve the problems that dispersed copper is difficult to braze and the brazing performance is low, and provides a method for plating Cu and Ni on a dispersed copper vacuum brazing film, which improves the brazing performance by plating a metal film on the surface of the dispersed copper, in particular improves the brazing performance of the dispersed copper by increasing the bonding force between the metal film and the surface of the dispersed copper.
The technical scheme of the invention is as follows: a method for plating Cu and Ni on a dispersion copper vacuum brazing coating film comprises the following steps:
(1) removing impurities on the surface of dispersed copper: soaking the dispersed copper workpiece in cleaning solution (commercially available foamless metal surface cleaning agent) for 15-20min, and performing ultrasonic treatment for 10-15min to remove oil stains and oxidation film on the surface of the dispersed copper workpiece;
(2) coarsening the surface of the dispersed copper: placing the dispersed copper with the surface subjected to impurity removal in the step (1) in a vacuum chamber, and roughening the surface of the dispersed copper by adopting a pulse laser etching technology to form a plurality of pits with the diameter of 1-1.5mm and the depth of 0.1-0.2 mm;
(3) surface modification of dispersed copper: spraying a treatment liquid containing a transition metal compound on the surface of the dispersion copper after the surface is roughened in the step (2), drying the treatment liquid in a vacuum furnace at a low temperature of 50-60 ℃ for forming a dense film layer with the thickness of 0.1-0.5mm on the surface of the dispersion copper, preserving the heat for 12-24h, and then carrying out gradient heating for burning off organic components in the film layer in a high-temperature environment or volatilizing the organic components to remove impurities, and leaving a transition metal oxide embedded on the surface of the dispersion copper as a surface modification connection point;
(4) plasma vacuum coating: placing the dispersed copper after the modification treatment in the step (3) into a vacuum chamber, vacuumizing to 10-15pa, performing irradiation treatment by using high-energy particles with energy of 10keV-100keV to excite electrons on the surface of the dispersed copper, and performing plasma spraying coating on the excited dispersed copper in a plasma spraying system to form a 200-500 mu m metal film;
(5) vacuum brazing: and placing the dispersed copper, the Ag-Cu-Ti solder and the kovar alloy with the surface subjected to impurity removal treatment in a vacuum brazing furnace, vacuumizing the vacuum brazing furnace, and keeping the temperature at 800-850 ℃ for 20-40min to quench so as to finish the vacuum brazing process.
Further, the process parameters of the pulse type laser etching technology in the step (2) are as follows: the pulse laser with the laser intensity of 10-20J/cm and the frequency of 4-5kHz has the pulse width of 100-150ns and the contact angle of 150-160 DEG rolling angle of 3 DEG with the surface of the dispersed copper. Compared with the sand blasting laser etching, the size is uniform and is easier to control, and impurities cannot be introduced.
Further step (3) the transition metal compound is a compound of boron, silicon, germanium, selenium, tellurium, polonium, arsenic or antimony. The transition metal and the compound thereof are easy to lose electrons, and are suitable to be used as a connector of a metal coating and dispersed copper in theory, and the effect of the compound of boron is optimal through comprehensive comparison.
Further step (3) of a transition metal-containing compoundThe treatment fluid comprises the following components in percentage by weight: 20 to 24 percent of boric acid and 0.1 to 0.5 percent of CeCl31-3% of film forming agent, 0.5-1.5% of wetting agent, 0.3-0.8% of flatting agent, 1.2-2.5% of antioxidant and the balance of ethanol. The boric acid is a transition metal compound, and can generate diboron trioxide after high-temperature calcination, and the energy difference between the ground state and the excited state of the transition metal compound is small, so that electronic transition is easy to occur, and the electronic transition can be excited by only needing lower energy, holes are left, and metal electrons of the coating are easy to receive, and the binding property is improved. Rare metal ion Ce3+The boride can be used as an activator for receiving high-energy particle rays, so that the absorptivity of the boride to the high-energy particle rays can be further improved. The film forming agent adopts a water-soluble acrylate wetting agent and the phosphate leveling agent adopts diacetone alcohol antioxidant as the propyl benzene trinitrogen file, so that the surface of the dispersed copper can be effectively prevented from being oxidized again. These polymer additives can be burned off at a high temperature of 300 ℃ or higher.
Further, the gradient temperature rise in the step (3) specifically includes: gradually raising the temperature to 200-240 ℃ at the speed of 5 ℃/min, gradually dehydrating the boric acid in the dense film layer, firstly converting the boric acid into metaboric acid, then converting the metaboric acid into tetraboric acid, preserving the heat for 20min to fully dehydrate and dry the tetraboric acid, and then raising the temperature to 400-650 ℃ at the speed of 10 ℃/min to continuously dehydrate the tetraboric acid and convert the tetraboric acid into a diboron trioxide melt. If the temperature is increased sharply without gradient temperature increase, boric acid cannot be completely converted into diboron trioxide, and the content of the final diboron trioxide is affected because the decomposition reaction violently causes the film to crack and peel. The boron trioxide can be used as a fluxing agent to improve the brazing performance of the dispersed copper, and the boron trioxide can be used as an acid oxide to react and combine with aluminum oxide which is used as an alkaline metal oxide in the dispersed copper in a molten state to generate more compact borate or metaborate with more stable property. When the borate is subjected to irradiation treatment by high-energy particles, energy is absorbed by the excited borate, and then electrons in the inner layer are transited to an outer layer orbit with high energy or are directly ionized to generate electron-hole pairs which can receive plating metal ions sprayed by plasma excitation to tightly connect a metal plating with dispersed copper, and the borate is used as an intermediate connecting layer to greatly improve the strength of the brazing connection of the dispersed copper.
The radiation dose of any one of α particles, β particles and gamma particles is 70-100particles/cm2. The dosage is lower than 70particles/cm2The energy is not enough to excite the electron to generate transition to form excited state, and the dose is higher than 100particles/cm2Particles are likely to cause radiation residue.
Further, in the step (4), the metal film is a Cu film or a Ni film.
The plasma spraying process method in the step (4) further comprises the following steps:
s1: selecting Cu powder or Ni powder with purity of more than 99.9% and particle size of 2-10 μm as spraying particle;
s2: firstly, introducing argon into a vacuum chamber with the vacuum degree of 10-15pa according to the flow of 100-110L/min until the pressure in the vacuum chamber is 0.2-0.4MPa, and then introducing hydrogen into the vacuum chamber according to the flow of 40-50L/min until the pressure in the vacuum chamber is 1-2MPa, and then starting to prepare for plasma spraying on the modified dispersed copper;
s3: adjusting the arc voltage of the plasma spraying equipment to be 55-70V, the arc current to be 1100-ion 1300A, the powder feeding speed to be 5-8g/min, the spraying distance to be 10-15cm, adopting a multi-layer spraying mode, wherein the spraying thickness of each layer is 20-40 mu m, and each layer of metal film is sprayed according to the volume ratio of argon to hydrogen of 2:1, introducing mixed gas into a vacuum chamber, increasing the pressure of the gas by 0.2-0.6MPa, and finally quenching the metal film with the final thickness of 200-ion 500 mu m. The metal coating is sprayed on a small number of times in multiple layers, and the internal pressure of the vacuum chamber is gradually increased along with the increase of the coating, so that the density of the metal film can be increased, the connection strength of the metal film and the dispersed copper can be increased, and the brazing performance of the dispersed copper can be improved.
The invention has the beneficial effects that: the invention adopts laser etching to coarsen the surface of the dispersed copper, compared with the sand blasting laser etching, the size is uniform and is easier to control, and impurities can not be introduced. The roughened surface of the dispersed copper is sprayed with a treatment liquid containing boric acid to form a film, one purpose of the film is to protect the roughened surface from being oxidized, the other purpose of the film is to dehydrate the boric acid in the film layer by heating to convert the boric acid into diboron trioxide to be embedded on the surface of the dispersed copper, and the method has the following advantages:
(1) the diboron trioxide is used as a fluxing agent to improve the easy brazing performance of the dispersed copper;
(2) the boron trioxide can be used as an acid oxide to react and combine with aluminum oxide which is used as an alkaline metal oxide in dispersed copper in a molten state to generate more compact and stable borate or metaborate pair which can form stronger bonding force with the dispersed copper;
(3) the diboron trioxide used as the transition metal oxide has small energy difference between the ground state and the excited state of the transition metal oxide and the transition metal, and is easy to generate electron transition, so that the electron transition can be excited by only needing lower energy, holes are left, metal electrons of the coating can be received more easily, and the binding property with the metal coating is improved.
In conclusion, the surface bonding force of the metal film layer and the dispersed copper can be effectively improved by embedding the boron trioxide on the surface of the dispersed copper as a connecting point, so that the brazing performance of the dispersed copper is improved.
Detailed Description
Example 1
A method for plating Cu and Ni on a dispersion copper vacuum brazing coating film comprises the following steps:
(1) removing impurities on the surface of dispersed copper: soaking the dispersed copper workpiece in cleaning solution (commercially available foamless metal surface cleaning agent) for 1min, and performing ultrasonic treatment for 10min to remove oil stains and oxidation film on the surface of the dispersed copper workpiece;
(2) coarsening the surface of the dispersed copper: placing the dispersed copper with the surface subjected to impurity removal in the step (1) in a vacuum chamber, and roughening the surface of the dispersed copper by adopting a pulse laser etching technology to form a plurality of pits with the diameter of 1mm and the depth of 0.1 mm; the process parameters of the pulse type laser etching technology are as follows: the pulse width of the pulse laser with the laser intensity of 10J/cm and the frequency of 4kHz is 100ns, and the contact angle between the pulse width of the pulse laser and the surface of the dispersed copper is 15 degrees, and the rolling angle is 3 degrees. Compared with the sand blasting laser etching, the size is uniform and is easier to control, and impurities cannot be introduced.
(3) Surface modification of dispersed copper: spraying transition metal compound on the roughened surface of the dispersed copper in the step (2)Drying the treatment liquid in a vacuum furnace at a low temperature of 50 ℃ for forming a compact film layer with the thickness of 0.1mm on the surface of the dispersed copper and preserving heat for 12 hours; wherein the treatment fluid containing the transition metal compound comprises the following components in percentage by weight: 20% boric acid, 0.1% CeCl31 percent of film forming agent, 0.5 percent of wetting agent, 0.3 percent of flatting agent, 1.2 percent of antioxidant and the balance of ethanol. The boric acid is a transition metal compound, and can generate diboron trioxide after high-temperature calcination, and the energy difference between the ground state and the excited state of the transition metal compound is small, so that electronic transition is easy to occur, and the electronic transition can be excited by only needing lower energy, holes are left, and metal electrons of the coating are easy to receive, and the binding property is improved. Rare metal ion Ce3+The boride can be used as an activator for receiving high-energy particle rays, so that the absorptivity of the boride to the high-energy particle rays can be further improved. The film forming agent adopts a water-soluble acrylate wetting agent and the phosphate leveling agent adopts diacetone alcohol antioxidant as the propyl benzene trinitrogen file, so that the surface of the dispersed copper can be effectively prevented from being oxidized again. These polymer additives can be burned off at a high temperature of 300 ℃ or higher.
Then the gradient temperature rise specifically comprises the following steps: gradually heating to 200 ℃ at the speed of 5 ℃/min, gradually dehydrating boric acid in the dense film layer, converting the boric acid into metaboric acid, converting the metaboric acid into tetraboric acid, preserving the heat for 20min to fully dehydrate and dry the tetraboric acid, and then heating to 400 ℃ at the speed of 10 ℃/min to continuously dehydrate the tetraboric acid and convert the tetraboric acid into a diboron trioxide melt. If the temperature is increased sharply without gradient temperature increase, boric acid cannot be completely converted into diboron trioxide, and the content of the final diboron trioxide is affected because the decomposition reaction violently causes the film to crack and peel. The boron trioxide can be used as a fluxing agent to improve the brazing performance of the dispersed copper, and the boron trioxide can be used as an acid oxide to react and combine with aluminum oxide which is used as an alkaline metal oxide in the dispersed copper in a molten state to generate more compact borate or metaborate with more stable property. When the borate is subjected to irradiation treatment by high-energy particles, energy is absorbed by the excited borate, and then electrons in the inner layer are transited to an outer layer orbit with high energy or are directly ionized to generate electron-hole pairs which can receive plating metal ions sprayed by plasma excitation to tightly connect a metal plating with dispersed copper, and the borate is used as an intermediate connecting layer to greatly improve the strength of the brazing connection of the dispersed copper. The surface modification connecting point is used for removing impurities by burning or volatilizing organic components in the film layer under a high-temperature environment and leaving transition metal oxide embedded on the surface of the dispersed copper as a surface modification connecting point;
(4) and (3) plasma vacuum coating, namely putting the dispersed copper subjected to modification treatment in the step (3) into a vacuum chamber, vacuumizing to 10pa, and performing irradiation treatment by using high-energy particles with the energy of 10keV to excite any one of α particles, β particles and gamma particles on the surface of the dispersed copper, wherein the radiation dose of the high-energy particles is 70particles/cm2. The dosage is lower than 70particles/cm2The energy is not enough to excite the electron to generate transition to form excited state, and the dose is higher than 100particles/cm2Particles are likely to cause radiation residue. Then plasma spraying coating is carried out on the excited state dispersed copper in a plasma spraying system to form a Cu film with the thickness of 200-500 mu m; the plasma spraying process method comprises the following steps:
s1: selecting Cu powder with the purity of more than 99.9% and the particle size of 2 mu m as spraying particles;
s2: firstly, introducing argon into a vacuum chamber with the vacuum degree of 10pa according to the flow of 100L/min until the pressure in the vacuum chamber is 0.2MPa, and then introducing hydrogen into the vacuum chamber according to the flow of 40L/min until the pressure in the vacuum chamber is 1MPa to prepare for plasma spraying on the modified dispersed copper;
s3: the arc voltage of the plasma spraying equipment is adjusted to be 55V, the arc current is 1100A, the powder feeding speed is 5g/min, and a Cu film with the thickness of 200 mu m is sprayed and sprayed at the spraying distance of 10 cm.
(5) Vacuum brazing: and placing the dispersed copper, the Ag-Cu-Ti solder and the kovar alloy with the surface being subjected to impurity removal treatment in a vacuum brazing furnace, vacuumizing the vacuum brazing furnace, and preserving the heat at 800 ℃ for 20min to quench so as to finish the vacuum brazing process.
Example 2
A method for plating Cu and Ni on a dispersion copper vacuum brazing coating film comprises the following steps:
(1) removing impurities on the surface of dispersed copper: soaking the dispersed copper workpiece in cleaning solution (commercially available foamless metal surface cleaning agent can be adopted) for 15min, and then carrying out ultrasonic treatment for 10min to remove oil stains and oxidation films on the surface of the dispersed copper workpiece;
(2) coarsening the surface of the dispersed copper: placing the dispersed copper with the surface subjected to impurity removal in the step (1) in a vacuum chamber, and roughening the surface of the dispersed copper by adopting a pulse laser etching technology to form a plurality of pits with the diameter of 1.2mm and the depth of 0.15 mm; the process parameters of the pulse type laser etching technology are as follows: the pulse width of the pulse laser with the laser intensity of 15J/cm and the frequency of 4.5kHz is 100ns, and the contact angle between the pulse width of the pulse laser and the surface of the dispersed copper is 155 degrees, and the rolling angle is 3 degrees.
(3) Surface modification of dispersed copper: spraying a treatment liquid containing a transition metal compound on the surface of the dispersion copper after the surface is roughened in the step (2), and drying the treatment liquid in a vacuum furnace at a low temperature of 55 ℃ for forming a dense film layer with the thickness of 0.25mm on the surface of the dispersion copper and preserving heat for 20 hours; wherein the treatment fluid containing the transition metal compound comprises the following components in percentage by weight: 22% boric acid, 0.3% CeCl32 percent of film forming agent, 1.0 percent of wetting agent, 0.5 percent of flatting agent, 2.0 percent of antioxidant and the balance of ethanol.
Then the gradient temperature rise specifically comprises the following steps: gradually heating to 220 ℃ at the speed of 5 ℃/min, gradually dehydrating boric acid in the dense film layer, converting the boric acid into metaboric acid, converting the metaboric acid into tetraboric acid, preserving the heat for 20min to fully dehydrate and dry the tetraboric acid, and then heating to 550 ℃ at the speed of 10 ℃/min to continuously dehydrate the tetraboric acid and convert the tetraboric acid into a diboron trioxide melt. The surface modification connecting point is used for removing impurities by burning or volatilizing organic components in the film layer under a high-temperature environment and leaving transition metal oxide embedded on the surface of the dispersed copper as a surface modification connecting point;
(4) placing the dispersed copper after the modification treatment in the step (3) into a vacuum chamber, vacuumizing to 12pa, and performing irradiation treatment by using high-energy particles with the energy of 50keV to excite the electron high-energy particles on the surface of the dispersed copper to be α particles, β particles or gamma particles, wherein the radiation dose of any one high-energy particle is 80particles/cm2. Then plasma spraying coating is carried out on the excited state dispersion copper in a plasma spraying system to form a Cu film with the thickness of 300 microns; the plasma sprayThe coating process method comprises the following steps:
s1: selecting Cu powder with purity of more than 99.9% and particle size of 2-10 μm as spraying particles;
s2: firstly, introducing argon into a vacuum chamber with the vacuum degree of 13pa according to the flow of 105L/min until the pressure in the vacuum chamber is 0.3MPa, and then introducing hydrogen into the vacuum chamber according to the flow of 45L/min until the pressure in the vacuum chamber is 1.5MPa to start to prepare for plasma spraying on the modified dispersed copper;
s3: the arc voltage of the plasma spraying equipment is adjusted to be 60V, the arc current is 1200A, the powder feeding speed is 6g/min, and a Cu film with the thickness of 300 mu m is sprayed and the spraying distance is 13 cm.
(5) Vacuum brazing: and placing the dispersed copper, the Ag-Cu-Ti solder and the kovar alloy with the surface subjected to impurity removal treatment in a vacuum brazing furnace, vacuumizing the vacuum brazing furnace, and keeping the temperature at 810 ℃ for 30min to quench so as to finish the vacuum brazing process.
Example 3
A method for plating Cu and Ni on a dispersion copper vacuum brazing coating film comprises the following steps:
(1) removing impurities on the surface of dispersed copper: soaking the dispersed copper workpiece in cleaning solution (commercially available foamless metal surface cleaning agent can be adopted) for 20min, and then carrying out ultrasonic treatment for 15min to remove oil stains and oxidation films on the surface of the dispersed copper workpiece;
(2) coarsening the surface of the dispersed copper: placing the dispersed copper with the surface subjected to impurity removal in the step (1) in a vacuum chamber, and roughening the surface of the dispersed copper by adopting a pulse laser etching technology to form a plurality of pits with the diameter of 1.5mm and the depth of 0.2 mm; the process parameters of the pulse type laser etching technology are as follows: the pulse width of the pulse laser with the laser intensity of 20J/cm and the frequency of 5kHz is 100-150ns, and the contact angle between the pulse laser and the surface of the dispersed copper is 160 DEG, and the rolling angle is 3 deg.
(3) Surface modification of dispersed copper: spraying a treatment liquid containing a transition metal compound on the surface of the dispersion copper after the surface is roughened in the step (2), and drying the treatment liquid in a vacuum furnace at a low temperature of 60 ℃ for forming a dense film layer with the thickness of 0.5mm on the surface of the dispersion copper and preserving heat for 24 hours; wherein the treatment fluid containing the transition metal compound comprises the following components in percentage by weight: 24% boric acid、0.5％CeCl33 percent of film forming agent, 1.5 percent of wetting agent, 0.8 percent of flatting agent, 2.5 percent of antioxidant and the balance of ethanol.
Then the gradient temperature rise specifically comprises the following steps: gradually heating to 240 ℃ at the speed of 5 ℃/min, gradually dehydrating boric acid in the dense film layer, converting the boric acid into metaboric acid, converting the metaboric acid into tetraboric acid, preserving the heat for 20min to fully dehydrate and dry the tetraboric acid, and then heating to 650 ℃ at the speed of 10 ℃/min to continuously dehydrate the tetraboric acid and convert the tetraboric acid into a diboron trioxide melt. The surface modification connecting point is used for removing impurities by burning or volatilizing organic components in the film layer under a high-temperature environment and leaving transition metal oxide embedded on the surface of the dispersed copper as a surface modification connecting point;
(4) placing the dispersed copper after the modification treatment in the step (3) into a vacuum chamber, vacuumizing to 15pa, and performing irradiation treatment by using high-energy particles with the energy of 100keV to excite the high-energy particles of any one of α particles, β particles and gamma particles on the surface of the dispersed copper, wherein the radiation dose of any one of the high-energy particles is 100particles/cm2. Then plasma spraying coating is carried out on the excited state dispersion copper in a plasma spraying system to form a Cu film with the thickness of 500 mu m; the plasma spraying process method comprises the following steps:
s1: selecting Cu powder with the purity of more than 99.9% and the particle size of 10 mu m as spraying particles;
s2: firstly, introducing argon into a vacuum chamber with the vacuum degree of 15pa according to the flow of 110L/min until the pressure in the vacuum chamber is 0.4MPa, and then introducing hydrogen into the vacuum chamber according to the flow of 50L/min until the pressure in the vacuum chamber is 2MPa to prepare for plasma spraying on the modified dispersed copper;
s3: the arc voltage of the plasma spraying equipment is adjusted to be 70V, the arc current is 1300A, the powder feeding speed is 8g/min, the spraying distance is 15cm, and the sprayed Cu film with the thickness of 500 mu m is formed.
(5) Vacuum brazing: and placing the dispersed copper, the Ag-Cu-Ti solder and the kovar alloy with the surface being subjected to impurity removal treatment in a vacuum brazing furnace, vacuumizing the vacuum brazing furnace, and preserving the heat at the temperature of 850 ℃ for 40min to quench so as to finish the vacuum brazing process.
Example 4
This example is substantially the same as example 2 except that Ni powder having a purity of more than 99.9% and a particle diameter of 5 μm is selected as spray particles to be finally plated with a Ni film on the surface of the dispersed copper.
Example 5
The present embodiment is substantially the same as embodiment 2 except that the treating solution containing the transition metal compound in step (3) of the present embodiment includes, by weight: 22% silicic acid, 0.3% CeCl32 percent of film forming agent, 1.0 percent of wetting agent, 0.5 percent of flatting agent, 2.0 percent of antioxidant and the balance of ethanol.
Example 6
The present embodiment is substantially the same as embodiment 2 except that the treating solution containing the transition metal compound in step (3) of the present embodiment includes, by weight: 22% of silicic acid, 2% of film forming agent, 1.0% of wetting agent, 0.5% of flatting agent, 2.0% of antioxidant and the balance of ethanol.
Example 7
This example is substantially the same as example 2 except that the present application does not have the step of modifying the surface of the dispersed copper with the treatment liquid containing the transition metal compound in step (3).
Example 8
The present embodiment is substantially the same as embodiment 2 except that the plasma spraying process in step (4) includes:
s1: selecting Cu powder or Ni powder with purity of more than 99.9% and particle size of 2-10 μm as spraying particle;
s2: firstly, introducing argon into a vacuum chamber with the vacuum degree of 13pa according to the flow of 105L/min until the pressure in the vacuum chamber is 0.3MPa, and then introducing hydrogen into the vacuum chamber according to the flow of 45L/min until the pressure in the vacuum chamber is 1.5MPa to start to prepare for plasma spraying on the modified dispersed copper;
s3: adjusting the arc voltage of a plasma spraying device to be 60V, setting the arc current to be 1200A, setting the powder feeding speed to be 13cm, adopting a multi-layer spraying mode, spraying the powder with the thickness of 30 mu m, spraying one layer of metal film with the thickness of 300 mu m, introducing mixed gas into a vacuum chamber according to the volume ratio of argon to hydrogen of 2:1, increasing the pressure in the vacuum chamber by 0.4MPa, and finally quenching the metal film with the thickness of 300 mu m. The metal coating is sprayed on a small number of times in multiple layers, and the internal pressure of the vacuum chamber is gradually increased along with the increase of the coating, so that the density of the metal film can be increased, the connection strength of the metal film and the dispersed copper can be increased, and the brazing performance of the dispersed copper can be improved.
Examples of the experiments
The method for testing the brazing performance (tensile strength, hardness and conductivity of the brazed joint) of the dispersion copper workpieces brazed in examples 1 to 8 was as follows:
1. the method for testing the tensile strength of the soldered joint comprises the following steps: the tensile rate of the brazed test piece was 5mm/mnin at room temperature in a CMT5205 electronic universal tester. Refer to the GB228-2002 'method for testing tensile strength of metal materials at room temperature' and GB11363-89 'method for testing strength of soldered joints' standards.
2. Hardness test and conductivity test methods: firstly, a brazing joint is ground on coarse abrasive paper to remove an oxide layer, then the thickness of the surface of the brazing joint is ground on a pre-grinding machine to be 1-2 mm, so that the measured value is guaranteed, and a flat sample is precisely ground on No. 1 abrasive paper to enable the surface to be smooth.
The hardness of the brazed joint area was measured by means of a Vickers hardness testing machine model HV-120 according to GB4340-1984 "Metal Vickers hardness test". And placing the ground sample on a workbench by adopting a 50 kg load, adjusting the focus, beating the pressure mark, and reading the length of the diagonal line to obtain the hardness value.
The conductivity of the brazed dispersion copper workpiece is tested by an FQR7501 eddy current conductivity meter according to standard HB/T5420-1989 for resistance welding electrode alloy and auxiliary device copper and copper alloy.
The test results are shown in table 1:
TABLE 1 braze Performance test results for dispersed copper workpieces after brazing examples 1-8
Tensile strength (MPa) Electrical conductivity (% IACS) Hardness (HV50)
Example 1 336 24 234
Example 2 342 28 238
Example 3 338 25 239
Example 4 341 27 235
Example 5 316 22 219
Example 6 330 23 230
Example 7 276 21 165
Example 8 345 27 243
As can be seen from table 1:
(1) it can be seen from comparison of examples 1-3 that the tensile strength of the brazed joint obtained by the better parameters of example 2 under the same process steps and different process parameters is 342MPa at the highest, which is closer to 350MPa of the tensile strength of the bulk of the dispersed copper, and the hardness and conductivity are better than those of examples 1 and 3.
(2) Comparative example 2 and example 4 the properties of the Cu-plated film and the Ni-plated film with respect to the brazing strength were not much different under the same process parameters and conditions, that is, both were selected.
(3) It is understood from comparative examples 2 and 5 that boric acid is preferable as an important additive in the treating fluid because boric acid itself serves as a flux to improve the brazing property of dispersed copper, although it is a transition metal compound, because the treating fluid of example 5 uses silicic acid instead of boric acid, and therefore, boric acid is preferable as another transition metal compound because it is more suitable than boric acid.
(4) Comparison of example 2 and example 6 shows that the brazing performance of example 6 is slightly inferior to that of example 2, probably due to the reduction of CeCl in the treatment solution for modifying the surface of dispersed copper in example 6 compared to example 23So that rare metal ions Ce are reduced when boride receives high-energy particle energy3+As an activator to reduce the binding force of boron trioxide on the copper plating.
(5) Comparative example 2 and example 7 the braze properties were the lowest in example 7 because the surface of the dispersed copper was not modified directly with the boric acid containing treatment solution.
(6) Comparing example 2 and example 8, it can be seen that example 8 is slightly better than example 2 in every brazing performance, which illustrates the improvement in improving brazing performance using the multi-layer spray pattern with gradual pressurization.

Claims (7)

1. A method for plating Cu and Ni on a dispersion copper vacuum brazing coating film is characterized by comprising the following steps:
(1) removing impurities on the surface of dispersed copper: soaking the dispersed copper workpiece in cleaning solution for 15-20min, and performing ultrasonic treatment for 10-15min to remove oil stains and oxidation films on the surface of the dispersed copper;
(2) coarsening the surface of the dispersed copper: placing the dispersed copper with the surface subjected to impurity removal in the step (1) in a vacuum chamber, and roughening the surface of the dispersed copper by adopting a pulse laser etching technology to form a plurality of pits with the diameter of 1-1.5mm and the depth of 0.1-0.2 mm;
(3) surface modification of dispersed copper: spraying a treatment liquid containing a transition metal compound on the surface of the dispersion copper after the surface is roughened in the step (2), drying the treatment liquid in a vacuum furnace at a low temperature of 50-60 ℃ for forming a dense film layer with the thickness of 0.1-0.5mm on the surface of the dispersion copper, preserving the heat for 12-24h, and then carrying out gradient heating for burning off organic components in the film layer in a high-temperature environment or volatilizing the organic components to remove impurities, and leaving a transition metal oxide embedded on the surface of the dispersion copper as a surface modification connection point;
(4) plasma vacuum coating: placing the dispersed copper after the modification treatment in the step (3) into a vacuum chamber, vacuumizing to 10-15pa, performing irradiation treatment by using high-energy particles with energy of 10keV-100keV to excite electrons on the surface of the dispersed copper, and performing plasma spraying coating on the excited dispersed copper in a plasma spraying system to form a 200-500 mu m metal film;
(5) vacuum brazing: and placing the dispersed copper, the brazing filler metal and the kovar alloy with the surface being plated with the metal film into a vacuum brazing furnace, vacuumizing the vacuum brazing furnace, and keeping the temperature at 800-850 ℃ for 20-40min to quench so as to finish the vacuum brazing process.
2. The method for plating the Cu and Ni on the dispersed copper vacuum brazing coating film according to claim 1, wherein the process parameters of the pulse type laser etching technology in the step (2) are as follows: the pulse laser with the laser intensity of 10-20J/cm and the frequency of 4-5kHz has the pulse width of 100-150ns and the contact angle of 150-160 DEG rolling angle of 3 DEG with the surface of the dispersed copper.
3. The method of claim 1, wherein the transition metal compound of step (3) is a compound of boron, silicon, germanium, selenium, tellurium, polonium, arsenic or antimony.
4. The method for plating Cu and Ni on the dispersed copper vacuum brazing coating film according to claim 1, wherein the treatment solution containing the transition metal compound in the step (3) comprises the following components in percentage by weight: 20 to 24 percent of boric acid and 0.1 to 0.5 percent of CeCl31-3% of film forming agent, 0.5-1.5% of wetting agent, 0.3-0.8% of flatting agent, 1.2-2.5% of antioxidant and the balance of ethanol.
5. The method for plating Cu and Ni on a dispersed copper vacuum brazing film according to claim 1, wherein the radiation dose of the high-energy particles selected from α particles, β particles and gamma particles is 70-100particles/cm2。
6. The method for plating Cu and Ni on a dispersed copper vacuum brazing film according to claim 1, wherein the metal film in the step (4) is a Cu film or a Ni film.
7. The method for plating Cu and Ni on the dispersed copper vacuum brazing coating film according to claim 1, wherein the plasma spraying process in the step (4) comprises the following steps:
s1: selecting Cu powder or Ni powder with purity of more than 99.9% and particle size of 2-10 μm as spraying particle;
s2: firstly, introducing argon into a vacuum chamber with the vacuum degree of 10-15pa according to the flow of 100-110L/min until the pressure in the vacuum chamber is 0.2-0.4MPa, and then introducing hydrogen into the vacuum chamber according to the flow of 40-50L/min until the pressure in the vacuum chamber is 1-2MPa, and then starting to prepare for plasma spraying on the modified dispersed copper;
s3: adjusting the arc voltage of the plasma spraying equipment to be 55-70V, the arc current to be 1100-ion 1300A, the powder feeding speed to be 5-8g/min, the spraying distance to be 10-15cm, adopting a multi-layer spraying mode, wherein the spraying thickness of each layer is 20-40 mu m, and each layer of metal film is sprayed according to the volume ratio of argon to hydrogen of 2:1, introducing mixed gas into a vacuum chamber, increasing the pressure of the gas by 0.2-0.6MPa, and finally quenching the metal film with the final thickness of 200-ion 500 mu m.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103447668A (en) * 2013-08-27 2013-12-18 中国船舶重工集团公司第七二五研究所 Welding method for dispersion copper
CN105418131A (en) * 2015-12-30 2016-03-23 哈尔滨工业大学 Alumina ceramic low temperature brazing connection method
CN106000476A (en) * 2016-05-19 2016-10-12 武汉凯迪工程技术研究总院有限公司 Preparation method of boron modified alumina

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103447668A (en) * 2013-08-27 2013-12-18 中国船舶重工集团公司第七二五研究所 Welding method for dispersion copper
CN105418131A (en) * 2015-12-30 2016-03-23 哈尔滨工业大学 Alumina ceramic low temperature brazing connection method
CN106000476A (en) * 2016-05-19 2016-10-12 武汉凯迪工程技术研究总院有限公司 Preparation method of boron modified alumina

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