CN114055010A - Copper-based alloy brazing filler metal containing trace Ge, preparation method and brazing method thereof - Google Patents
Copper-based alloy brazing filler metal containing trace Ge, preparation method and brazing method thereof Download PDFInfo
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- CN114055010A CN114055010A CN202111307103.9A CN202111307103A CN114055010A CN 114055010 A CN114055010 A CN 114055010A CN 202111307103 A CN202111307103 A CN 202111307103A CN 114055010 A CN114055010 A CN 114055010A
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- 239000000956 alloy Substances 0.000 title claims abstract description 106
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 106
- 238000005219 brazing Methods 0.000 title claims abstract description 87
- 239000010949 copper Substances 0.000 title claims abstract description 54
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims description 40
- 239000002184 metal Substances 0.000 title claims description 40
- 239000000945 filler Substances 0.000 title claims description 23
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910000679 solder Inorganic materials 0.000 claims abstract description 100
- 238000002844 melting Methods 0.000 claims abstract description 34
- 230000008018 melting Effects 0.000 claims abstract description 33
- 238000003723 Smelting Methods 0.000 claims abstract description 13
- 239000003082 abrasive agent Substances 0.000 claims abstract description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 238000004140 cleaning Methods 0.000 claims description 30
- 229910000831 Steel Inorganic materials 0.000 claims description 29
- 239000010959 steel Substances 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 229910052732 germanium Inorganic materials 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 238000005498 polishing Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
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- 238000007605 air drying Methods 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims 1
- 229910003460 diamond Inorganic materials 0.000 description 37
- 239000010432 diamond Substances 0.000 description 37
- 229910000927 Ge alloy Inorganic materials 0.000 description 15
- 239000000853 adhesive Substances 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 9
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Classifications
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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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/302—Cu as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/10—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration
- B08B3/12—Cleaning involving contact with liquid with additional treatment of the liquid or of the object being cleaned, e.g. by heat, by electricity or by vibration by sonic or ultrasonic vibrations
-
- 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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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention relates to the technical field of superhard abrasives, in particular to a copper-based alloy solder containing trace Ge, a preparation method and a brazing method thereof, wherein the alloy solder comprises, by mass, 64-70% of Cu, 17-20% of Sn, 7-10% of Ti, 1-5% of Ga and 0-5% of Ge. When the content of Ge is too much, a brittle phase can be generated, and the alloy solder obtained by smelting the formula in a vacuum arc furnace has the advantages of low price, low melting point, high hardness and wear resistance, high shear strength and the like.
Description
Technical Field
The invention relates to the technical field of superhard abrasives, in particular to a copper-based alloy solder containing trace Ge, a preparation method and a brazing method thereof.
Background
With the rapid development of modern industry, the material processing enters the era of high-efficiency precision operation, and the diamond has the advantages of high hardness, excellent physical and mechanical properties and the like, so that the use of diamond manufacturing tools becomes industrial hot tide. However, diamond also has certain limitation, because diamond has extremely high interface energy with alloy and metal, the wettability between low-melting point alloy and diamond particles is very poor, the cohesiveness is very poor, in the traditional process, the utilization rate of diamond in most impregnated tools is low, and a large amount of expensive diamond falls off to become scraps in the work. This is because the diamond particles are embedded in the matrix metal matrix only by mechanical clamping forces and do not form metallurgical bonds and strong chemical bonds, so that the diamond particles are easily detached during use, greatly reducing the life and performance levels of the diamond tool. In forest-growing and the like, a diamond surface metallization technology is firstly utilized to endow the diamond surface with a plurality of new characteristics, such as high wear resistance, excellent heat conductivity and electrical conductivity, high heat stability, improved physical and chemical properties, improved wettability of diamond to metal or alloy and the like. Recently, many researchers have attempted to use brazing to make diamond tools and have raised a hot tide of brazing diamond tools.
In view of the above-mentioned drawbacks, the inventors of the present invention have finally obtained the present invention through a long period of research and practice.
Disclosure of Invention
The invention aims to solve the problems of poor fluidity, low climbing height, poor wettability and easy caking of the existing copper-based brazing filler metal, and provides a copper-based alloy brazing filler metal containing trace Ge, a preparation method and a brazing method thereof.
In order to realize the aim, the invention discloses a copper-based alloy solder containing trace Ge, which comprises the following components in percentage by mass: 64-70% of Cu, 17-20% of Sn, 7-10% of Ti, 1-5% of Ga and 0-5% of Ge.
The invention also discloses a preparation method of the copper-based alloy solder containing trace Ge, which comprises the following steps:
s1: weighing 64-70% of Cu, 17-20% of Sn, 7-10% of Ti, 1-5% of Ga and 0-5% of Ge in percentage by mass, cleaning under ultrasonic waves, and then air-drying, thereby further removing oxides and impurities;
s2: vacuum melting the Cu, Ti and Ge in the step S1 under the current of 2A-5A to obtain alloy ingot Cu-Ti-Ge;
s3: and putting Sn and Ga into a furnace chamber, and smelting under vacuum by using current of 2A-5A to obtain the alloy solder Cu-Sn-Ti-Ga-Ge.
The specific process of cleaning under ultrasonic waves and air-drying in the step S1 is as follows: and cleaning the symmetrically-taken raw materials by using acetone under ultrasonic waves for 5-10 min, cleaning by using alcohol under ultrasonic waves for 5-10 min, and finally naturally drying.
In the step S2, Ar gas is used as protective gas to fill the vacuum arc furnace during smelting.
And the times of smelting the alloy ingots in the steps S2 and S3 are 2-3 times.
The invention also discloses a brazing method of the copper-based alloy brazing filler metal containing trace Ge, which comprises the following steps:
(1) placing the alloy solder Cu-Sn-Ti-Ga-Ge into a melting pit of a furnace chamber, installing a suction casting mold below the melting pit, melting the alloy solder under the current of 2A-5A, flowing into the suction casting mold below, and cooling to obtain a sheet alloy solder;
(2) taking the superhard abrasive and a steel substrate, and polishing and cleaning;
(3) ultrasonic cleaning the sheet alloy solder obtained in the step (1), the superhard abrasive material treated in the step (2) and the steel substrate respectively by acetone and alcohol, coating a binder on the steel substrate, putting the sheet alloy solder on the binder, and then putting the sheet alloy solder on the binder at a vacuum degree of 1 multiplied by 10-3And (4) brazing below Pa, heating to 940 ℃, preserving heat for 6min, cooling to room temperature, and taking out a brazed sample.
In the step (1), the flaky alloy brazing filler metal needs to be ground to be 0.5mm thick by 600#, 1000#, 1500# abrasive paper after suction casting.
And (2) wiping the furnace chamber and the suction casting mold with alcohol before suction casting in the step (1).
And (3) screening and selecting the superhard abrasive material in the step (2), wherein the size of the superhard abrasive material is 40 meshes.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with other brazing filler metals, the alloy brazing filler metal obtained by the invention has higher shearing strength, so that the shearing strength of the joint of a brazed product is high, the effect of fully connecting the superhard abrasive material and the alloy brazing filler metal is facilitated, and the strength of the welded joint is improved. Meanwhile, the brazing filler metal can effectively improve the matching between the brazing filler metal and a base metal in welding, and the residual stress of a welding joint is greatly reduced.
(2) Among the elements selected by the alloy solder, Sn belongs to the melting reduction element, so that the wettability of the alloy solder can be obviously improved, and Ti can greatly improve the bonding strength of the alloy solder and diamond; ga belongs to melting point reducing elements, can effectively reduce the melting point and simultaneously increase the wettability of the alloy solder. The main function of adding trace alloy elements is as follows: the liquidus temperature of the alloy solder is reduced, so that the wettability of the solder is increased; the hardness and the wear resistance of the alloy solder are improved; the components of the alloy solder are homogenized, and the performance is improved; wherein, the function of adding the trace alloy elements is as follows:
cu: the fluidity and the wettability of the alloy solder are improved, and the corrosion resistance, the plasticity and the ductility of a welding joint are enhanced;
sn: the grains are refined, the wear resistance is improved, and the melting point is reduced;
ti: precipitation strengthening is performed, and the hardness and the shear strength are improved;
ga: belongs to melting reduction elements and improves the wettability;
ge: the conductivity, the creep resistance and the wear resistance are improved, the aging hardening and strengthening effects of the alloy are enhanced, the activity is high in the surface growth process, and the wettability is increased;
(3) the invention firstly researches and develops Cu20Sn10Ti0.1GaxThe novel Ge Cu-based solder is researched based on a brazing principle and an alloying theory, and through comparison and optimization of performances of alloy solders with different components, the melting point of the solder is reduced when trace Ge is added, and the aging strengthening effect and the mechanical property of a soldered joint are improved;
(4) the invention provides a step-by-step smelting process for solving the problem of non-uniform alloy elements in the smelting process. The alloy ingot smelted by the process is smooth and flat, and has no holes and black spots.
(5) The novel Cu-based alloy solder prepared by the invention greatly changes the microscopic morphology of the alloy structure, when the content of Ge is 1%, the crystal grains are obviously refined, and when the content of Ge is too high, the crystal grains are obviously coarse;
(6) the novel Cu-based alloy solder prepared by the invention greatly improves the shear strength of the alloy solder from 310.9MPa when the Ge content is 0 percent to 486.7MPa when the Ge content is 1 percent;
(7) the novel Cu-based alloy solder prepared by the invention greatly improves the Vickers hardness of the alloy solder from 218.17 when the content of Ge is 0% to 414.13 when the content of Ge is 4%.
Drawings
FIG. 1 is a schematic view of the step-wise melting of an alloy according to the present invention;
FIG. 2 is a SEM illustration of a Cu-based alloy solder made with 0%, 1%, 2%, 3%, 4% Ge;
FIG. 3 is a DSC curve of a Cu-based alloy solder made with 0%, 1%, 2%, 3%, 4% Ge;
FIG. 4 is a shear strength line graph of a Cu-based alloy solder made with 0%, 1%, 2%, 3%, 4% Ge;
FIG. 5 is a schematic diagram of a Cu-based alloy solder shear fracture morphology made of 0%, 1%, 2%, 3%, 4% Ge;
FIG. 6 is a Vickers hardness broken line diagram of a Cu-based alloy solder containing 0%, 1%, 2%, 3%, 4% Ge.
Detailed Description
The above and further features and advantages of the present invention are described in more detail below with reference to the accompanying drawings.
Example 1
The preparation method of the Cu-based alloy solder containing Ge and the brazing method using the solder of the embodiment comprise the following steps:
(1) taking Cu, Sn, Ti, Ga and Ge metal ingots, polishing impurities such as surface oxides by using metallographic abrasive paper of No. 320 and No. 600, then weighing 6.8g of Cu, 2g of Sn, 1g of Ti, 0.1g of Ga and 0.1g of Ge by using an electronic balance, putting the weighed metal ingots in a beaker, adding acetone, cleaning for 5-10 min under ultrasonic, adding alcohol, cleaning for 5-10 min under ultrasonic, and finally drying;
(2) firstly, placing a dried spare Cu, Ti and Ge metal ingot in a vacuum arc furnace, vacuumizing, filling high-purity Ar gas as protective gas, and smelting for 2-3 times under the current of 2-5A;
(3) taking out the Cu-Ti-Ge alloy, placing Sn and Ga in a melting pit, adding the Cu-Ti-Ge alloy, vacuumizing, and melting the alloy for 2-3 times under the current of 2-5A in a tungsten electrode melting arc heating mode; after cooling to room temperature, taking out the alloy solder Cu-Sn-Ti-Ga-Ge from the vacuum arc furnace;
(4) sampling: the alloy cast ingot is made into a sheet solder with the thickness of 0.5mm by suction casting and then is polished, and the sheet solder is made into a regular block solder with the size of 3.5 multiplied by 6 multiplied by 20mm by cutting and polishing, wherein the sheet solder is used for soldering diamond, and the regular block solder is used for measuring the shear strength of the alloy solder;
(5) placing the sieved diamond in a beaker, adding acetone, ultrasonically cleaning for 8min to remove impurities such as oil stain, oxide skin and the like, then placing the beaker with alcohol, ultrasonically cleaning for 8min, blow-drying, and drying the diamond in a drying oven;
(6) the steel for test is 45# steel, all surfaces of a steel matrix, particularly brazing surfaces, are polished by using metallographic abrasive paper of 180#, 320#, 600#, and 1000# respectively until the surfaces are flat and smooth, then ultrasonic cleaning is carried out in acetone and alcohol for 10min respectively, and a blower blows and dries;
(7) smearing adhesive on cleaned steel substrate, putting brazing sheet on the adhesive to ensure vacuum degree of 1X 10 in furnace-3Brazing is carried out below Pa, the temperature is heated to 940 ℃, and the heat preservation is carried out for 6 min; when the temperature in the furnace is cooled to be lower than 100 ℃, closing the furnace, and taking out the brazing sample when the temperature in the furnace is cooled to be room temperature;
(8) uniformly spreading diamond on the brazing sample obtained by pre-brazing, brazing in a vacuum induction unidirectional hot pressing furnace, and maintaining the vacuum in the furnace at 1 × 10-3Heating to 940 deg.C below Pa, and keeping the temperature for 6 min; when the temperature in the furnace is cooled to room temperature, the brazing sample is taken out, and a sample of the brazing joint with good performance is obtained.
Example 2
The preparation method of the Cu-based alloy solder containing Ge and the brazing method using the solder of the embodiment comprise the following steps:
(1) taking Cu, Sn, Ti, Ga and Ge, grinding impurities such as surface oxides by using metallographic abrasive paper of No. 320 and No. 600, weighing 6.7g of Cu, 2g of Sn, 1g of Ti, 0.1g of Ga and 0.2g of Ge, putting the weighed metal ingot into a beaker, adding acetone, ultrasonically cleaning for 5-10 min, adding alcohol, ultrasonically cleaning for 5-10 min, and finally drying;
(2) firstly, placing a dried spare Cu, Ti and Ge metal ingot in a vacuum arc furnace, vacuumizing, filling high-purity Ar gas as protective gas, and smelting for 2-3 times under the current of 2-5A to obtain Cu-Ti-Ge alloy;
(3) taking out the Cu-Ti-Ge alloy, placing Sn and Ga in a melting pit, adding the Cu-Ti-Ge alloy, vacuumizing, and melting the alloy for 2-3 times under the current of 2-5A in a tungsten electrode melting arc heating mode; and cooling to room temperature, and taking the alloy solder Cu-Sn-Ti-Ga-Ge out of the vacuum arc furnace.
(4) Sampling: the alloy cast ingot is made into a sheet solder with the thickness of 0.5mm by suction casting and then is polished, and the sheet solder is made into a regular block solder with the size of 3.5 multiplied by 6 multiplied by 20mm by cutting and polishing, wherein the sheet solder is used for soldering diamond, and the block solder is used for measuring the shear strength of the alloy solder;
(5) placing the sieved diamond in a beaker, adding acetone, ultrasonically cleaning for 8min to remove impurities such as oil stain, oxide skin and the like, then placing the beaker with alcohol, ultrasonically cleaning for 8min, blow-drying, and drying the diamond in a drying oven;
(6) the steel for test is 45# steel, all surfaces of a steel matrix, particularly brazing surfaces, are polished by using metallographic abrasive paper of 180#, 320#, 600# and 1000# respectively until the surfaces are flat and smooth, then ultrasonic cleaning is carried out in acetone and alcohol for 10min respectively, and a blower blows and dries;
(7) smearing adhesive on cleaned steel substrate, putting brazing sheet on the adhesive to ensure vacuum degree of 1X 10 in furnace-3Brazing is carried out below Pa, the temperature is heated to 940 ℃, and the heat preservation is carried out for 6 min; when the temperature in the furnace is cooled to be lower than 100 ℃, closing the furnace, and taking out the brazing sample when the temperature in the furnace is cooled to be room temperature;
(8) coating adhesive on cleaned steel substrate, putting brazing sheet on the adhesive, and maintaining vacuum in furnace at 1 × 10-3Heating to 940 deg.C below Pa, and keeping the temperature for 6 min; when the temperature in the furnace is cooled to room temperature, the brazing sample is taken out, and a sample of the brazing joint with good performance is obtained.
Example 3
(1) Taking Cu, Sn, Ti, Ga and Ge metal ingots, polishing impurities such as surface oxides by using metallographic abrasive paper of No. 320 and No. 600, then weighing 6.6g of Cu, 2g of Sn, 1g of Ti, 0.1g of Ga and 0.3gGe by using an electronic balance, putting the weighed metal ingots in a beaker, adding acetone, ultrasonically cleaning for 5-10 min, then adding alcohol, ultrasonically cleaning for 5-10 min, and finally drying;
(2) firstly, placing a dried spare Cu, Ti and Ge metal ingot in a vacuum arc furnace, vacuumizing, filling high-purity Ar gas as protective gas, and smelting for 2-3 times under the current of 2-5A to obtain Cu-Ti-Ge alloy;
(3) taking out the Cu-Ti-Ge alloy, placing Sn and Ga in a melting pit, adding the Cu-Ti-Ge alloy, vacuumizing, and melting the alloy for 2-3 times under the current of 2-5A in a tungsten electrode melting arc heating mode; after cooling to room temperature, taking out the alloy solder Cu-Sn-Ti-Ga-Ge from the vacuum arc furnace;
(4) sampling: the alloy cast ingot is made into a sheet solder with the thickness of 0.5mm by suction casting and then is polished, and the sheet solder is made into a regular block solder with the size of 3.5 multiplied by 6 multiplied by 20mm by cutting and polishing, wherein the sheet solder is used for soldering diamond, and the block solder is used for measuring the shear strength of the alloy solder;
(5) placing the sieved diamond in a beaker, adding acetone, ultrasonically cleaning for 8min to remove impurities such as oil stain, oxide skin and the like, then placing the beaker with alcohol, ultrasonically cleaning for 8min, blow-drying, and drying the diamond in a drying oven;
(6) the steel for test is 45# steel, all surfaces of a steel matrix, particularly brazing surfaces, are polished by using metallographic abrasive paper of 180#, 320#, 600#, and 1000# respectively until the surfaces are flat and smooth, then ultrasonic cleaning is carried out in acetone and alcohol for 10min respectively, and a blower blows and dries;
(7) smearing adhesive on cleaned steel substrate, putting brazing sheet on the adhesive to ensure vacuum degree of 1X 10 in furnace-3Brazing is carried out below Pa, the temperature is heated to 940 ℃, and the heat preservation is carried out for 6 min; when the temperature in the furnace is cooled to be lower than 200 ℃, closing the furnace, and taking out the brazing sample when the temperature in the furnace is cooled to be room temperature;
(8) uniformly spreading diamond on the brazing sample obtained by pre-brazing, brazing in a vacuum induction unidirectional hot pressing furnace, and maintaining the vacuum in the furnace at 1 × 10-3Pa or less, heating toKeeping the temperature at 940 ℃ for 6 min; and when the temperature in the furnace is cooled to room temperature, taking out the brazing sample to obtain a sample of the brazing joint with good performance.
Example 4
(1) Taking Cu, Sn, Ti, Ga and Ge metal ingots, polishing impurities such as surface oxides by using metallographic abrasive paper of No. 320 and No. 600, then weighing 6.5g of Cu, 2g of Sn, 1g of Ti, 0.1g of Ga and 0.4gGe by using an electronic balance, putting the weighed metal ingots in a beaker, adding acetone, ultrasonically cleaning for 5-10 min, then adding alcohol, ultrasonically cleaning for 5-10 min, and finally drying;
(2) firstly, placing a dried spare Cu, Ti and Ge metal ingot in a vacuum arc furnace, vacuumizing, filling high-purity Ar gas as protective gas, and smelting for 2-3 times under the current of 2-5A to obtain Cu-Ti-Ge alloy;
(3) taking out the Cu-Ti-Ge alloy, placing Sn and Ga in a melting pit, adding the Cu-Ti-Ge alloy, vacuumizing, and melting the alloy for 2-3 times under the current of 2-5A in a tungsten electrode melting arc heating mode; after cooling to room temperature, taking out the alloy solder Cu-Sn-Ti-Ga-Ge from the vacuum arc furnace;
(4) sampling: the alloy cast ingot is made into a sheet solder with the thickness of 0.5mm by suction casting and then is polished, and the sheet solder is made into a regular block solder with the size of 3.5 multiplied by 6 multiplied by 20mm by cutting and polishing, wherein the sheet solder is used for soldering diamond, and the block solder is used for measuring the shear strength of the alloy solder;
(5) placing the sieved diamond in a beaker, adding acetone, ultrasonically cleaning for 8min to remove impurities such as oil stain, oxide skin and the like, then placing the beaker with alcohol, ultrasonically cleaning for 8min, blow-drying, and drying the diamond in a drying oven;
(6) the steel for test is 45# steel, all surfaces of a steel matrix, particularly brazing surfaces, are polished by using metallographic abrasive paper of 180#, 320#, 600#, and 1000# respectively until the surfaces are flat and smooth, then ultrasonic cleaning is carried out in acetone and alcohol for 10min respectively, and a blower blows and dries;
(7) smearing adhesive on cleaned steel substrate, putting brazing sheet on the adhesive to ensure vacuum degree of 1X 10 in furnace-3The brazing is carried out under Pa, and the brazing is carried out,heating to 940 deg.C, and maintaining the temperature for 6 min; when the temperature in the furnace is cooled to be lower than 100 ℃, closing the furnace, and taking out the brazing sample when the temperature in the furnace is cooled to be room temperature;
(8) uniformly spreading diamond on the brazing sample obtained by pre-brazing, brazing in a vacuum induction unidirectional hot pressing furnace, and maintaining the vacuum in the furnace at 1 × 10-3Heating to 940 deg.C below Pa, and keeping the temperature for 6 min; and when the temperature in the furnace is cooled to room temperature, taking out the brazing sample to obtain a sample of the brazing joint with good performance.
Comparative example
(1) Taking Cu, Sn, Ti and Ga metal ingots, polishing impurities such as surface oxides by using metallographic abrasive paper of No. 320 and No. 600, then weighing 6.9g of Cu, 2g of Sn, 1g of Ti and 0.1g of Ga by using an electronic balance, putting the weighed metal ingots in a beaker, adding acetone, ultrasonically cleaning for 5-10 min, then adding alcohol, ultrasonically cleaning for 5-10 min, and finally drying;
(2) firstly, placing a dried spare Cu and Ti metal ingot in a vacuum arc furnace, vacuumizing, filling high-purity Ar gas as protective gas, and smelting for 2-3 times under the current of 2-5A to obtain Cu-Ti-Ge alloy;
(3) taking out the Cu-Ti-Ge alloy, placing Sn and Ga in a melting pit, adding the Cu-Ti-Ge alloy, melting for 2-3 times under vacuum by using current of 2-5A, and obtaining Cu-Sn-Ti-Ga-Ge alloy solder after the alloy is cooled to room temperature;
(4) sampling: suction casting and polishing the alloy cast ingot to prepare a sheet solder with the thickness of 0.5mm, and cutting and polishing the alloy cast ingot to prepare a regular block solder with the size of 3.5 multiplied by 6 multiplied by 20mm, wherein the sheet solder is used for soldering diamond, and the block solder is used for measuring the shear strength of the alloy solder;
(5) placing the sieved diamond in a beaker, adding acetone, ultrasonically cleaning for 8min to remove impurities such as oil stain, oxide skin and the like, then placing the beaker with alcohol, ultrasonically cleaning for 8min, blow-drying, and drying the diamond in a drying oven;
(6) the steel for the test is 45# steel, all surfaces of a steel matrix, particularly a brazing surface, are polished by 180#, 320#, and 600# abrasive paper respectively before use until the surface is flat and smooth, then the steel matrix is ultrasonically cleaned in acetone and alcohol for 10min respectively, and a blower blows the steel matrix for drying;
(7) smearing adhesive on cleaned steel substrate, putting brazing sheet on the adhesive to ensure vacuum degree of 1X 10 in furnace-3Brazing is carried out below Pa, the temperature is heated to 940 ℃, and the heat preservation is carried out for 6 min; when the temperature in the furnace is cooled to be lower than 100 ℃, closing the furnace, and taking out the brazing sample when the temperature in the furnace is cooled to be room temperature;
(8) uniformly spreading diamond on the brazing sample obtained by pre-brazing, brazing in a vacuum induction unidirectional hot pressing furnace, and maintaining the vacuum in the furnace at 1 × 10-3Heating to 940 deg.C below Pa, and keeping the temperature for 6 min; and when the temperature in the furnace is cooled to room temperature, taking out the brazing sample to obtain a sample of the brazing joint with good performance.
The performance of the copper-based total brazing filler metal prepared in the examples 1 to 4 and the comparative example was tested, and the test results were as follows:
1. micro-morphology
FIG. 2 is a microstructure diagram of the alloy solder with 0%, 1%, 2%, 3% and 4% Ge added, and it can be known from the diagrams (a), (b), (c), (d) and (e) that the structure of the alloy solder is uniformly refined, the structure is compact and has no defects, which meets the requirements; when 0%, 2% and 3% of Ge is added, the structure of the alloy solder is coarse, the structure is sparse, and particularly when the content of Ge is more than or equal to 2%, the structure is coarse and is in a block shape, because Ge elements are enriched at an interface and are in solid solution with Cu atoms, the diffusion among atoms and the generation of a Cu-rich phase are hindered.
2. DSC testing of solder
A differential scanning calorimeter is adopted to test a relation curve of heat flow to temperature to obtain a DSC curve shown in figure 3, the melting point of the alloy solder in figure 3 does not change greatly along with the increase of Ge content, but the general trend of gradual reduction is shown, which shows that the melting point can be reduced by adding Ge element, but the effect is not obvious. It can be seen that the liquidus temperature of the solder is 885.1 deg.C for the desired effect, so the brazing temperature can be performed on it in the examples.
3. Shear strength of brazing filler metal
After the shearing experiments were performed on the brazing filler metals prepared in examples 1 to 4 and comparative example 1, a graph showing the relationship between the shearing strength and the Ge content of the alloy brazing filler metal shown in fig. 4 was obtained, and it is known that the shear strength of the alloy brazing filler metal gradually decreased when the Ge element content in the alloy brazing filler metal was 2%, 3%, and 4%. This is because too much Ge element causes enrichment at the interface and produces a brittle phase, hindering diffusion between atoms and formation of CuSn3Ti5 phase. When the content of Ge is 1%, a small amount of Ge element is enriched at the interface, but a brittle phase is not generated, the shear strength of the brazing filler metal reaches the maximum value of 486.7MPa, the shear strength of the alloy brazing filler metal with the content of Ge of 0% is only 310.9MPa, and the performance is remarkably improved.
4. Shear fracture morphology of brazing filler metal
After the alloy solders prepared in examples 1 to 4 and comparative example 1 were subjected to a shearing experiment, fracture morphology was observed, and from the fracture morphology with different Ge contents in fig. 5, it can be seen that when the Ge content is 1%, fracture pits are more, and cleavage planes are fewer, which indicates ductile fracture. Fracture morphology pits with Ge contents of 0%, 2%, 3% and 4% are few and cleavage planes are much. The alloy solder has more pits, which indicates that the solder has better plasticity and high shear strength.
5. Micro hardness test of brazing
From the graph of the relationship between the microhardness and the Ge content in fig. 6, it can be known that the microhardness of the alloy solder increases with the increase of the Ge content, because the addition of trace Ge element can refine the crystal grains, thereby improving the hardness of the alloy, and when the Ge content increases to a certain value, the hardness of the alloy solder further increases due to the generation of brittle phases.
In conclusion, the copper-based composite brazing filler metal for brazing the diamond provided by the invention has the advantages of uniform and refined structure, high hardness and wear resistance, high shear strength, good plasticity and toughness and excellent performance. The alloy solder has low melting point, and can effectively reduce the heat damage of the diamond during soldering.
The foregoing is merely a preferred embodiment of the invention, which is intended to be illustrative and not limiting. It will be understood by those skilled in the art that various changes, modifications and equivalents may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The copper-based alloy brazing filler metal containing trace Ge is characterized by comprising the following components in percentage by mass: 64-70% of Cu, 17-20% of Sn, 7-10% of Ti, 1-5% of Ga and 0-5% of Ge.
2. A method for preparing a copper base alloy solder containing trace Ge according to claim 1, characterized by comprising the steps of:
s1: weighing 64-70% of Cu, 17-20% of Sn, 7-10% of Ti, 1-5% of Ga and 0-5% of Ge in percentage by mass, cleaning under ultrasonic waves, and then air-drying, thereby further removing oxides and impurities;
s2: vacuum melting the Cu, Ti and Ge in the step S1 under the current of 2A-5A to obtain alloy ingot Cu-Ti-Ge;
s3: and putting Sn and Ga into a furnace chamber, and smelting under vacuum by using current of 2A-5A to obtain the alloy solder Cu-Sn-Ti-Ga-Ge.
3. The method for preparing the copper-based alloy solder containing the trace amount of Ge according to claim 2, wherein the specific process of air-drying after cleaning under ultrasonic waves in the step S1 is as follows: and cleaning the symmetrically-taken raw materials by using acetone under ultrasonic waves for 5-10 min, cleaning by using alcohol under ultrasonic waves for 5-10 min, and finally naturally drying.
4. The method for preparing the copper-based alloy solder containing the trace amount of Ge according to claim 2, wherein in the step S2, Ar gas is used as a protective gas to be filled into a vacuum arc furnace during smelting.
5. The method for preparing the copper-based alloy solder containing the trace Ge according to claim 2, wherein the alloy ingots are melted in the steps S2 and S3 for 2-3 times.
6. The brazing method of the brazing filler metal of the copper base alloy containing the trace amount of Ge according to claim 1, comprising the steps of:
(1) placing the alloy solder Cu-Sn-Ti-Ga-Ge into a melting pit of a furnace chamber, installing a suction casting mold below the melting pit, melting the alloy solder under the current of 2A-5A, flowing into the suction casting mold below, and cooling to obtain a sheet alloy solder;
(2) taking the superhard abrasive and a steel substrate, and polishing and cleaning;
(3) ultrasonic cleaning the sheet alloy solder obtained in the step (1), the superhard abrasive material treated in the step (2) and the steel substrate respectively by acetone and alcohol, coating a binder on the steel substrate, putting the sheet alloy solder on the binder, and then putting the sheet alloy solder on the binder at a vacuum degree of 1 multiplied by 10-3And (4) brazing below Pa, heating to 940 ℃, preserving heat for 6min, cooling to room temperature, and taking out a brazed sample.
7. The brazing method of the copper-based alloy solder containing the trace amount of Ge according to claim 6, wherein the thickness of the flaky alloy solder in the step (1) needs to be ground to 0.5mm by 600#, 1000#, 1500# sandpaper respectively after suction casting.
8. The brazing method of the copper-based alloy solder containing the trace amount of Ge according to claim 6, wherein an alcohol is used for wiping the furnace chamber and the suction casting mold clean before suction casting in the step (1).
9. The brazing method of the copper-based alloy solder containing the trace Ge according to claim 6, wherein the super-hard abrasive material in the step (2) is selected by sieving, and the size of the super-hard abrasive material is 40 meshes.
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| CN115351461A (en) * | 2022-09-14 | 2022-11-18 | 安徽工业大学 | Copper-based composite alloy brazing filler metal containing trace Zr, and preparation method and brazing method thereof |
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