CN111299905A - Composite brazing filler metal containing WC and ZrC simultaneously, preparation method thereof and brazing method - Google Patents
Composite brazing filler metal containing WC and ZrC simultaneously, preparation method thereof and brazing method Download PDFInfo
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- CN111299905A CN111299905A CN202010201302.0A CN202010201302A CN111299905A CN 111299905 A CN111299905 A CN 111299905A CN 202010201302 A CN202010201302 A CN 202010201302A CN 111299905 A CN111299905 A CN 111299905A
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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
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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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/008—Soldering within a furnace
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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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
Abstract
The invention discloses a composite brazing filler metal containing WC and ZrC simultaneously, a preparation method thereof and a brazing method, and belongs to the field of manufacturing of superhard abrasive tools. The composite brazing filler metal comprises a CuSnTi alloy phase and a reinforcing phase, wherein the CuSnTi alloy phase comprises, by mass, 70-75% of Cu powder, 15-20% of Sn powder and 5-10% of Ti powder, and the reinforcing phase is mixed powder of WC and ZrC, wherein the reinforcing phase accounts for 5-40% of the CuSnTi alloy phase by volume; the CuSnTi alloy phase and the reinforcing phase are mechanically mixed for a period of time, then a binder made of 5 percent of acrylic acid and 95 percent of p-xylene is added to be arranged between the welding surfaces of diamond and Q460 steel, and then the mixture is arranged in a vacuum brazing furnace for vacuum brazing. The diamond tool prepared after brazing is used for grinding experiments, the diamond holding force is high, and the particle grinding effect is good.
Description
Technical Field
The invention belongs to the field of manufacturing of superhard abrasive tools, and particularly relates to a composite brazing filler metal simultaneously containing WC and ZrC, a preparation method of the composite brazing filler metal and a brazing method.
Background
Because the diamond has ultrahigh hardness, wear resistance and corrosion resistance, the diamond is often used for preparing grinding tools, is mostly applied to industries such as energy, aerospace machinery, metallurgy, electronics, wood, stone processing and the like, and along with the increasing trend of precision and high efficiency of the production of diamond tools, great attention of various industry strong countries to the field is brought.
According to the machining theory, the machining performance of the diamond grinding tool is determined by two aspects: on one hand, the capacity of bearing load of the diamond, namely the strength of the diamond and the holding capacity of a bonding agent to the diamond; on the other hand, the shape of the diamond arrangement is very important for a single-layer fixed abrasive tool. At present, the processing method of the diamond grinding tool mostly adopts a brazing method, the bonding strength of diamond and a substrate is changed through brazing, and the brazing process is studied in detail, so that the brazing diamond grinding tool plays a positive role in developing the brazing diamond. The brazing method is used for manufacturing the diamond tool, and active brazing filler metals (such as Ag-Cu-Ti, Ni-Cr, Cu-Sn-Ti and the like) are used as bonding materials, so that the diamond and a substrate are combined with high strength. However, the solder containing noble metals such as silver is expensive, so that the cost is high; the Ni-Cr alloy has high melting point and contains catalytic elements such as Ni and Fe, so that the heat damage to diamond is easily caused in the brazing process; although Cu-Sn-Ti has low cost, low melting point and small thermal damage to diamond, the diamond grinding wheel abrasive particles have low holding strength, and are easy to fall off early in the grinding process to cause the whole grinding tool to lose efficacy. TiH is commonly used in the prior art for taking Cu-Sn-Ti alloy as brazing filler metal2The powder serves as a Ti source.
For example, chinese patent application No. 201410005561.0, published as 2014, and patent application No. 28/5, discloses a method for manufacturing a brazed single layer diamond grinding wheel. The manufacturing method of the patent comprises the following steps: preparing a matrix of the diamond grinding wheel by using a machining method, and removing oil and rust; adopts Cu powder, Sn powder and TiH powder2The mixture of the powder and the WC powder is used as brazing filler metal for brazing the diamond grinding wheel and is mechanically stirred uniformly; arranging a matrix of the diamond grinding wheel, brazing filler metal and diamond abrasive particles in sequence to manufacture a tool forming blank; and (3) putting the tool forming blank into a vacuum furnace, carrying out chemical reaction on the brazing filler metal and the diamond abrasive particles by adopting a brazing process, cooling the brazing filler metal and the diamond abrasive particles along with the furnace to room temperature, and discharging the brazing filler metal from the furnace. The invention uses TiH2The Ti source can reduce the cost of raw materials to a certain extent and simultaneously avoid oxidation pollution; to Cu powder, Sn powder, TiH2The superfine WC powder is added into the mixed powder of the powder, so that the wear resistance and the heat resistance of the brazing filler metal can be enhanced, and the graphitization of diamond can be reduced, thereby reducing the thermal damage of the diamond and fully exerting the performance of a diamond abrasive tool. However, the graphitization temperature of diamond in a vacuum atmosphere is generally about 1500 ℃, and CuSnTi solder generally does not have graphitization. The preparation technology of the Ti powder is more mature nowadays, and the cost of the Ti powder is compared with that of TiH2Lower; and TiH2At high temperatures, H may decompose2Pores are generated in a brazing filler metal layer, so that residual stress is increased, the bonding strength of diamond is seriously reduced, the diamond is easy to fall off in a grinding process, the bonding strength of the diamond is not greatly improved, and the wettability and climbing height of the brazing filler metal are not good.
For another example, chinese patent application No. 201710412312.7, published as 2017, 11, 7 discloses a Cu-Sn-Ti diamond brazing coating and a preparation method thereof. The diamond coating comprises a titanium powder layer, a tin coating and a copper coating attached to diamond, wherein the tin coating is positioned between the copper coating and the titanium powder layer. Wherein the components are as follows by mass percent: 60-80% of copper, 10-25% of tin and 5-15% of titanium. The invention also discloses a preparation method using electroplating, which comprises the steps of plating a copper layer and a tin layer on the surface of the diamond, and then mixing and sintering the plated diamond and titanium powder to obtain the Cu-Sn-Ti diamond brazing solder coating. The invention has high bonding strength with the diamond interface, and the diamond coated with the brazing solder coating has better bonding force with other bonding materials during sintering. On one hand, Ti powder is an element with high activity, when Ti is used in a heating process of a brazing experiment in a layered mode, oxygen remaining in a hot pressing furnace and exposed Ti powder can generate a chemical reaction to inactivate the Ti, the Ti is an important element in the brazing process, the Ti element is an active element, a carbide layer is generated by combining the diffusion of the element and the C element in the brazing process to achieve the tight connection between diamond and a steel matrix, and the oxidation of the Ti element can influence the bonding strength of the diamond; on the other hand, since the Ti powder needs to play a dual role of an active element and isolating diamond in the brazing process, if the Ti powder and the brazing filler metal powder are mixed in a layered manner, the added amount of the Ti powder is too large, the Ti powder is easy to oxidize in the brazing process, and can form a solid solution compound with elements such as Cu, and the Cu-Ti solid solution compound is dispersed in the matrix, so that the strength of the brazing filler metal layer is improved to a certain extent, but if the amount is too large, the brittleness of the brazing filler metal layer is increased.
Therefore, in order to improve the wettability and climbing height of the brazing filler metal, prevent the brazing filler metal from caking due to uneven distribution of the reinforcing phase, and improve the bonding strength of a diamond grinding tool and the grinding performance of diamond, the development of a composite brazing filler metal for diamond brazing, a preparation method thereof and a brazing method thereof is required.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of poor wettability and climbing height of the existing copper-based brazing filler metal and easy caking caused by uneven distribution of the brazing filler metal, the invention provides the composite brazing filler metal simultaneously containing WC and ZrC, and the wettability and climbing height of the brazing filler metal are improved and the brazing filler metal is prevented from caking by optimizing the formula of the brazing filler metal.
The invention also provides a preparation method of the composite solder containing WC and ZrC simultaneously, and aims to uniformly mix the solder.
The invention also provides a method for brazing the composite brazing filler metal containing WC and ZrC simultaneously, and aims to solve the problems that the bonding strength of diamond and a matrix is not high, the prepared diamond tool is easy to fall off in the grinding process, and the grinding performance of the diamond is poor, so that the diamond grinding tool with excellent grinding performance is obtained.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the composite brazing filler metal simultaneously containing WC and ZrC comprises a CuSnTi alloy phase and a reinforcing phase, wherein the CuSnTi alloy phase comprises, by mass, 70-75% of Cu powder, 15-20% of Sn powder and 5-10% of Ti powder, and the reinforcing phase is mixed powder of WC and ZrC, wherein the reinforcing phase accounts for 5-40% of the CuSnTi alloy phase by volume.
Further, the mass ratio of WC powder to ZrC powder in the reinforcing phase is (2-4): 1.
further, the mixing mass ratio of the Cu powder, the Sn powder and the Ti powder is 70: 20: 10; the reinforcing phase accounts for 10 to 30 percent of the volume percentage of the CuSnTi alloy phase.
Furthermore, the WC powder or the ZrC powder is micron-sized powder, wherein the grain size of the WC powder is 40-50 microns, and the grain size of the ZrC powder is 1-5 microns.
A preparation method of the composite solder comprises the following steps: the Cu powder, the Sn powder and the Ti powder are uniformly mixed to form a CuSnTi alloy phase, and then a reinforcing phase is added into the CuSnTi alloy phase for ball milling treatment for a period of time to obtain the composite solder.
Further, the ball milling treatment is carried out in a ball milling tank.
Further, the mass ratio of ball materials subjected to ball milling is 15:1, the rotating speed of the ball milling is 200-300 r/min, and the time of the ball milling is 2-5 h
A method for brazing a composite brazing filler metal containing WC and ZrC simultaneously comprises the following steps:
s101, mixing the composite solder prepared in the claim 5 and a binder into paste solder, and drying the surface moisture of the paste solder for later use;
s102, grinding and polishing the to-be-welded surface of the substrate, ultrasonically cleaning the diamond and the substrate for 20-25 min by using acetone, taking out, and naturally drying;
s103, coating an adhesive on the to-be-welded surface of the substrate to form a first adhesive layer, uniformly coating the paste brazing filler metal with the surface moisture dried in the step S101 on the first adhesive layer to form a brazing filler metal layer, coating the adhesive on the brazing filler metal layer to form a second adhesive layer, and uniformly spreading the diamond on the second adhesive layer to obtain a to-be-welded sample;
and S104, placing the to-be-welded sample obtained in the step S103 in a vacuum environment, accelerating to heat to 1020-1050 ℃, preserving heat for 15-20 min, accelerating to cool to 150-200 ℃, and then cooling to room temperature to complete the brazing of the diamond and the substrate.
Further, in the step S101, the binder is formed by mixing 5% of acrylic acid and 95% of xylene in percentage by mass, the mixing mass ratio of the composite solder to the binder is 95:5, and the paste solder is dried at the temperature of 80-100 ℃ for 10-15 min and placed in a drying oven for later use.
Further, in step S102, the substrate is Q460 steel; in step S103, the first binder layer and the second binder layer are formed by mixing and coating 5% by mass of acrylic acid and 95% by mass of xylene, and the thicknesses of the first binder layer, the second binder layer and the brazing filler metal layer are all 0.5-1 mm.
Further, in step S103, 2/5-3/5 of the diamond volume is exposed to air.
Further, in step S104, the vacuum degree of the vacuum environment is 8.0 × 10-3～5.0×10-2Pa, the heating rate is 8-10 ℃/min, and the cooling rate is 5-8 ℃/min.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the reinforcing phase is formed by mixing the micron-sized WC powder and the ZrC powder, and compared with the method that the reinforcing phase is not added or the WC powder and the ZrC powder are added separately, the reinforcing phase is further improved, the inventor finds that the joint strength and the wear resistance of the brazing filler metal alloy can be effectively improved by adding the micron-sized WC powder alone, but the bonding strength of diamond is not greatly improved; the single addition of the micron-sized ZrC powder can effectively improve the bonding strength of the diamond and simultaneously has a strengthening effect on the brazing filler metal structure, but the powder can be agglomerated in the brazing filler metal to influence the uniform distribution of the powder; by adding micron WC powder and micron ZrC mixed reinforcing phase powder into CuSnTi solder powder, micron WC can be uniformly diffused and mixed with micron ZrC, ZrC can be freely diffused between gaps formed by micron WC particles to avoid agglomeration, and the two kinds of powder with different particle sizes are mixed, so that cracks caused by stress concentration easily occurring on a reaction layer at the junction surface of diamond and a substrate after the existing solder is used for brazing are avoided, the strength and the wear resistance of a solder alloy can be improved simultaneously, the wettability and the climbing height of the solder are improved, and the bonding strength of the diamond is improved, so that the grinding performance of the diamond is improved; in addition, the hardness of the brazing filler metal can be improved by the two hard particles;
(2) the volume percentage of the reinforcing phase in the CuSnTi alloy phase is 5-40%, when the volume percentage is less than 5%, the diamond section matrix has poor shaping, the brazing filler metal flows and is seriously accumulated, so that the brazing filler metal in the diamond section matrix collapses, when the volume percentage is more than 40%, the particle proportion of the reinforcing phase is larger, the fluidity of the brazing filler metal is reduced, the wettability is reduced, and obvious cracks appear in the diamond brazing process; in the process of repeated tests, the inventor finds that the mixing mass ratio of the Cu powder, the Sn powder and the Ti powder is 70: 20: when 10 hours, the reinforcing phase accounts for 10-30% of the volume percent of the CuSnTi alloy phase, the bonding strength after diamond brazing is optimal, the grinding performance of the diamond grinding tool is optimal, diamond brazing can be basically completed when the grinding performance is lower than 10% and higher than 30%, the product quality is superior to that of a brazing filler metal without the reinforcing phase, but compared with 10-30%, the shape of a brazing matrix section is poorer when the grinding performance is lower than 10%, the brazing filler metal wraps the diamond in a complete manner, the exposed area of a cutting edge is smaller, the brazing effect is poorer, diamond cracks higher than 30% still exist, and the diamond section has obvious burning loss;
(3) the mass ratio of WC powder to ZrC powder in the reinforcing phase is (2-4): 1, when the ratio is lower than 2:1, the brazing filler metal is difficult to uniformly mix, the brazing filler metal is too dry, the brazing filler metal is easy to crack in a brazing experiment, and when the ratio is higher than 4:1, the ZrC particles account for a small amount, so that the diamond brazing effect is improved slightly;
(4) according to the invention, by adding a proper amount of hard reinforcing phase particles into the CuSnTi alloy phase, the addition amount of Ti powder can be reduced, WC and ZrC particles with low cost and high-temperature stability are selected as reinforcing phase particles, and the particle size of the mixed particles is controlled to be in a micron order, namely the particle size of WC powder is 40-50 μm, the particle size of ZrC powder is 1-5 μm, the wettability improvement effect of 40-50 μmWC powder and 1-5 μm ZrC powder on the brazing filler metal is basically equal to that of any reinforcing phase added independently, and the improvement on the brazing effect after mixing is more obvious, so that the optimal process performance is achieved;
(5) the preparation method of the composite solder of the invention utilizes a ball milling process to carry out alloying treatment on the CuSnTi alloy phase and the reinforcing phase to prepare the active copper-based solder, and the mechanical ball milling means that metal or alloy powder is subjected to long-time violent collision, extrusion and impact between the powder and a grinding ball in a high-energy ball mill, so that the powder particles generate repeated fracture, cold welding and plastic deformation, the powder tissue structure is continuously refined, and increase atomic diffusion in the powder particles, thereby obtaining an alloyed powder, the copper-based brazing filler metal prepared by the ball milling method has good uniformity, is not easy to generate enrichment of a reinforcing phase, and is beneficial to improving the bonding strength and the grinding performance of diamond after brazing;
(6) in the brazing method, the composite brazing filler metal and the binder are mixed into paste brazing filler metal and then dried for 15min at the temperature of 80 ℃ in order to remove moisture on the surface layer, and the moisture on the surface of the brazing filler metal and other residual liquid substances are removed after drying, so that the viscosity of the brazing filler metal is basically unchanged, and the uniform spreading can be met; the purpose of using 5% acrylic acid and 95% xylene to mix the binder is that the binder will directly evaporate at a temperature of about 300 ℃, and the gas amount after the organic mixture volatilizes is small, and the influence on the high vacuum is small;
(7) in the brazing method of the invention, the first binder layer is used for fixing the brazing filler metal on the surface to be brazed, the second binder layer is also coated between the diamond and the brazing filler metal, in order to fix the position of the diamond, so that the diamond is brazed basically and orderly, the two binder layers are both thin (about 0.5mm) and do not influence the brazing process, meanwhile, the binding effect of the second binder layer ensures that the part coated in the brazing filler metal is smaller when the diamond is brazed, the successful brazing can be realized under the condition that about 3/5-volume diamond is kept in the air, and the reinforcing phase of the invention is used in a matching way, the wettability of the brazing filler metal can be improved, compared with the pure CuSnTi brazing filler metal, the height of the brazing filler metal climbing on the surface of the diamond is effectively controlled, the grinding area of the diamond is improved to the maximum extent, and after multiple times of grinding, the diamond does not substantially fall off.
Drawings
FIG. 1 is a schematic structural diagram of a sample to be welded according to the present invention;
FIG. 2 is a scanning electron microscope topography of a solder alloy brazing sample with 15% reinforcing phase added in example 1;
FIG. 3 is a scanning electron microscope topography of a solder alloy brazing sample with 10% reinforcing phase added in example 3;
FIG. 4 is a scanning electron microscope topography of a solder alloy brazing sample with 30% reinforcing phase added in example 4;
FIG. 5 is a scanning electron microscope topography of a brazing filler metal alloy brazing sample without adding a reinforcing phase in comparative example 1;
FIG. 6 is a scanning electron microscope topography of a brazing filler metal alloy brazing sample with 15% WC powder added alone in comparative example 2;
FIG. 7 is a scanning electron microscope topography of a solder alloy brazing sample with 15% ZrC powder added alone in comparative example 3;
FIG. 8 is a graph of wear after frictional wear testing of brazed test specimens according to examples and comparative examples of the present invention versus time;
FIG. 9 is a graph of coefficient of friction versus time after a fretting test of a brazed specimen of the present invention.
Detailed Description
The invention is further described with reference to specific examples.
The composite brazing filler metal provided by the invention adopts the WC and ZrC added without proportion as the reinforcing phase, experiments prove that the brazing effect better than that of the existing brazing filler metal can be achieved, and the WC and ZrC proportion with the best effect is selected in the following five examples to carry out a series of experiments and tests.
Example 1
The composite brazing filler metal containing both WC and ZrC of the embodiment comprises a CuSnTi alloy phase and a WC and ZrC mixed reinforcing phase, wherein the CuSnTi alloy phase comprises 70% of Cu, 20% of Sn and 10% of Ti, the addition amount of WC powder is 10% of the volume percentage of the CuSnTi alloy phase, the granularity of WC powder is 50 μm, the addition amount of ZrC powder is 5% of the volume percentage of the CuSnTi alloy phase, and the granularity of ZrC powder is 1 μm.
The composite brazing filler metal containing WC and ZrC is used for connecting diamond and Q460 steel into a diamond grinding tool through a brazing method, and specifically, the preparation method of the composite brazing filler metal and the brazing method of the composite brazing filler metal comprise the following steps:
(1) uniformly mixing 70% of Cu powder, 20% of Sn powder and 10% of Ti powder according to mass percent to obtain a CuSnTi alloy phase;
(2) adding WC powder accounting for 10% of the volume percent of the CuSnTi alloy phase and ZrC powder accounting for 5% of the volume percent of the CuSnTi alloy phase into the CuSnTi alloy phase, putting the CuSnTi alloy phase into a ball milling tank, and carrying out ball milling treatment for 3.5 hours at a rotating speed of 250r/min to obtain the composite brazing filler metal of the embodiment, wherein the mass ratio of ball materials in the ball milling tank is 15: 1;
(3) mixing the composite solder obtained in the step (2) and a binder (5% of acrylic acid and 95% of dimethylbenzene) to form a paste solder, wherein the mixing mass ratio of the composite solder to the binder is 95: 5; drying the obtained paste solder for 15min at the temperature of 80 ℃, and placing the paste solder in a drying oven for brazing;
(4) grinding the surface to be welded of the Q460 steel by using a grinding wheel, then grinding and flattening by using metallographic abrasive paper of No. 120, No. 400, No. 600, No. 800 and No. 1000, and then polishing the surface to be welded of the Q460 steel on a polishing machine; ultrasonically cleaning the diamond and the treated steel substrate with acetone for 20min, taking out, and naturally drying;
(5) coating a first binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the surface to be welded of Q460 steel, uniformly coating the pasty brazing filler metal with the surface moisture dried in the step (3) on the binder to be welded to form a brazing filler metal layer, wherein the thickness of the brazing filler metal layer is 0.5mm, coating a second binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the brazing filler metal layer, clamping and uniformly spreading the blow-dried diamond on the second binder layer by using a pair of tweezers to obtain a sample to be welded, and as shown in figure 1, the structural schematic diagram of the sample to be welded is obtained, wherein 3/5 keeping the volume of the diamond is exposed in the air;
(6) placing the sample A to be welded obtained in the step (5) in a vacuum brazing furnace, and vacuumizing to 8.0 x 10-3～5.0×10-2Pa, heating the to-be-welded piece to 1050 ℃ at a heating speed of 10 ℃/min, preserving heat for 15min, then cooling to 200 ℃ at a speed of 5 ℃/min, and then cooling to room temperature along with the furnace, thus completing the method for brazing by connecting the diamond and the Q460 steel by using the composite brazing filler metal of the embodiment.
Example 2
The composite brazing filler metal containing both WC and ZrC of the embodiment comprises a CuSnTi alloy phase and a WC and ZrC mixed reinforcing phase, wherein the CuSnTi alloy phase comprises 70% of Cu, 20% of Sn and 10% of Ti, the addition amount of WC powder is 3.5% of the volume percentage of the CuSnTi alloy phase, the granularity of WC powder is 40 μm, the addition amount of ZrC powder is 1.5% of the volume percentage of the CuSnTi alloy phase, and the granularity of ZrC powder is 2 μm.
The composite brazing filler metal containing WC and ZrC is used for connecting diamond and Q460 steel into a diamond grinding tool through a brazing method, and specifically, the preparation method of the composite brazing filler metal and the brazing method of the composite brazing filler metal comprise the following steps:
(1) uniformly mixing 70% of Cu powder, 20% of Sn powder and 10% of Ti powder according to mass percent to obtain a CuSnTi alloy phase;
(2) adding WC powder accounting for 3.5% of the volume percent of the CuSnTi alloy phase and ZrC powder accounting for 1.5% of the volume percent of the CuSnTi alloy phase into the CuSnTi alloy phase, putting the CuSnTi alloy phase into a ball milling tank, and carrying out ball milling treatment for 2 hours at the rotating speed of 300r/min to obtain the composite brazing filler metal of the embodiment, wherein the mass ratio of ball materials in the ball milling tank is 15: 1;
(3) mixing the composite solder obtained in the step (2) and a binder (5% of acrylic acid and 95% of dimethylbenzene) to form a paste solder, wherein the mixing mass ratio of the composite solder to the binder is 95: 5; drying the obtained paste solder for 10min at the temperature of 100 ℃, and placing the paste solder in a drying oven for brazing;
(4) grinding the surface to be welded of the Q460 steel by using a grinding wheel, then grinding and flattening by using metallographic abrasive paper of No. 120, No. 400, No. 600, No. 800 and No. 1000, and then polishing the surface to be welded of the Q460 steel on a polishing machine; ultrasonically cleaning the diamond and the treated steel substrate with acetone for 25min, taking out, and naturally drying;
(5) coating a first binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the surface to be welded of Q460 steel, uniformly coating the pasty brazing filler metal with the surface moisture dried in the step (3) on the binder to be welded to form a brazing filler metal layer, wherein the thickness of the brazing filler metal layer is 1mm, coating a second binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the brazing filler metal layer, clamping and uniformly spreading the blow-dried diamond on the second binder layer by using tweezers to obtain a sample to be welded, and as shown in FIG. 1, the structural schematic diagram of the sample to be welded is obtained, wherein 2/5 for keeping the volume of the diamond is exposed in the air;
(6) placing the sample A to be welded obtained in the step (5) in a vacuum brazing furnace, and vacuumizing to 8.0 x 10-3～5.0×10-2Pa, heating the to-be-welded piece to 1050 ℃ at a heating speed of 10 ℃/min, preserving heat for 15min, then cooling to 200 ℃ at a speed of 5 ℃/min, and then cooling to room temperature along with the furnace, thus completing the method for brazing by connecting the diamond and the Q460 steel by using the composite brazing filler metal of the embodiment.
Example 3
The composite brazing filler metal containing both WC and ZrC of the embodiment comprises a CuSnTi alloy phase and a WC and ZrC mixed reinforcing phase, wherein the CuSnTi alloy phase comprises 70% of Cu, 20% of Sn and 10% of Ti, the addition amount of WC powder is 8% of the volume percentage of the CuSnTi alloy phase, the granularity of WC powder is 45 μm, the addition amount of ZrC powder is 2% of the volume percentage of the CuSnTi alloy phase, and the granularity of ZrC powder is 3 μm.
The composite brazing filler metal containing WC and ZrC is used for connecting diamond and Q460 steel into a diamond grinding tool through a brazing method, and specifically, the preparation method of the composite brazing filler metal and the brazing method of the composite brazing filler metal comprise the following steps:
(1) uniformly mixing 70% of Cu powder, 20% of Sn powder and 10% of Ti powder according to mass percent to obtain a CuSnTi alloy phase;
(2) adding WC powder accounting for 8% of the volume percent of the CuSnTi alloy phase and ZrC powder accounting for 2% of the volume percent of the CuSnTi alloy phase into the CuSnTi alloy phase, putting the CuSnTi alloy phase into a ball milling tank, and carrying out ball milling treatment for 4 hours at a rotating speed of 300r/min to obtain the composite brazing filler metal of the embodiment, wherein the mass ratio of ball materials in the ball milling tank is 15: 1;
(3) mixing the composite solder obtained in the step (2) and a binder (5% of acrylic acid and 95% of dimethylbenzene) to form a paste solder, wherein the mixing mass ratio of the composite solder to the binder is 95: 5; drying the obtained paste solder for 15min at the temperature of 80 ℃, and placing the paste solder in a drying oven for brazing;
(4) grinding the surface to be welded of the Q460 steel by using a grinding wheel, then grinding and flattening by using metallographic abrasive paper of No. 120, No. 400, No. 600, No. 800 and No. 1000, and then polishing the surface to be welded of the Q460 steel on a polishing machine; ultrasonically cleaning the diamond and the treated steel substrate with acetone for 20min, taking out, and naturally drying;
(5) coating a first binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the surface to be welded of Q460 steel, uniformly coating the pasty brazing filler metal with the surface moisture dried in the step (3) on the binder to be welded to form a brazing filler metal layer, wherein the thickness of the brazing filler metal layer is 0.7mm, coating a second binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the brazing filler metal layer, clamping and uniformly spreading the blow-dried diamond on the second binder layer by using a pair of tweezers to obtain a sample to be welded, and as shown in figure 1, the structural schematic diagram of the sample to be welded is obtained, wherein 4/5 keeping the volume of the diamond is exposed in the air;
(6) the sample to be welded obtained in the step (5) is subjected toA is put in a vacuum brazing furnace and vacuumized to 8.0 multiplied by 10-3～5.0×10-2Pa, heating the to-be-welded piece to 1050 ℃ at a heating speed of 10 ℃/min, preserving heat for 15min, then cooling to 200 ℃ at a speed of 5 ℃/min, and then cooling to room temperature along with the furnace, thus completing the method for brazing by connecting the diamond and the Q460 steel by using the composite brazing filler metal of the embodiment.
Example 4
The composite brazing filler metal containing both WC and ZrC of the embodiment comprises a CuSnTi alloy phase and a WC and ZrC mixed reinforcing phase, wherein the CuSnTi alloy phase comprises 70% of Cu, 20% of Sn and 10% of Ti, the addition amount of WC powder is 20% of the volume percentage of the CuSnTi alloy phase, the granularity of WC powder is 50 μm, the addition amount of ZrC powder is 10% of the volume percentage of the CuSnTi alloy phase, and the granularity of ZrC powder is 4 μm.
The composite brazing filler metal containing WC and ZrC is used for connecting diamond and Q460 steel into a diamond grinding tool through a brazing method, and specifically, the preparation method of the composite brazing filler metal and the brazing method of the composite brazing filler metal comprise the following steps:
(1) uniformly mixing 70% of Cu powder, 20% of Sn powder and 10% of Ti powder according to mass percent to obtain a CuSnTi alloy phase;
(2) adding WC powder accounting for 20% of the volume percent of the CuSnTi alloy phase and ZrC powder accounting for 10% of the volume percent of the CuSnTi alloy phase into the CuSnTi alloy phase, putting the CuSnTi alloy phase into a ball milling tank, and carrying out ball milling treatment for 4 hours at a rotating speed of 300r/min to obtain the composite brazing filler metal of the embodiment, wherein the mass ratio of ball materials in the ball milling tank is 15: 1;
(3) mixing the composite solder obtained in the step (2) and a binder (5% of acrylic acid and 95% of dimethylbenzene) to form a paste solder, wherein the mixing mass ratio of the composite solder to the binder is 95: 5; drying the obtained paste solder for 15min at the temperature of 80 ℃, and placing the paste solder in a drying oven for brazing;
(4) grinding the surface to be welded of the Q460 steel by using a grinding wheel, then grinding and flattening by using metallographic abrasive paper of No. 120, No. 400, No. 600, No. 800 and No. 1000, and then polishing the surface to be welded of the Q460 steel on a polishing machine; ultrasonically cleaning the diamond and the treated steel substrate with acetone for 20min, taking out, and naturally drying;
(5) coating a first binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the surface to be welded of Q460 steel, uniformly coating the pasty brazing filler metal with the surface moisture dried in the step (3) on the binder to be welded to form a brazing filler metal layer, wherein the thickness of the brazing filler metal layer is 0.5mm, coating a second binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the brazing filler metal layer, clamping and uniformly spreading the blow-dried diamond on the second binder layer by using a pair of tweezers to obtain a sample to be welded, and as shown in figure 1, the structural schematic diagram of the sample to be welded is obtained, wherein 1/2 keeping the volume of the diamond is exposed in the air;
(6) placing the sample A to be welded obtained in the step (5) in a vacuum brazing furnace, and vacuumizing to 8.0 x 10-3～5.0×10-2Pa, heating the to-be-welded piece to 1050 ℃ at a heating speed of 10 ℃/min, preserving heat for 15min, then cooling to 200 ℃ at a speed of 5 ℃/min, and then cooling to room temperature along with the furnace, thus completing the method for brazing by connecting the diamond and the Q460 steel by using the composite brazing filler metal of the embodiment.
Example 5
The composite brazing filler metal containing both WC and ZrC of the embodiment comprises a CuSnTi alloy phase and a WC and ZrC mixed reinforcing phase, wherein the CuSnTi alloy phase comprises 70% of Cu, 20% of Sn and 10% of Ti, the addition amount of WC powder is 30% of the volume percentage of the CuSnTi alloy phase, the granularity of WC powder is 50 μm, the addition amount of ZrC powder is 10% of the volume percentage of the CuSnTi alloy phase, and the granularity of ZrC powder is 5 μm.
The composite brazing filler metal containing WC and ZrC is used for connecting diamond and Q460 steel into a diamond grinding tool through a brazing method, and specifically, the preparation method of the composite brazing filler metal and the brazing method of the composite brazing filler metal comprise the following steps:
(1) uniformly mixing 70% of Cu powder, 20% of Sn powder and 10% of Ti powder according to mass percent to obtain a CuSnTi alloy phase;
(2) adding WC powder accounting for 30% of the volume percent of the CuSnTi alloy phase and ZrC powder accounting for 10% of the volume percent of the CuSnTi alloy phase into the CuSnTi alloy phase, putting the CuSnTi alloy phase into a ball milling tank, and carrying out ball milling treatment for 4 hours at a rotating speed of 300r/min to obtain the composite brazing filler metal of the embodiment, wherein the mass ratio of ball materials in the ball milling tank is 15: 1;
(3) mixing the composite solder obtained in the step (2) and a binder (5% of acrylic acid and 95% of dimethylbenzene) to form a paste solder, wherein the mixing mass ratio of the composite solder to the binder is 95: 5; drying the obtained paste solder for 15min at the temperature of 80 ℃, and placing the paste solder in a drying oven for brazing;
(4) grinding the surface to be welded of the Q460 steel by using a grinding wheel, then grinding and flattening by using metallographic abrasive paper of No. 120, No. 400, No. 600, No. 800 and No. 1000, and then polishing the surface to be welded of the Q460 steel on a polishing machine; ultrasonically cleaning the diamond and the treated steel substrate with acetone for 20min, taking out, and naturally drying;
(5) coating a first binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the surface to be welded of Q460 steel, uniformly coating the pasty brazing filler metal with the surface moisture dried in the step (3) on the binder to be welded to form a brazing filler metal layer, wherein the thickness of the brazing filler metal layer is 0.5mm, coating a second binder layer (formed by mixing and coating 5% acrylic acid and 95% xylene) with the thickness of 0.5mm on the brazing filler metal layer, clamping and uniformly spreading the blow-dried diamond on the second binder layer by using a pair of tweezers to obtain a sample to be welded, and as shown in figure 1, the structural schematic diagram of the sample to be welded is obtained, wherein 3/5 keeping the volume of the diamond is exposed in the air;
(6) placing the sample A to be welded obtained in the step (5) in a vacuum brazing furnace, and vacuumizing to 8.0 x 10-3～5.0×10-2Pa, heating the to-be-welded piece to 1050 ℃ at a heating speed of 10 ℃/min, preserving heat for 15min, then cooling to 200 ℃ at a speed of 5 ℃/min, and then cooling to room temperature along with the furnace, thus completing the method for brazing by connecting the diamond and the Q460 steel by using the composite brazing filler metal of the embodiment.
Comparative example 1
This comparative example is essentially the same as example 1, except that: in comparative example 1, no reinforcing phase was added, and a sample to be welded was prepared in the same process, and vacuum brazing was performed on the sample to be welded in the same process.
The scanning electron microscope photo of the comparative example is shown in fig. 7, and the poor diamond bonding condition and the poor diamond grinding performance can be obtained by comparing the morphology charts of the brazing samples of the examples 1-3 without adding any reinforcing phase particles.
Comparative example 2
This comparative example is essentially the same as example 1, except that: in comparative example 1, WC reinforcing phase powder 15% by volume of the CuSnTi alloy phase was separately added, a sample to be welded was prepared by the same process, and the sample to be welded was vacuum brazed according to the same process.
Comparative example 3
This comparative example is essentially the same as example 1, except that: in comparative example 1, ZrC reinforcing phase powder accounting for 15% of the volume of the CuSnTi alloy phase was separately added, a sample to be welded was prepared in the same process, and the sample to be welded was vacuum brazed in the same process.
Performance testing
Solder wettability test
As shown in fig. 2, 3 and 4, which are compared with fig. 5, 6 and 7, respectively, fig. 2, 3 and 4 (examples 1, 3 and 4) show that the overall appearance of the diamond is relatively complete, the brazing filler metal is uniformly coated, the climbing height of the brazing filler metal is not high, the fluidity of the brazing filler metal is not strong, the wettability of the brazing filler metal has a good effect of improving the coating layer of the brazing filler metal, and the diamond routing height is 2/5-3/5 of the whole; compared with the figure 5 (comparative example 1), the diamond shape is complete, the coating of the brazing filler metal is more uniform, and the diamond brazing effect is obviously improved by adding the mixed reinforcing phase particles. Comparing fig. 6 and 7 (comparative examples 2 and 3), the climbing height of the brazing filler metal is small, the exposure of the diamond is high, the shape of the diamond is complete, and no obvious thermal damage is seen. But the corresponding bonding strength is also reduced, and the cutting performance is related to the exposure and bonding strength of diamond, so that the cutting performance is not obviously changed.
The method can obtain that the solder is spread more uniformly after the micron ZrC particles are added, but the wettability of the solder is lower than that of micron WC, so that the exposed edge area of the diamond is larger, and the grindable area is increased; but the bonding strength of the diamond is relatively low, the diamond is more prone to falling off in the grinding process, and the grinding performance of the diamond is reduced. The inventors used micron-sized WC and ZrC mixed powders to improve the wettability of CuSnTi solder. The wettability of the brazing filler metal is related to the flowability of the brazing filler metal, the climbing area of the brazing filler metal is also determined by the wettability, the higher the climbing area of the brazing filler metal is, the stronger the wrapping performance of the brazing filler metal on diamond is, but the exposed area of the diamond is reduced, the cutting edge area of the diamond is reduced, and the cutting effect of the diamond is influenced. Comparing the macro morphology and SEM micro morphology after brazing, comparing the brazing alloy interface reaction layer of fig. 2 (example 1) with fig. 3 (example 3) and fig. 4 (example 4) respectively, when the addition amount is 15%, the brazing alloy interface reaction layer is relatively flat, and the 10% and 30% mixed reinforcing phase interface bonding layer has a small amount of cracks, which is caused by relatively large stress at the joint of diamond and the brazing alloy after high-temperature brazing, and the wettability of the brazing alloy is slightly weaker than that of example 1, but the effect is obviously better than that of the brazing alloy without the reinforcing phase or with WC or ZrC alone. The wettability of the solder is obviously improved by adding the mixed powder, and the wettability improvement effect is better when the addition amount accounts for 15 percent.
Secondly, testing climbing height of brazing filler metal
The climbing height of the brazing filler metal is related to the wettability of the brazing filler metal, the better the flowability of the brazing filler metal is, the wettability of the brazing filler metal is also improved, and the climbing area of the brazing filler metal is increased. The climbing area of the solder can be analyzed by testing. And performing SEM (500 x) analysis on the brazed diamond matrix, and judging the climbing height of the brazing filler metal according to the exposed height of the brazed diamond and the climbing height of the brazing filler metal along the diamond edge surface. Comparing the surface topography of the solder in fig. 2, 3 and 4 (examples 1, 3 and 4) with fig. 5, 6 and 7 (comparative examples 1, 2 and 3), respectively, the climbing height of the solder in fig. 2, 3 and 4 is lower than that in fig. 5, 6 and 7, the coating of the solder is more uniform, and the wettability of the solder is significantly improved. According to comparative analysis of FIGS. 2, 3 and 4, when the addition amount of WC and ZrC is 15%, the exposed area of diamond is about 2/5-3/5 of the whole, the cutting effect of diamond is optimal, and the climbing height of the brazing filler metal is optimal.
Third, microscopic morphology
The microscopic morphology of the diamond after vacuum brazing in the above examples 1, 3 and 4 and comparative examples 1 to 3 was observed by using a scanning electron microscope, and SEM images (fig. 2 to 4, respectively) obtained from each set of examples were compared with SEM images (fig. 5 to 7, respectively) obtained from a pure CuSnTi brazing filler metal without adding a reinforcing phase in the comparative examples. FIGS. 2 to 4 are microstructure diagrams of diamond segments after brazing by adding mixed WC and ZrC powder; FIG. 5 is a control of comparative example 1 without any reinforcing phase powder added; FIGS. 6 to 7 are morphology diagrams of diamond after brazing of comparative examples 2 and 3 with 15% WC and ZrC reinforcing phase powder added.
By SEM atlas comparative analysis, as shown in FIGS. 2, 3 and 4 (examples 1, 3 and 4), the diamond bonding was better after the brazing by adding the mixed powder of 10% WC + 5% ZrC, the brazing filler metal spreading was smoother, the exposure of the diamond grinding edge was higher, and the wettability of the brazing filler metal was greatly improved. It was analyzed in conjunction with fig. 5 (comparative example 1) that the addition of a proper amount of the mixed powder of WC and ZrC was advantageous for improving the large-area stacking of the brazing filler metal in fig. 5, which was a result of effective improvement of wettability. In contrast to fig. 2, 3 and 4, the brazing effect of examples 3 and 4 is slightly inferior to that of example 1, and the interface reaction layer of the brazing filler metal in examples 3 and 4 has a small amount of cracks, so that the brazing effect of the mixed reinforcing phase containing 15% of WC and ZrC is the best among the three. However, the bonding effect after diamond brazing of fig. 2, 3 and 4 is better and the diamond exposure is higher than that of fig. 5 (without adding any reinforcing phase), so that the grinding performance after diamond brazing with the added mixed reinforcing phase is better than that of the pure CuSnTi brazing filler metal comparative example, and the brazing filler metal is not accumulated, which shows that the wettability of the brazing filler metal with the added WC and ZrC mixed reinforcing phase is effectively improved.
Fourth, frictional wear test
The friction coefficient and the wear loss of the piece to be ground are important parameters for representing the grinding performance of the diamond brazing piece, the brazing diamond samples prepared in examples 1 to 5 and comparative examples 1 to 3 are subjected to a friction and wear test on an MFT-3000 testing machine, and the measured wear loss and friction coefficient are shown in figures 8 and 9.
Comparing the curves in fig. 8, it can be seen that: compared with the comparative example 1, the wear magnitude of the grinded pieces in the examples 1-5 is overall larger, and the friction coefficient values of the examples 1-5 combined with the graph of FIG. 9 are also at a lower level; the grinding performance of the brazing diamond of the Cu-based brazing filler metal added with the mixed reinforcing phase is obviously improved compared with that of the pure Cu-based brazing filler metal. Compared with the examples 2-5, the friction coefficient and the abrasion loss are better in the curve in the example 1, and the grinding performance of the brazing diamond by the Cu-based brazing filler metal added with the 15% mixed reinforcing phase is better.
In conclusion, the result of adding the micron WC powder and the nanometer ZrC mixed reinforcing phase powder into the CuSnTi solder powder proves that the strength and the wear resistance of the solder alloy are both improved, and meanwhile, the wettability and the climbing height of the solder are improved, so that the bonding strength of diamond is improved, and the grinding performance of diamond is improved; in addition, the addition of two hard particles can improve the hardness of the brazing filler metal.
It should be noted that, the parameters of the control conditions of the brazing method in the above embodiments may fluctuate within a reasonable range, and the range of the parameters is not the innovative point of the present invention, so that only some parameter variations are listed in the embodiments, and those skilled in the art select the parameters within a reasonable range, and still fall within the protection scope of the present invention under the situation of the innovative point of the present invention.
Claims (10)
1. The composite brazing filler metal simultaneously containing WC and ZrC is characterized in that: the alloy comprises a CuSnTi alloy phase and a reinforcing phase, wherein the CuSnTi alloy phase comprises, by mass, 70-75% of Cu powder, 15-20% of Sn powder and 5-10% of Ti powder, and the reinforcing phase is mixed powder of WC and ZrC, wherein the reinforcing phase accounts for 5-40% of the CuSnTi alloy phase by volume.
2. The composite solder containing WC and ZrC at the same time as in claim 1, wherein: the mass ratio of WC powder to ZrC powder in the reinforcing phase is (2-4): 1.
3. the composite solder containing WC and ZrC at the same time as in claim 1, wherein: the mixing mass ratio of the Cu powder to the Sn powder to the Ti powder is 70: 20: 10; the reinforcing phase accounts for 10 to 30 percent of the volume percentage of the CuSnTi alloy phase.
4. The composite solder containing WC and ZrC at the same time as in claim 3, wherein: the WC powder and the ZrC powder are micron-sized powder, wherein the grain size of the WC powder is 40-50 mu m, and the grain size of the ZrC powder is 1-5 mu m.
5. A preparation method of the composite solder as claimed in any one of claims 1 to 4, characterized in that: the method comprises the following steps: the Cu powder, the Sn powder and the Ti powder are uniformly mixed to form a CuSnTi alloy phase, then a reinforcing phase is added into the CuSnTi alloy phase, and the CuSnTi alloy phase is subjected to ball milling treatment for a period of time to obtain the composite brazing filler metal.
6. The method for preparing the composite filler metal according to claim 5, characterized in that: the mass ratio of the ball materials subjected to ball milling is 15:1, the rotating speed of the ball milling is 200-300 r/min, and the ball milling time is 2-5 h.
7. A method for brazing a composite brazing filler metal containing WC and ZrC simultaneously is characterized by comprising the following steps: the method comprises the following steps:
s101, mixing the composite solder prepared in the claim 6 and a binder into a paste solder, and drying the surface moisture of the paste solder for later use;
s102, grinding and polishing the to-be-welded surface of the substrate, ultrasonically cleaning the diamond and the substrate for 20-25 min by using acetone, taking out, and naturally drying;
s103, coating an adhesive on the to-be-welded surface of the substrate to form a first adhesive layer, uniformly coating the paste solder in the step S101 on the first adhesive layer of the to-be-welded surface to form a solder layer, coating the adhesive on the solder layer to form a second adhesive layer, and uniformly spreading the diamond on the second adhesive layer to obtain a to-be-welded sample;
and S104, placing the to-be-welded sample obtained in the step S103 in a vacuum environment, accelerating to heat to 1020-1050 ℃, preserving heat for 15-20 min, accelerating to cool to 150-200 ℃, and then cooling to room temperature to complete the brazing of the diamond and the substrate.
8. The method for brazing the composite brazing filler metal containing WC and ZrC simultaneously according to the claim 7, wherein: in the step S101, the binder is formed by mixing 5% of acrylic acid and 95% of dimethylbenzene in percentage by mass, the mixing mass ratio of the composite solder to the binder is 95:5, and the pasty solder is dried for 10-15 min at the temperature of 80-100 ℃ and placed in a drying oven for later use.
9. The method for brazing the composite brazing filler metal containing WC and ZrC simultaneously according to the claim 7, wherein: in step S102, the substrate is Q460 steel; in the step S103, the first binder layer and the second binder layer are formed by mixing and coating 5% by mass of acrylic acid and 95% by mass of xylene, and the thicknesses of the first binder layer, the second binder layer and the brazing filler metal layer are all 0.5-1 mm; 2/5-3/5 of the diamond volume are exposed to air.
10. The method for brazing the composite brazing filler metal containing WC and ZrC simultaneously according to any one of claims 7 to 9, wherein the method comprises the following steps: in step S104, the vacuum degree of the vacuum environment is 8.0 × 10-3～5.0×10-2Pa, the heating rate is 8-10 ℃/min, and the cooling rate is 5-8 ℃/min.
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