CN111037150A - Composite brazing filler metal for brazing metal ceramic and alloy and preparation method thereof - Google Patents
Composite brazing filler metal for brazing metal ceramic and alloy and preparation method thereof Download PDFInfo
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- CN111037150A CN111037150A CN201911284377.3A CN201911284377A CN111037150A CN 111037150 A CN111037150 A CN 111037150A CN 201911284377 A CN201911284377 A CN 201911284377A CN 111037150 A CN111037150 A CN 111037150A
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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
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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
- B23K35/3006—Ag as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
The invention discloses a composite brazing filler metal for brazing metal ceramics and alloy and a preparation method thereof. The composite brazing filler metal comprises an AgCuTi alloy matrix and addition phase MoNi alloy particles. The preparation method of the composite solder comprises the following steps: mechanically alloying the Ag, Cu and Ti elemental powder, and mechanically alloying the Ni and Mo elemental powder; mixing the two mechanical alloying powders and ball-milling; adding an organic solvent to prepare the metal mixed powder into a paste-shaped brazing filler metal. The novel composite brazing filler metal, the metal ceramic and the alloy have good high-temperature wettability, the expansion coefficient is adjustable, the preparation process is simple, the problems of high residual stress of a welding joint of the Ti (C, N) -based metal ceramic and the alloy and poor wetting of the brazing filler metal and the ceramic are effectively solved, and the average shear strength of the welding joint obtained after the welding joint is brazed with 45 steel at room temperature can reach 263 MPa.
Description
Technical Field
The invention relates to the field of brazing, in particular to a composite brazing filler metal for brazing metal ceramics and alloy and a preparation method thereof.
Background
The Ti (C, N) -based cermet is developed on the basis of TiC-based cermet, has good high-temperature strength, hardness, wear resistance, red hardness, chemical stability and corrosion resistance, and is widely applied to the fields of molds, machining, manufacturing and the like. But the processability is poor due to the cermet and the impact resistance is poor. Cermets are often used in combination with alloyed materials such as steel when used in tools of complex shape and under impact loading. Therefore, the reliable connection of the Ti (C, N) -based cermet and the alloy has important significance and value. In addition, conventional arc welding cannot achieve their connection due to the great difference in physical and mechanical properties between ceramics and metals. Many welding methods are currently used for joining ceramics to metals, such as transition liquid phase joining, microwave joining, self-propagating high temperature composite joining, brazing, diffusion welding, and the like. Wherein brazing is widely used in its simple process and at a low cost.
However, there are two major difficulties in the joining of Ti (C, N) -based cermets to metals: the first is that the wettability of the brazing filler metal on the surface of the ceramic is poor, and some metal brazing filler metals are difficult to wet the ceramic after being melted, so that the interface combination of the ceramic and the brazing filler metal is weak; the second is that the thermal expansion coefficient and the elastic modulus of the ceramic and the metal are greatly different, which causes the joint to generate large residual stress, and is the main reason of lower joint strength. Some progress has been made in the study of the joining of Ti (C, N) -based cermets to metals. Gemcolog et al use AgCuZn alloy solder to braze Ti (C, N) -based metal ceramic and 45 steel in vacuum, and the highest shear strength of the joint is 145.2MPa when the brazing temperature is 850 ℃, the heat preservation time is 15min and the thickness of the solder is 0.4 mm. Among them, the low bonding strength of the interface between the ceramic and the brazing material and the large residual stress in the joint are the main reasons for the low strength of the joint.
Disclosure of Invention
The invention relates to a composite solder for brazing metal ceramics and alloy and a preparation method thereof, which mainly solve the problems of high joint residual stress and poor ceramic interface wettability in the existing process of connecting Ti (C, N) -based metal ceramics and alloy, realize the reliable connection of the Ti (C, N) -based metal ceramics and alloy and obtain a brazed joint with higher strength.
In order to solve the technical problems, the invention provides a composite brazing filler metal for brazing metal ceramics and alloy, which comprises an AgCuTi alloy matrix and MoNi alloy particles, wherein the mass percent of Ag, Cu and Ti in the AgCuTi alloy matrix is 50-80%, 10-30% and 3-10% respectively; the addition amount of the MoNi alloy particles accounts for 5-40% of the total mass of the AgCuTi alloy matrix.
Further, the metal ceramic is Ti (C, N) -based metal ceramic, and the metal ceramic comprises the following components in percentage by mass: TiC is more than or equal to 32% and less than or equal to 67%, TiN is more than or equal to 5% and less than or equal to 55%, Ni is more than or equal to 10% and less than or equal to 42%, Mo is more than or equal to 5% and less than or equal to 16%, WC is more than or equal to 4% and less than or equal to 20%, C is more than or equal to 0% and less than or equal to 1.2%, and a trace.
Further, the micro-additive phase comprises one or more of tantalum carbide, chromium carbide and niobium carbide.
Furthermore, the mass ratio of Mo to Ni in the MoNi alloy particles is 1: 1-5: 1, and the particle size of the alloy particles is 0.1-100 μm.
The invention provides a preparation method of a composite solder for brazing metal ceramics and alloy, which comprises the following steps:
mixing Ag, Cu and Ti metal powder according to the mass percent, uniformly mixing, and carrying out mechanical alloying to obtain an alloyed Ag-based alloy;
mixing Mo and Ni metal powder according to the mass percent, uniformly mixing, and carrying out mechanical alloying to obtain MoNi alloy particles;
carrying out ball milling and mixing on the alloyed Ag-based alloy and MoNi alloy particles to obtain mixed powder;
and taking out the mixed powder after mixing, adding the mixed powder into a mixed solution of octyl acetate and nitrocellulose, and uniformly stirring to obtain the paste solder.
Further, the mechanical alloying method comprises the following steps: putting Ag, Cu and Ti metal powder into a ball milling tank and putting the ball milling tank into a planetary ball mill under the protection of argon to be uniformly mixed.
Further, in the mechanical alloying process, the ball milling speed is 300-500 rpm, the ball milling time is 12-48 h, and the ball-to-material ratio is 10: 1-30: 1.
Further, the ball milling and mixing are carried out on a planetary ball mill, and argon is filled into a ball milling tank for protection.
Further, the ball milling rotation speed of the ball milling mixed material is 180-280 rpm, the ball milling time is 0.5-2 hours, and the ball material ratio is 5: 1-10: 1.
Further, the volume ratio of the octyl acetate to the nitrocellulose solution is 1: 1-5: 1.
The invention achieves the following beneficial effects:
1. in the invention, the active element Ti is added on the basis of the silver-based brazing filler metal, and the Ti element can react with the ceramic matrix in the brazing process to generate a reaction layer, so that the ceramic can be well wetted.
2. According to the invention, MoNi alloy particles with lower thermal expansion coefficient are added into the AgCuTi brazing filler metal, so that the overall thermal expansion coefficient of the composite brazing filler metal can be reduced, the mismatching of the thermal expansion coefficients between the ceramic and the brazing filler metal can be reduced, and the residual stress of the joint can be relieved finally.
3. The added MoNi alloy particles can improve the bonding capacity of the solder with a matrix and steel, so that the strength of a welding joint can be improved.
4. The invention adopts ball milling mixing and adds in octyl acetate and nitrocellulose organic mixed solution to prepare paste composite solder, the solder components are easy to control, the operation is simple and efficient, and the cost is lower.
5. The composite brazing filler metal prepared by the invention is applied to brazing of metal ceramics and alloy, and the shear strength of a welding joint of the composite brazing filler metal is not lower than 200 MPa. In the brazing between the Ti (C, N) -based cermet and 45 steel, the maximum value of the shear strength is 263MPa, which is obviously improved compared with the joints brazed by other brazing filler metals.
Drawings
FIG. 1 is a back-scattered electron image of a microstructure of a Ti (C, N) -based cermet/45 steel joint.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1:
according to the mass percentage: ag 69.12%, Cu 26.88% and Ti 7.84%, weighing 300-mesh Ag, Cu and Ti powders, putting the metal powders prepared in proportion into a ball milling tank, filling argon for protection, and then performing mechanical alloying on a planetary ball mill. Wherein the ball-material ratio is 10:1, the rotating speed is 300r/min, and the ball milling time is 12 h. Mo and Ni powder are weighed according to the mass percentage of 1:1 and put into a ball milling tank, argon is filled for protection, and then mechanical alloying is carried out on a planetary ball mill. Wherein the ball-material ratio is 10:1, the rotating speed is 300r/min, and the ball milling time is 24 h.
And after the mechanical alloying is finished, performing ball milling and mixing on 95% of AgCuTi powder and 5% of MoNi alloy particles in percentage by mass, and filling argon for protection. After the ball milling is finished, adding mixed powder into mixed solution of octyl acetate and nitrocellulose (volume ratio is 1: 1) to prepare paste-shaped brazing filler metal. The brazing filler metal is applied to vacuum brazing of Ti (C, N) -based metal ceramic and 45 steel, and performance detection is carried out on a brazed joint, so that the shear strength of the brazing filler metal is 245 MPa. FIG. 1 is a back-scattered electron image of a microstructure of a Ti (C, N) -based cermet/45 steel joint.
Example 2:
according to the mass percentage: ag 62%, Cu 28% and Ti 10%, weighing 300-mesh Ag, Cu and Ti powders, putting the metal powders prepared in proportion into a ball milling tank, filling argon for protection, and then carrying out mechanical alloying on a planetary ball mill. Wherein the ball-material ratio is 15:1, the rotating speed is 350r/min, and the ball milling time is 24 h. Mo and Ni powder are weighed according to the mass percentage of 2:1 and put into a ball milling tank, argon is filled for protection, and then mechanical alloying is carried out on a planetary ball mill. Wherein the ball-material ratio is 15:1, the rotating speed is 320r/min, and the ball milling time is 12 h.
And after the mechanical alloying is finished, ball-milling and mixing 93% of AgCuTi powder and 7% of MoNi alloy particles in percentage by mass, and filling argon for protection. After the ball milling is finished, adding mixed powder into mixed solution of octyl acetate and nitrocellulose (volume ratio is 2: 1) to prepare paste-shaped brazing filler metal. The brazing filler metal is applied to vacuum brazing of Ti (C, N) -based cermet and H13 steel, and performance detection is carried out on a brazed joint, so that the shear strength of the brazing filler metal is 223 MPa.
Example 3
According to the mass percentage: ag 70.82%, Cu 23.65% and Ti 5.53%, weighing 300-mesh Ag, Cu and Ti powders, putting the metal powders prepared in proportion into a ball milling tank, filling argon for protection, and then performing mechanical alloying on a planetary ball mill. Wherein the ball-material ratio is 18:1, the rotating speed is 350r/min, and the ball milling time is 48 h. Mo and Ni powder are weighed according to the mass percentage of 3:1 and put into a ball milling tank, argon is filled for protection, and then mechanical alloying is carried out on a planetary ball mill. Wherein the ball-material ratio is 20:1, the rotating speed is 350r/min, and the ball milling time is 36 h.
And after the mechanical alloying is finished, performing ball milling and mixing on 92% of AgCuTi powder and 8% of MoNi alloy particles in mass percent, and filling argon for protection. After the ball milling is finished, adding mixed powder into mixed solution of octyl acetate and nitrocellulose (volume ratio is 3: 1) to prepare paste-shaped brazing filler metal. The brazing filler metal is applied to vacuum brazing of Ti (C, N) -based metal ceramic and FeCr alloy, and then performance detection is carried out on a brazed joint, and the result shows that the shearing strength of the brazing filler metal is 204 MPa.
Example 4
According to the mass percentage: ag 65.59%, Cu 27.72% and Ti 7.68%, weighing 300-mesh Ag, Cu and Ti powders, putting the prepared metal powders into a ball milling tank in proportion, filling argon for protection, and then performing mechanical alloying on a planetary ball mill. Wherein the ball-material ratio is 20:1, the rotating speed is 500r/min, and the ball milling time is 36 h. Mo and Ni powder are weighed according to the mass percentage of 4:1 and put into a ball milling tank, argon is filled for protection, and then mechanical alloying is carried out on a planetary ball mill. Wherein the ball-material ratio is 18:1, the rotating speed is 400r/min, and the ball milling time is 48 h.
And after the mechanical alloying is finished, performing ball milling and mixing on 92% of AgCuTi powder and 8% of MoNi alloy particles in mass percent, and filling argon for protection. After the ball milling is finished, adding mixed powder into mixed solution of octyl acetate and nitrocellulose (volume ratio is 4: 1) to prepare paste-shaped brazing filler metal. The brazing filler metal is applied to vacuum brazing of Ti (C, N) -based metal ceramic and NiCr stainless steel, and performance detection is carried out on a brazed joint, so that the shear strength of the brazing filler metal is 227 MPa.
Example 5
According to the mass percentage: weighing 300-mesh Ag, Cu and Ti powders, putting the metal powders prepared in proportion into a ball milling tank, filling argon for protection, and then carrying out mechanical alloying on a planetary ball mill. Wherein the ball-material ratio is 20:1, the rotating speed is 500r/min, and the ball milling time is 32 h. Mo and Ni powder are weighed according to the mass percentage of 5:1 and put into a ball milling tank, argon is filled for protection, and then mechanical alloying is carried out on a planetary ball mill. Wherein the ball-material ratio is 20:1, the rotating speed is 300r/min, and the ball milling time is 48 h.
And after the mechanical alloying is finished, performing ball milling and mixing on 92% of AgCuTi powder and 8% of MoNi alloy particles in mass percent, and filling argon for protection. After the ball milling is finished, adding mixed powder into mixed solution of octyl acetate and nitrocellulose (volume ratio is 5: 1) to prepare paste-shaped brazing filler metal. The brazing filler metal is applied to vacuum brazing of Ti (C, N) -based cermet and 316 stainless steel, and performance detection is carried out on a brazed joint, so that the shear strength of the brazing filler metal is 227 MPa.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A composite brazing filler metal for brazing metal ceramics and alloy is characterized in that: the material comprises an AgCuTi alloy matrix and MoNi alloy particles, wherein the mass percentages of Ag, Cu and Ti in the AgCuTi alloy matrix are that Ag is between 50 and 80 percent, Cu is between 10 and 30 percent, and Ti is between 3 and 10 percent; the addition amount of the MoNi alloy particles accounts for 5-40% of the total mass of the AgCuTi alloy matrix.
2. A composite filler metal for cermet and alloy brazing according to claim 1, characterised in that: the metal ceramic is Ti (C, N) -based metal ceramic, and the metal ceramic comprises the following components in percentage by mass: TiC is more than or equal to 32% and less than or equal to 67%, TiN is more than or equal to 5% and less than or equal to 55%, Ni is more than or equal to 10% and less than or equal to 42%, Mo is more than or equal to 5% and less than or equal to 16%, WC is more than or equal to 4% and less than or equal to 20%, C is more than or equal to 0% and less than or equal to 1.2%, and a trace.
3. A composite filler metal for cermet and alloy brazing according to claim 2, characterised in that: the micro-additive phase comprises one or more of tantalum carbide, chromium carbide and niobium carbide.
4. A composite filler metal for cermet and alloy brazing according to claim 1, characterised in that: the mass ratio of Mo to Ni in the MoNi alloy particles is 1: 1-5: 1, and the particle size of the alloy particles is 0.1-100 mu m.
5. A method for preparing a composite filler metal for brazing cermet and alloy according to anyone of claims 1-4, characterized in that: the method comprises the following steps:
preparing Ag, Cu and Ti metal powder according to the mass percent of claim 1, uniformly mixing, and carrying out mechanical alloying to obtain an alloyed Ag-based alloy;
mixing Mo and Ni metal powder according to the mass percent in claim 4, uniformly mixing, and carrying out mechanical alloying to obtain MoNi alloy particles;
carrying out ball milling and mixing on the alloyed Ag-based alloy and MoNi alloy particles to obtain mixed powder;
and taking out the mixed powder after mixing, adding the mixed powder into a mixed solution of octyl acetate and nitrocellulose, and uniformly stirring to obtain the paste solder.
6. The method for preparing the composite solder for brazing the metal ceramic and the alloy according to claim 5, wherein the method comprises the following steps: the mechanical alloying method comprises the following steps: putting Ag, Cu and Ti metal powder into a ball milling tank and putting the ball milling tank into a planetary ball mill under the protection of argon to be uniformly mixed.
7. The method for preparing the composite solder for brazing the metal ceramic and the alloy according to claim 5, wherein the method comprises the following steps: in the mechanical alloying process, the ball milling speed is 300-500 rpm, the ball milling time is 12-48 h, and the ball-to-material ratio is 10: 1-30: 1.
8. The method for preparing the composite solder for brazing the metal ceramic and the alloy according to claim 5, wherein the method comprises the following steps: the ball milling and mixing are carried out on a planetary ball mill, and argon is filled into a ball milling tank for protection.
9. The method for preparing the composite solder for brazing the metal ceramic and the alloy according to claim 5, wherein the method comprises the following steps: the ball milling rotation speed of the ball milling mixed material is 180-280 rpm, the ball milling time is 0.5-2 h, and the ball material ratio is 5: 1-10: 1.
10. The method for preparing the composite solder for brazing the metal ceramic and the alloy according to claim 5, wherein the method comprises the following steps: the volume ratio of the octyl acetate to the nitrocellulose solution is 1: 1-5: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112372179A (en) * | 2020-10-29 | 2021-02-19 | 西北工业大学 | Alloy solder for connecting stainless steel and carbon/carbon composite material and preparation and use method thereof |
| CN114473289A (en) * | 2022-01-20 | 2022-05-13 | 浙江亚通焊材有限公司 | AgCu-based brazing filler metal and method for brazing and connecting diamond and copper by using AgCu-based brazing filler metal |
| CN115846934A (en) * | 2022-12-12 | 2023-03-28 | 广东华智芯电子科技有限公司 | Composite solder and preparation method and packaging method thereof |
| CN116477969A (en) * | 2023-04-27 | 2023-07-25 | 无锡湃泰电子材料科技有限公司 | Active molybdenum-silver copper titanium slurry for ceramic metallized packaging and preparation method thereof |
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| CN114473289A (en) * | 2022-01-20 | 2022-05-13 | 浙江亚通焊材有限公司 | AgCu-based brazing filler metal and method for brazing and connecting diamond and copper by using AgCu-based brazing filler metal |
| CN115846934A (en) * | 2022-12-12 | 2023-03-28 | 广东华智芯电子科技有限公司 | Composite solder and preparation method and packaging method thereof |
| CN116477969A (en) * | 2023-04-27 | 2023-07-25 | 无锡湃泰电子材料科技有限公司 | Active molybdenum-silver copper titanium slurry for ceramic metallized packaging and preparation method thereof |
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Application publication date: 20200421 |