CN110616451B - Method for enhancing strength of welding interface of hard alloy and metal - Google Patents

Method for enhancing strength of welding interface of hard alloy and metal Download PDF

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CN110616451B
CN110616451B CN201910544617.2A CN201910544617A CN110616451B CN 110616451 B CN110616451 B CN 110616451B CN 201910544617 A CN201910544617 A CN 201910544617A CN 110616451 B CN110616451 B CN 110616451B
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welding
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hard alloy
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plating solution
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CN110616451A (en
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李远星
王尧
朱宗涛
石鑫
郑向博
陈辉
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Southwest Jiaotong University
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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
    • B23K1/06—Soldering, e.g. brazing, or unsoldering making use of vibrations, e.g. supersonic 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

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Abstract

The invention discloses a method for enhancing the strength of a welding interface of hard alloy and metal, which comprises the steps of adding ceramic particles into a plating solution in a sol mode to form a sol-metal substrate composite coating on a substrate, and connecting the substrate with the sol-metal substrate composite coating by a brazing method. The interface bonding strength and the mechanical property of the joint can be enhanced after welding by the method.

Description

Method for enhancing strength of welding interface of hard alloy and metal
Technical Field
The invention belongs to the field of material interface enhancement, and particularly relates to a method for enhancing the strength of a welding interface of hard alloy and metal.
Background
In recent years, with the rapid development of urban underground traffic in China and the development of large-scale projects such as the Tibetan line, shield machines are more and more in shield operation. For underground tunneling operation under different geological conditions, parts of the shield tunneling machine are required to be long-life hard alloy and metal connecting joints, higher requirements are put on welding of key parts of the shield tunneling machine, such as scrapers, and the like, wherein a welding technology of massive hard alloy and metal represented by the shield tunneling machine scrapers becomes a key technology for limiting development of the welding technology. In the tunneling process, the failure of the shield machine scraper is often caused by the fact that a large number of hard alloy blocks fall off due to low interface strength of a welding joint and poor impact load resistance. In addition, higher requirements are also put on the surface wear resistance of the hard alloy.
The most important problems of the welding member of hard alloy and steel represented by a shield machine scraper and the like are as follows: firstly, the wettability of the brazing filler metal to the hard alloy is poor, so that the interface connection strength is low, and the joint is usually damaged from the interface; secondly, when Ag-based or Cu-based brazing filler metal is adopted, the wetting to the metal side is poor, so that the connection strength of the steel side interface is low; and thirdly, the brazing filler metal mostly adopts Ag-based brazing filler metal and Cu-based brazing filler metal, and the hardness of brazing seams is low.
The following problems still exist for large components of cemented carbide and steel:
1. although a method for strengthening a brazing seam in the connection of hard alloy and metal is already proposed, the problem of weak connection of interfaces on two sides is still not solved, and the problem of chipping caused by low interface strength in the welding process of large hard alloy blocks cannot be solved.
2. Although the interface connection can be promoted by the current methods such as ultrasonic-assisted brazing, the method has the limitation of the thickness of the hard alloy sheet and the metal sheet, the thickness which can be processed is usually less than 5mm, and the method cannot be applied to large hard alloy welding pieces such as a shield machine.
3. The existing method can not solve the problems of insufficient wear resistance and insufficient hardness of the surface of the welded hard alloy.
Disclosure of Invention
The invention aims to provide a method for enhancing the strength of a welding interface of hard alloy and metal, aiming at solving the problem that hard alloy blocks fall off in the operation process due to poor impact resistance, low joint strength and poor interface strength of hard alloy components such as a large shield machine and the like. Meanwhile, the method can be applied to the strengthened interface welding between hard alloys.
The technical scheme adopted by the invention is as follows:
a welding method for enhancing a welding interface of hard alloy and metal comprises the following steps: taking hard alloy and metal as base materials, adding sol containing ceramic phase into plating solution, then electroplating a composite plating layer on the surface of at least one base material, and then welding the surface of the base material, wherein the metal comprises metal alloy.
The sol is 10-500 nm-grade nano sol containing ceramic particles.
The volume ratio of the plating solution to the sol is 1000-10: 1; preferably, the volume ratio of the plating solution to the nanosol is 500-20: 1. The plating effect of the electroplating in the range is optimal.
The thickness of the plating layer is 2-30 μm, preferably, the thickness of the plating layer is 10-20 μm, and the welding effect is better.
The preparation method of the sol comprises the following steps: mixing alkoxide containing ceramic phase with distilled water, adding alcohol solvent, regulating pH value to 3-4 with acid, and stirring at 60-80 deg.c to obtain 10-500nm level nanometer sol.
The method for electroplating the plating solution on the hard alloy and/or the metal comprises the following steps: and (3) after the surface of the base material is pretreated, putting the base material into a plating solution added with sol, and stirring until the electroplating is finished.
The welding is to weld the base material plated with the plating layer and other base materials.
The ceramic particles include: oxides, carbides, silicates and nitrides of Ti, W, Si, Al, Fe, etc. elements singly or in mixture.
The base material is pretreated, including the steps of mechanically polishing the hard alloy, then removing oil through alkalinity and acidity, and then sealing holes; and (3) sanding the metal with sand paper, then mechanically polishing, and then carrying out electrolytic polishing on the mechanically polished sample at the temperature of-25-30 ℃.
The welding mode is brazing.
The innovation point of the invention is that a coating is prepared on the surfaces of the hard alloy and the metal or the metal alloy material by a method of adding sol into the plating solution, and then the material coated with the composite coating is welded. The sol is added into the plating solution to obtain a composite plating layer which is smoothly and uniformly distributed on the surface of the substrate. The base materials plated with the composite plating layer are welded, so that a welding layer with an enhanced interface can be obtained, and the strength of a welding joint between the base materials is improved. The hardness and the wear resistance of the surface of the welded metal or alloy are greatly improved, and the service life of the engineering machinery can be prolonged.
The invention aims at the welding technology of massive hard alloy and metal represented by a shield machine scraper, and a special composite coating is plated and a welding connection mode is adopted to strengthen a welding interface. The effects of enhancing the interface strength of the welding joint and the impact load resistance are achieved.
The method adopts the following technical scheme:
a. and (4) preparing the nano sol. Mixing alkoxide containing aluminum element and distilled water in certain proportion and adding alcohol solvent. And adjusting the pH value of the solution to be between 3 and 4 by using an acid substance. Stirring is continued at a temperature of 60-80 ℃ until the solution becomes clear, so that the size of the sol is between 10-500 nm.
b. And plating a composite plating layer. Electroplating or chemical plating is adopted for plating. And (b) after the surface of the base material is pretreated, putting the base material into a plating solution, and adding the alumina nano sol obtained in the step a into the plating solution at a ratio of 1-100 ml per liter of the plating solution and stirring until the plating layer is finished.
c. And (3) welding: and welding the surface of the base material after plating. The treated sample can be subjected to high-frequency induction heating ultrasonic-assisted brazing by adopting an Ag-based or Cu-based brazing filler metal.
The main component of the hard alloy can be any metal-based element such as cobalt, nickel, molybdenum and the like as a binder, and the hard particles can be carbide or nitride ceramic particles formed by group IVB, VB and VIB metals and carbon or a mixture thereof, such as WC or TiC. Pure metal materials and alloys thereof, which may include metals and alloys thereof including but not limited to Fe, Ti, Zr, Sn, Zn, Cu, Al, Mg, Ni, Co, etc.
The sol is ceramic particle sol, and the sol can be oxide, carbide, silicate or nitride, such as oxide, carbide, silicate or nitride of Ti, W, Si, Al, Fe, etc. or their mixture.
The base material electroplated in the electroplating method is Ni or Ni-P formula. The current density is 60-150mA/cm2The temperature is room temperature, and the electroplating time is 6-20 min.
A metal base material is subjected to a pretreatment mode of mechanical polishing and electrolytic polishing; the method comprises the steps of mechanically polishing a hard alloy sample, removing oil through alkalinity and acidity, and carrying out hole sealing on the hard alloy for pretreatment. The thickness of the plating layer is controlled to be 2-30 μm.
The welding method may employ various brazing methods including, but not limited to, furnace brazing, vacuum brazing, laser brazing, arc brazing, flux brazing, scratch brazing, ultrasonic assisted brazing, and the like.
During welding, the surface nano sol composite electroplated coating can be prepared on the surfaces of the hard alloy and the metal at the same time and then welded, or the nano sol composite electroplated coating can be prepared on one side of the hard alloy or the metal and then welded.
After the hard alloy and the metal are subjected to the treatment of the nano sol composite coating, welding is carried out, and the interfaces (two sides or one side) of the welding joint have interfaces reinforced by the ceramic nano particles.
The surface side of the cemented carbide can be strengthened after welding, and the cemented carbide has good wear resistance.
The present invention was tested using a compression shear test method using an Instron-5569 electronic universal tensile machine manufactured by Instron corporation, USA.
The invention has the beneficial effects that:
1. the method of the invention utilizes the sol method to uniformly prepare the nano sol in the plating solution, and uniformly prepares the nano sol on the surfaces of the hard alloy and the metal base material by the electroplating method, the preparation method of the nano sol is simple, the cost is low, the thickness of the obtained composite electroplated layer is uniform, and the process is stable and easy to realize.
2. The nano sol composite coating prepared by the invention can greatly improve the hardness of hard alloy and metal, can also greatly improve the interface bonding strength and the mechanical property of a joint after welding, plays a role in interface strengthening, and prevents the problem of hard alloy sheet falling failure when a large-scale welding structure bears an impact load.
3. The surface of the hard alloy treated by the method of the invention also has a composite coating, and the surface of the welding joint also has high hardness and wear resistance.
4. The invention can select the corresponding welding process method according to the specific equipment and the service conditions, has flexible process and high production efficiency, and is suitable for industrial production application.
Drawings
FIG. 1 is a schematic view of a welding mode of a nano sol composite electroplated layer for enhancing interface strength. Reference numerals: 1-hard alloy, 2-composite coating, 3-welding layer, 4-composite coating, 5-metal or metal alloy, and 6-clamping device.
FIG. 2 shows the surface morphology of a metal or metal alloy nanosol composite electroplated coating.
FIG. 3 shows the cross-sectional morphology of a metal or metal alloy nanosol composite electroplated coating.
FIG. 4 shows the microstructure of the joint between the nano sol composite coating on the metal or metal alloy substrate side and the hard alloy.
FIG. 5 shows the surface morphology of a composite electroplated layer of cemented carbide nanosol.
FIG. 6 shows the cross-sectional morphology of a composite electroplated layer of a cemented carbide nanosol.
FIG. 7 shows the microstructure of the joint between the composite coating of nano sol on the side of cemented carbide and cemented carbide.
FIG. 8 shows the surface morphology of the composite electroplated layer of the hard alloy nano sol when the plating solution and the nano sol are added according to the volume ratio of 250: 3.
FIG. 9 shows the cross-sectional morphology of the composite electroplated layer of the hard alloy nano sol when the plating solution and the nano sol are added according to the volume ratio of 250: 3.
FIG. 10 shows the microstructure of the joint between the hard alloy-side nanosol composite coating and the hard alloy when added in a volume ratio of 250:3 of the plating solution to the nanosol.
FIG. 11 is a graph of post-weld shear strength of the materials of the various embodiments.
Detailed Description
In order to further illustrate the technical effects of the present invention, the present invention is specifically described below by way of examples.
Example 1
a. Preparing nano sol, namely mixing aluminum sec-butoxide and distilled water in a mass molar ratio of 0.01:12.4 under magnetic stirring, adding 5ml of alcohol, adjusting the pH value by using 1mol/l of nitric acid to ensure that the pH value of the solution is 3.5 +/-0.5, and continuously stirring at the temperature of 60-80 ℃ until the solution becomes clear to obtain the alumina nano sol.
b. According to the electroplating scheme, the composite coating electroplating method of the steel side comprises the steps of firstly grinding steel by using sand paper, then carrying out mechanical polishing, then carrying out electrolytic polishing on a sample after the mechanical polishing, mixing absolute ethyl alcohol, water and perchloric acid according to a volume ratio of 20:3:2, carrying out the electrolytic polishing on the sample at a temperature of between 25 ℃ below zero and 30 ℃ after the mechanical polishing, wherein the voltage is 1.5V, and the polishing time is 20 s. Electroplating the steel after electrolytic polishing in a plating solution with a formula of NiSO46H2O、NiCl26H2O、H3BO3The plating solution has the mixture ratio of 300g/L, 45g/L and 40g/L respectively, the current density of 100mA/cm2, the temperature of room temperature, the plating time of 10min, the rotating speed of a stirrer of 120r/min and the pH value of 3.5 +/-0.5. In the process, according to the volume ratio of the plating solution to the nano sol of 250:1, the alumina nano sol obtained in the step a is added into the plating solution and stirred until the electroplating process is completed, the surface appearance and the cross-section appearance of the obtained plating layer are shown in fig. 2 and fig. 3, and the plating layer with good combination, uniformity and no crack can be obtained, and the surface of the plating layer is smooth and uniform.
c. And (3) welding: the steel with the coating and the hard alloy without the coating are subjected to high-frequency induction heating ultrasonic auxiliary brazing at 750 ℃ by adopting the brazing filler metal and the Ag-based brazing filler metal, and a brazing seam with enhanced interface is obtained as shown in figure 4, so that a layer of Ni-Al with uniform thickness is arranged on the steel side interface2O3The interface layer is compounded, so that the interface wetting of the steel side is good, the interface strength can be greatly improved, and the shear strength of the joint obtained under the process condition is 447 MPa.
Example 2
a. Preparing nano sol, namely mixing aluminum sec-butoxide and distilled water in a mass molar ratio of 0.01:30 under magnetic stirring, adding 5ml of alcohol, adjusting the pH value by using 1mol/l of nitric acid to ensure that the pH value of the solution is 3.5 +/-0.5, and continuously stirring at the temperature of 60-80 ℃ until the solution becomes clear to obtain the alumina nano sol.
b. The electroplating scheme is that the composite coating electroplating method of the hard alloy side firstly polishes the hard alloy by sand paper and then carries out mechanical polishing, and then carries out alkaline washing and acid washing degreasing on the sample after mechanical polishing, wherein the alkaline degreasing formula comprises the following steps: sodium hydroxide, anhydrous sodium carbonate, sodium silicate and sodium phosphate, and the proportion is as follows: 80g/L, anhydrous sodium carbonate: 30g/L, sodium silicate: 15g/L, sodium phosphate: 45g/L, the sample was immersed in the solution and degreased at a temperature of 80 ℃ for 15 min. The pickling formula is to soak the materials in 15 percent sulfuric acid for 2 min. And soaking the hard alloy subjected to acid washing and alkali washing in boiling water for 1 hour for hole sealing treatment. Electroplating the hard alloy subjected to acid and alkali washing and hole sealing in a plating solution to obtain NiSO46H2O、NiCl26H2O、H3BO3Plating solution with the mass ratio of 60:9:8, and adding 1g/L sodium dodecyl sulfate into the plating solution. The current density is 100mA/cm2, the temperature is room temperature, the electroplating time is 10min, the rotating speed of the stirrer is 420r/min, and the pH value of the solution is 3.5 +/-0.5. In the process, according to the volume ratio of the plating solution to the nano sol of 1000:1, the alumina nano sol obtained in the step a is added into the plating solution and stirred until the electroplating process is completed, the surface appearance and the cross-section appearance of the obtained plating layer are shown in fig. 5 and 6, and the plating layer with good combination, uniformity and no crack can be obtained, and the surface of the plating layer is smooth and uniform.
c. And (3) welding: the brazing filler metal is adopted to carry out induction brazing on the plated hard alloy and the steel which is not plated by the Cu-based brazing filler metal at 900 ℃, brazing seams with enhanced interfaces are obtained, as shown in figure 7, a layer of Ni-Al with uniform thickness is arranged on the side interface of the hard alloy2O3The interface layer is compounded, so that the interface of the hard alloy side is well wetted, the interface strength can be greatly improved, and the shear strength of the joint obtained under the process condition is 400MPa。
Example 3
a. Preparing nano sol, namely mixing aluminum sec-butoxide and distilled water in a mass molar ratio of 0.01:30 under magnetic stirring, adding 5ml of alcohol, adjusting the pH value by using 1mol/l of nitric acid to ensure that the pH value of the solution is 3.5 +/-0.5, and continuously stirring at the temperature of 60-80 ℃ until the solution becomes clear to obtain the alumina nano sol.
b. The electroplating scheme is that the composite coating electroplating method of the hard alloy side firstly polishes the hard alloy by sand paper and then carries out mechanical polishing, and then carries out alkaline washing and acid washing degreasing on the sample after mechanical polishing, wherein the alkaline degreasing formula comprises the following steps: sodium hydroxide, anhydrous sodium carbonate, sodium silicate and sodium phosphate, and the proportion is as follows: 80g/L, anhydrous sodium carbonate: 30g/L, sodium silicate: 15g/L, sodium phosphate: 45g/L, the sample was immersed in the solution and degreased at a temperature of 80 ℃ for 15 min. The pickling formula is to soak the materials in 15 percent sulfuric acid for 2 min. And soaking the hard alloy subjected to acid washing and alkali washing in boiling water for 1 hour for hole sealing treatment. Electroplating the hard alloy subjected to acid and alkali washing and hole sealing in a plating solution to obtain NiSO46H2O、NiCl26H2O、H3BO3Plating solution with the mass ratio of 60:9:8, and adding 1g/L sodium dodecyl sulfate into the plating solution. The current density is 100mA/cm2, the temperature is room temperature, the electroplating time is 10min, the rotating speed of the stirrer is 420r/min, and the pH value of the solution is 3.5 +/-0.5. In the process, according to the volume ratio of the plating solution to the nano sol of 250:3, the alumina nano sol obtained in the step a is added into the plating solution and stirred until the electroplating process is completed, the surface appearance and the cross-section appearance of the obtained plating layer are shown in fig. 8 and 9, and the plating layer with good combination, uniformity and no crack can be obtained, and the surface of the plating layer is smooth and uniform. The thickness of the plating layer is controlled to be 10-20 μm.
c. And (3) welding: adopting brazing filler metal to carry out induction brazing on the plated hard alloy and the steel which is not plated by adopting Cu-based brazing filler metal at 900 ℃ to obtain brazing seams with enhanced interfaces, and thus a layer of Ni-Al with uniform thickness is arranged on the side interface of the hard alloy2O3The interface layer is compounded, so that the interface on the hard alloy side is well wetted, and the interface can be greatly improvedThe shear strength of the joint obtained under the process condition is 563 MPa.
Example 4
a. Preparing the nano sol containing the ceramic phase. Taking alkoxide containing aluminum element as a precursor, stirring and mixing the alkoxide and distilled water according to a proportion, adding an alcohol solvent, adjusting the pH value to be 3.5 +/-0.5 by using an acid compound, continuously stirring at the temperature of 60-80 ℃ until the solution becomes clear, and obtaining the alumina nano sol, wherein the size of the sol is 10-500 nm.
b. And (7) plating. Selecting a metal matrix as a substrate, pretreating the surface of the substrate, adopting 20g/L nickel sulfate, 45g/L ammonium citrate, 10g/L potassium iodide, 10g/L succinic acid, 5g/L ammonium chloride, pH value of 8-9, plating solution temperature of 60 ℃, chemically plating for 1h, adding the prepared nano sol into the plating solution, and stirring until the plating layer is finished. The thickness of the plating layer is controlled to be 10-20 μm. In the process, according to the volume ratio of the plating solution to the nano sol of 250:3, the alumina nano sol obtained in the step a is added into the plating solution and stirred until the plating process is finished.
c. And (6) welding. The hard alloy and the metal material coated with the composite coating are subjected to induction brazing at 750 ℃ by adopting Ag-based brazing filler metal to obtain brazing seams with enhanced interfaces, and the shear strength of the joint obtained under the process condition is improved by more than 20% compared with that of the joint without the coating.
Example 5
a. Preparing the nano sol containing the ceramic phase. Taking alkoxide containing aluminum element as a precursor, stirring and mixing the alkoxide and distilled water according to a proportion, adding an alcohol solvent, adjusting the pH value to be 3.5 +/-0.5 by using an acid compound, continuously stirring at the temperature of 60-80 ℃ until the solution becomes clear, and obtaining the alumina nano sol, wherein the size of the sol is 10-500 nm.
b. And (7) plating. Selecting two hard alloys as a base material, polishing the surface of the base material by sand paper, then performing mechanical polishing, and then performing alkaline washing and acid washing oil removal on a sample after the mechanical polishing, wherein the alkaline oil removal formula comprises the following steps: sodium hydroxide, anhydrous sodium carbonate, sodium silicate and sodium phosphate, and the proportion is as follows: 80g/L, anhydrous sodium carbonate: 30g/L, sodium silicate: 15g/L, sodium phosphate: 45 g/greaterL, immersing the sample in the solution, and degreasing at 80 ℃ for 15 min. The pickling formula is to soak the materials in 15 percent sulfuric acid for 2 min. Electroplating the hard alloy subjected to acid washing and alkali washing in a plating solution, wherein NiSO46H2O、NiCl26H2O、H3BO3Plating solution with the mass ratio of 60:9:8, and adding 1g/L sodium dodecyl sulfate into the plating solution. The current density is 100mA/cm2, the temperature is room temperature, the electroplating time is 10min, the rotating speed of the stirrer is 420r/min, and the pH value of the solution is 3.5 +/-0.5. In the process, according to the volume ratio of the plating solution to the nano sol of 250:3, the alumina nano sol obtained in the step a is added into the plating solution and stirred until the electroplating process is finished, the prepared nano sol is added into the plating solution and stirred until the plating layer is finished. The thickness of the plating layer is controlled to be 5-10 μm.
c. And (6) welding. The hard alloy plated with the composite plating layer and the other hard alloy plated with the composite plating layer are subjected to induction brazing at 900 ℃ by using Cu-based brazing filler metal to obtain brazing seams with enhanced interfaces, and the shear strength of the joint obtained under the process condition is improved by more than 15%.
Example 6
a. Preparing the nano sol containing the ceramic phase. Taking alkoxide containing aluminum element as a precursor, stirring and mixing the alkoxide and distilled water according to a proportion, adding an alcohol solvent, adjusting the pH value to be 3.5 +/-0.5 by using an acid compound, continuously stirring at the temperature of 60 ℃ until the solution becomes clear, and obtaining the alumina nano sol, wherein the size of the sol is 10-200 nm.
b. And (7) plating. Two metal alloys are selected as base materials, and the electroplating method of the composite coating on the metal or alloy side comprises the steps of firstly grinding steel by using sand paper, then carrying out mechanical polishing, and then carrying out electrolytic polishing on the sample after the mechanical polishing. Electroplating Ni on the electropolished metal or alloy in a plating solution, wherein the formula of the plating solution is NiSO46H2O、 NiCl26H2O、H3BO3The plating solution has the mixture ratio of 300g/L, 45g/L and 40g/L respectively, the current density of 100mA/cm2, the temperature of room temperature, the plating time of 10min, the rotating speed of a stirrer of 120r/min and the pH value of 3.5 +/-0.5. In the process pressAnd (b) adding the alumina nano sol obtained in the step (a) into the plating solution according to the volume ratio of the plating solution to the nano sol of 250:1, and stirring until the electroplating process is finished.
c. And (6) welding. The metal alloy material plated with the composite plating layer on the hard alloy plated with the composite plating layer is subjected to induction brazing at 900 ℃ by using Cu-based brazing filler metal to obtain brazing seams with enhanced interfaces, and the shear strength of the joint obtained under the process condition is improved by over 25 percent.
Example 7
a. Preparing nano sol, namely mixing aluminum sec-butoxide and distilled water in a mass molar ratio of 0.01:30 under magnetic stirring, adding 5ml of alcohol, adjusting the pH value by using 1mol/l of nitric acid to ensure that the pH value of the solution is 3.5 +/-0.5, and continuously stirring at the temperature of 60-80 ℃ until the solution becomes clear to obtain the alumina nano sol.
b. The electroplating scheme is that the composite coating electroplating method of the hard alloy side firstly polishes the hard alloy by sand paper and then carries out mechanical polishing, and then carries out alkaline washing and acid washing degreasing on the sample after mechanical polishing, wherein the alkaline degreasing formula comprises the following steps: sodium hydroxide, anhydrous sodium carbonate, sodium silicate and sodium phosphate, and the proportion is as follows: 80g/L, anhydrous sodium carbonate: 30g/L, sodium silicate: 15g/L, sodium phosphate: 45g/L, the sample was immersed in the solution and degreased at a temperature of 80 ℃ for 15 min. The pickling formula is to soak the materials in 15 percent sulfuric acid for 2 min. And soaking the hard alloy subjected to acid washing and alkali washing in boiling water for 1 hour for hole sealing treatment. Electroplating the hard alloy subjected to acid and alkali washing and hole sealing in a plating solution to obtain NiSO46H2O、NiCl26H2O、H3BO3Plating solution with the mass ratio of 60:9:8, and adding 1g/L sodium dodecyl sulfate into the plating solution. The current density is 100mA/cm2, the temperature is room temperature, the electroplating time is 10min, the rotating speed of the stirrer is 420r/min, and the pH value of the solution is 3.5 +/-0.5. In the process, according to the volume ratio of the plating solution to the nano sol of 10:1, the alumina nano sol obtained in the step a is added into the plating solution and stirred until the electroplating process is finished, the surface appearance and the section appearance of the obtained plating layer are shown in figures 5 and 6, and the plating layer with good combination, uniformity and no crack can be obtained, and the surface of the plating layer is smoothAnd (4) uniformity.
c. And (3) welding: the brazing filler metal is adopted to carry out induction brazing on the plated hard alloy and the steel which is not plated by the Cu-based brazing filler metal at 900 ℃, brazing seams with enhanced interfaces are obtained, as shown in figure 7, a layer of Ni-Al with uniform thickness is arranged on the side interface of the hard alloy2O3The interface layer is compounded, so that the interface wetting of the hard alloy side is good, the interface strength can be greatly improved, and the shear strength of the joint obtained under the process condition is 440 MPa.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and although the technical solutions of the present invention are described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the present invention, which should be covered by the protection scope of the present invention.

Claims (11)

1. A welding method for enhancing a welding interface of hard alloy and metal is characterized by comprising the following steps: the method comprises the steps of taking hard alloy and metal as base materials, adding alumina nano sol into chemical nickel plating solution or electrolytic nickel plating solution, then chemically plating or electroplating a composite coating on at least one base material surface, and then welding the base material surface, wherein the metal comprises metal alloy.
2. The method of claim 1, wherein the welding comprises: the alumina nano sol is 10-500nm grade nano sol.
3. The method of claim 1 or 2, wherein the welding comprises: the volume ratio of the plating solution to the sol is 1000-10: 1.
4. The method of claim 3, wherein the welding comprises: the volume ratio of the plating solution to the nano sol is 500-20: 1.
5. The method of claim 1 or 2, wherein the welding comprises: the thickness of the plating layer is 2-30 μm.
6. The method of claim 5, wherein the welding comprises: the thickness of the plating layer is 10-20 μm.
7. The method of claim 1 or 2, wherein the welding comprises: the preparation method of the sol comprises the following steps: mixing alkoxide containing aluminum element with distilled water, adding alcohol solvent, regulating pH value to 3-4 with acid, and stirring at 60-80 deg.c to obtain 10-500nm level nanometer sol.
8. The method of claim 7, wherein the welding comprises: the method for electroplating the plating solution on the hard alloy and/or the metal comprises the following steps: and (3) after the surface of the base material is pretreated, putting the base material into a plating solution added with sol, and stirring until the electroplating is finished.
9. The method of claim 8, wherein the welding comprises: the welding is to weld the base material plated with the plating layer and other base materials.
10. The welding method of claim 9, wherein the pre-treating of the substrate comprises mechanically polishing the cemented carbide, then removing oil with alkali and acid, and sealing the hole; and/or grinding the metal by sand paper, then mechanically polishing, and then carrying out electrolytic polishing on the sample after mechanical polishing at the temperature of-25-30 ℃.
11. The method of claim 10, wherein the welding is brazing.
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