A nickel-based superalloy brazing adhesive tape filler metal, a preparation method and application thereof

Abstract

This invention relates to a nickel-based superalloy brazing adhesive tape, its preparation method, and its application, belonging to the field of superalloy vacuum brazing technology. The adhesive tape consists of 90%–95% alloy brazing alloy powder and the remainder an organic binder. The organic binder is an epoxy-based binder, composed of epoxy resin, a composite amine curing agent, a compound tackifier, and a reactive toughening agent. During preparation, the above components are stirred and mixed evenly, rolled into a tape, and then cured and packaged to obtain the adhesive tape. The thickness of this adhesive tape can be adjusted within the range of 0.1–2 mm, exhibiting good flexibility and a shelf life exceeding 12 months. During brazing, the organic binder completely volatilizes within the range of 350–550°C, leaving no residue. The wetting angle between the brazing alloy and the base material is less than 20°, enabling high-quality connections in complex structures. This invention features a simple preparation process, is environmentally friendly, produces low residual carbon after welding, and results in a uniform joint structure and excellent mechanical properties, meeting the technical requirements for vacuum brazing of nickel-based superalloy components in aerospace and other fields.

Description

Technical Field

[0001] This invention belongs to the field of brazing materials technology, specifically relating to a nickel-based high-temperature alloy brazing adhesive tape filler metal, its preparation method, and its application. Background Technology

[0002] Nickel-based superalloys are core materials for hot-end components of aero-engines and gas turbines, and the quality of their connections directly determines the service performance of the equipment. Brazing is a crucial process for achieving connections in the complex structures of these alloys. However, traditional powder or paste brazing fillers have limitations in terms of coating uniformity, positioning accuracy, and the ability to fill large gaps (0.15~0.8mm), making it difficult to meet the stringent requirements of precise filler placement and compositional consistency for complex components. To overcome these problems, adhesive-backed brazing fillers, as pre-formed fillers that can be cut and easily bonded, have attracted widespread attention, especially in the assembly of complex components such as aero-engine honeycomb sealing rings and hollow blades, demonstrating significant advantages and becoming an indispensable joining material in high-end manufacturing.

[0003] While adhesive solder tapes show significant potential for adaptability to complex structures, their overall performance is highly dependent on the rational design of the organic binder system. Currently, common binder formulations still suffer from a series of systemic defects in practical applications: for example, the binder system disclosed in patent (CN111872593B) relies on a combination of plasticizer (terpene resin) + first diluent, toughening agent (elastomer) + second diluent. The use of diluents not only easily leads to post-soldering residue but also reduces the storage stability of the adhesive tape; the polymethyl methacrylate system used in patent (CN117506223A) often relies on toxic solvents such as dichloroethane, posing a threat to the production environment and human health; while the polystyrene-based system in patent (CN116082964A) helps reduce residue, it easily leads to problems such as tape embrittlement and poor adhesion. Furthermore, existing patents lack a reasonable design for alloy powder particle size, resulting in poor filling uniformity, insufficient process adaptability, and unsatisfactory weld joint quality.

[0004] In summary, current adhesive brazing filler metal technology has not yet systematically solved the balance issues between environmental friendliness, residual carbon control, storage stability, and process adaptability. In particular, it lacks an integrated solution that can simultaneously achieve wide-range adjustable thickness, long-term flexibility, green low-residue properties, and excellent weld formation. Therefore, developing a novel flexible adhesive brazing filler metal suitable for nickel-based superalloy brazing to overcome existing technological bottlenecks has become crucial for improving the brazing quality and manufacturing efficiency of high-end equipment such as aero-engines. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a nickel-based superalloy brazing adhesive tape with excellent comprehensive performance, its preparation method and application. The adhesive tape brazing material can simultaneously meet the technical requirements of: adjustable thickness in the range of 0.1~2mm, shelf life of more than 12 months, complete volatilization of organic components at 350℃~550℃ without residue, and wetting angle with nickel-based superalloy base material of less than 20 degrees. Moreover, through the rational design of organic components and the precise particle size distribution of alloy brazing powder, the defects of existing technologies such as reliance on diluents, short shelf life, residual carbon after welding, and uneven filling are solved.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: In a first aspect, the present invention provides a nickel-based high-temperature alloy brazing adhesive tape, which, by mass percentage, consists of 90%~95% alloy brazing alloy powder and 5%~10% organic binder. The organic binder is a diluent-free two-component system. The adhesive tape has a shelf life of more than 12 months and a residual carbon content of less than 0.05% after welding. The organic binder contains 0.5%~1.5% of a nano-scale graphene oxide modifier, which is surface-treated with silane coupling agent KH550 and has a sheet thickness of 1~5 nm. The alloy brazing alloy powder also contains 0.1%~0.3% of nano-scale titanium carbide particles with a particle size of 50~200 nm, which are surface-modified with silane coupling agent KH560.

[0007] The alloy brazing powder is selected from one or more of B-Ni55NbCoWCrAlSiMoTi(C)-S, GHL-6-2, HBCo43CrNiWBSi, and HBCo51CrNiSiW; the alloy brazing powder adopts a precise three-level particle size distribution, with 10%~20% of the powder having a particle size of 74μm~150μm, 60%~80% of the powder having a particle size of 48μm~74μm, and 10%~20% of the powder having a particle size not greater than 48μm; the alloy brazing powder undergoes vacuum annealing treatment at an annealing temperature of 800℃~900℃ and a holding time of 2 hours~4 hours to reduce the oxide film thickness on the powder surface to below 5nm. During the vacuum annealing process, a mixed protective gas of 5%~10% by volume of hydrogen and argon is introduced to further remove impurities adsorbed on the powder surface.

[0008] The organic binder is composed of component A and component B mixed in an equimolar ratio. Component A contains epoxy resin, compound tackifier, and reactive toughening agent, while component B contains a composite amine curing agent. After mixing components A and B, the mixture needs to be allowed to stand at 15℃~25℃ for 5min~10min to eliminate air bubbles generated during the mixing process. The viscosity of the mixed system is controlled at 5000mPa·s~15000mPa·s to meet the requirements of subsequent rolling processes. 0.2%~0.5% of nano-sized silica dispersion is also added to component A. The solid content of the dispersion is 30%~40%, the dispersion medium is anhydrous ethanol, and the nano-sized silica has a particle size of 20~50nm.

[0009] Component A, by mass percentage, comprises 50%–80% epoxy resin, 30%–40% compounding tackifier, and 10%–30% reactive toughening agent. The epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic type epoxy resin. The epoxy equivalent of the bisphenol A type epoxy resin is 180 g / eq–240 g / eq, the epoxy equivalent of the bisphenol F type epoxy resin is 160 g / eq–190 g / eq, and the epoxy equivalent of the phenolic type epoxy resin is 168 g / eq–185 g / eq. When different types of epoxy resins are compounded, the proportion of bisphenol A type epoxy resin is not less than 50% of the total compound. 0.3%–0.8% of hindered phenolic antioxidant 1010 is added to the epoxy resin to improve the storage stability of the adhesive.

[0010] The compound tackifier is selected from one or more of poly-α-pinene resin, poly-β-pinene resin, terpene-styrene copolymer resin, and α / β-pinene copolymer resin, combined with rosin ester. The rosin ester is selected from one or more of glycerol rosin ester, pentaerythritol rosin ester, polymerized rosin ester, and maleic rosin ester. The softening point of the polyterpene resin is 80℃~125℃. The mass ratio of polyterpene resin to rosin ester in the compound tackifier is 1:0.5~1:1.5. The compound tackifier is subjected to vacuum dehydration treatment at 120℃~140℃ for 2 to 3 hours, and the moisture content is controlled below 0.1%.

[0011] The reactive toughening agent is selected from one or more of reactive liquid nitrile rubber and polyether polyol; the reactive liquid nitrile rubber is selected from one or more of carboxyl-terminated butadiene polymer, butadiene-acrylonitrile polymer, epoxy-terminated butadiene polymer, butadiene-acrylonitrile glycidyl ester polymer, epoxy-terminated butadiene-acrylonitrile resin adduct, methacrylate-terminated butadiene polymer, and butadiene-acrylonitrile polymer; the polyether polyol has a functionality of 2-3, a hydroxyl value of 20mgKOH / g-280mgKOH / g, an acid value of 0.05mgKOH / g-0.15mgKOH / g, and the proportion of propylene oxide units in the polyether polyol is not less than 60% of the total molecular structure. The reactivity index between the reactive toughening agent and the epoxy resin is controlled at 0.8-1.2 to ensure that the curing reaction is fully carried out.

[0012] Component B, by mass percentage, comprises 30%–80% polyamide, 5%–30% linear aliphatic polyamine, and 3%–15% cyclic aliphatic polyamine; the polyamide is selected from one or more of Versamid 140, Versamid 125, Aradur 450, and Aradur 115; the linear aliphatic polyamine is selected from one or more of triethylenetetramine, pentaethylenehexamine, and diethylenetriamine; the cyclic aliphatic polyamine is selected from one or more of isophorone diamine, 4,4'-diaminodicyclohexylmethane, and 1,4-cyclohexanediamine; during the preparation of component B, the heating temperature is controlled at 60°C–80°C, the stirring speed is 80 rpm–120 rpm, and 1%–3% of accelerator DMP-30 is added to component B to shorten the curing time and improve the degree of curing.

[0013] Secondly, the present invention also provides a method for preparing the above-mentioned adhesive solder, comprising the following steps: Step S1. Preparation of organic binder: Epoxy resin, compound tackifier, reactive toughening agent, antioxidant, and nano-scale graphene oxide modifier are added to a reaction vessel and heated to 60℃~80℃ and stirred for 30min~60min to obtain component A; polyamide, linear aliphatic polyamine, cyclic aliphatic polyamine, and accelerator are added to a reaction vessel and heated to 60℃~80℃ and stirred for 30min~60min to obtain component B; components A and B are mixed in equal proportions and stirred at 30rpm~500rpm for 10min~30min, and allowed to stand for 5min~10min to obtain the organic binder; Step S2. Preparation of brazing filler metal slurry: Weigh the vacuum-annealed alloy brazing filler metal powder and the organic binder obtained in step S1 according to the specified ratio, place them in a vacuum mixer, and heat them under a vacuum degree lower than 1×10⁻⁶. -1Under the condition of Pa, mix at a speed of 30 r / min to 60 r / min for 1 hour to 4 hours to obtain a paste-like brazing filler metal mixture; pre-cur at 25℃ to 35℃ for 12 hours to 48 hours to obtain a brazing filler metal slurry with preliminary strength. Step S3. Preparation of adhesive tape: Transfer the paste-like brazing filler metal mixture obtained in step S2 to a precision twin-roll mill and roll it repeatedly at room temperature 3 to 5 times. After each rolling, let it stand for 2 to 3 minutes to produce a flexible adhesive tape brazing filler metal with a thickness of 0.1 mm to 2.0 mm and a width of 10 mm to 100 mm. After cutting, attach single-sided silicone release paper, coil and package it, and store it in a cool and dry place. The relative humidity of the storage environment should be controlled at 30% to 60%. Before packaging, vacuum dry the adhesive tape brazing filler metal at 100℃ to 120℃ for 1 to 2 hours to remove residual trace moisture.

[0014] Thirdly, the present invention provides the application of the above-mentioned adhesive brazing filler metal in vacuum brazing or protective atmosphere brazing of nickel-based superalloys, comprising the following steps: Step S1. Grind the surface of the workpiece to be welded until smooth. Use acetone to ultrasonically clean the welding area of ​​the nickel-based high-temperature alloy component for 5 min to 10 min. After drying, attach the adhesive brazing filler to the welding area. The adhesion between the adhesive brazing filler and the welding area should not be less than 95%. After bonding, apply pressure of 0.1 MPa to 0.3 MPa for 10 min to 20 min to ensure tight contact at the interface. Step S2. Place the workpiece to be welded in a vacuum brazing furnace and evacuate it to a vacuum state with a vacuum degree of 1×10⁻⁶. -3 Pa ~ 1×10 -2 Pa, heated to 500℃~600℃ at a heating rate of 5℃ / min~10℃ / min, and held for 10min~15min; Step S3. Continue heating at a rate of 5℃ / min to 10℃ / min to 800℃ to 950℃, hold for 5 min to 10 min, then heat to the preset temperature at a rate of 5℃ / min to 10℃ / min and hold for 10 min to 15 min; cool to room temperature at a rate of 10℃ / min to complete the welding; the preset temperature is the melting temperature of the alloy solder powder in the adhesive solder, and the preset temperature fluctuation range does not exceed ±5℃. During the cooling process, a holding step of 5 min to 8 min is added in the 600℃ to 700℃ range to reduce thermal stress.

[0015] The adhesive brazing filler metal is suitable for brazing or repairing nickel-based superalloy components used in aero-engines and gas turbines. The organic binder completely evaporates without residue within the temperature range of 350℃ to 550℃. The wetting angle with the nickel-based superalloy base material is less than 20°. The welded joint has a uniform microstructure and low residual carbon content. The tensile strength of the joint at room temperature is not less than 850 MPa, and the tensile strength retention rate at 800℃ is not less than 70%. It is suitable for connecting nickel-based superalloy components with gaps of 0.05 mm to 1.0 mm. The joint corrosion resistance meets the requirement of no rust after 500 hours of neutral salt spray testing. The tensile strength retention rate of the brazed joint at 800℃ is 5% to 8% higher than that of brazing filler metal without added nano-sized titanium carbide particles and nano-sized silica dispersion, and the joint hardness is increased by 10% to 15%.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention effectively solves the technical problems of traditional adhesive brazing filler metals, such as reliance on diluents, poor storage stability, and easy residue of carbon impurities after welding, by optimizing the design of the organic binder system and the precise gradation of alloy brazing filler metal powder. At the same time, it significantly improves the wetting performance of the brazing filler metal and the nickel-based high-temperature alloy base material, ensuring the compactness and consistency of the connection of complex structural components, and providing a strong guarantee for the reliable connection of key components of high-end equipment.

[0017] 2. The adhesive brazing filler metal adopts a diluent-free two-component bonding system and an environmentally friendly preparation process, avoiding the harm of toxic solvents to the production environment and operators. Moreover, the adhesive can be completely decomposed and volatilized during the brazing process, leaving no harmful residues. It not only conforms to the concept of green manufacturing but also simplifies the production process and has the potential for large-scale industrial application.

[0018] 3. The adhesive brazing filler metal prepared by this invention has both good flexibility and shape retention. Its size can be precisely controlled according to actual needs, and it can be adapted to brazing or repair scenarios of nickel-based high-temperature alloy components with different gaps and structures. The welded joint has uniform structure and excellent mechanical properties, which can meet the stringent requirements of high-temperature service components in aerospace, gas turbine and other fields. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the adhesive solder preparation process in an embodiment of the present invention.

[0020] Figure 2 Figure a shows the physical images of the adhesive solder obtained in Embodiment 7 of the present invention. Figure a shows the freshly prepared adhesive solder, and Figure b shows the adhesive solder stored for 12 months.

[0021] Figure 3 These are experimental photos of the lap welding of GH3030 with the adhesive brazing filler metal obtained in Example 6 of the present invention. Figure a shows the result before welding, and Figure b shows the result after welding.

[0022] Figure 4 This is a photograph of the adhesive solder obtained in Example 6 of the present invention, which is impregnated with GH4169.

[0023] Figure 5 The TG-DSC curves are those of the adhesive solders prepared in Examples 4 to 7 of this invention. Detailed Implementation

[0024] To better understand the present invention, the following embodiments further illustrate the content of the present invention, but the content of the present invention is not limited to the following embodiments.

[0025] Example 1: Preparation of organic binder a1 Accurately weigh 150 parts of bisphenol A type epoxy resin E5, 15 parts of polyα-pinene resin, 5 parts of glycerol rosin ester, 10 parts of carboxyl-terminated butadiene-acrylonitrile polymer (CTBN), 20 parts of polyether polyol NJ-240, and 0.3 parts of nano-sized silica dispersion (solid content 35%, dispersion medium is anhydrous ethanol, particle size 30nm). Place them in a reaction vessel, heat to 70℃ and stir for 30 min to obtain component A. Accurately weigh 80 parts of polyamide Versamid 140, 5 parts of triethylenetetramine, 8 parts of pentaethylenehexamine, and 7 parts of 4,4'-diaminodicyclohexylmethane. Place them in a reaction vessel, heat to 70℃ and stir for 30 min to obtain component B. Mix components A and B in an equimolar ratio and stir at 200 r / min for 20 min to obtain organic binder a1.

[0026] Example 2: Preparation of organic binder a2 Accurately weigh 30 parts of bisphenol A type epoxy resin E44, 40 parts of bisphenol F type epoxy resin NPEF-170, 8 parts of terpene-styrene copolymer resin, 2 parts of pentaerythritol rosin ester, 20 parts of polyether polyol NJ-240, and 0.2 parts of nano-sized silica dispersion (solid content 30%, dispersion medium is anhydrous ethanol, particle size 20nm). Place them in a reaction vessel, heat to 65℃ and stir for 40 min to obtain component A. Accurately weigh 80 parts of polyamide Versamid 140, 15 parts of pentaethylenehexamine, and 5 parts of isophorone diamine. Place them in a reaction vessel, heat to 65℃ and stir for 40 min to obtain component B. Mix components A and B in an equimolar ratio and stir at 250 r / min for 15 min to obtain organic binder a2.

[0027] Example 3: Preparation of organic binder a3 Accurately weigh 140 parts of bisphenol A type epoxy resin E5, 10 parts of bisphenol F type epoxy resin NPEF-170, 6 parts of α / β-pinene copolymer resin, 4 parts of polymeric rosin ester, 30 parts of polyether polyol NJ-240, 10 parts of polyether polyol NJ-2080D, and 0.2 parts of nano-sized silica dispersion (solid content 30%, dispersion medium is anhydrous ethanol, particle size 20nm). Place them in a reaction vessel, heat to 75℃ and stir for 35 min to obtain component A. Accurately weigh 50 parts of polyamide Versamid 140, 30 parts of Versamid 125, 15 parts of pentaethylenehexamine, and 5 parts of isophorone diamine. Place them in a reaction vessel, heat to 75℃ and stir for 35 min to obtain component B. Mix components A and B in an equimolar ratio and stir at 180 r / min for 25 min to obtain organic binder a3.

[0028] Example 4: Preparation of adhesive solder based on B-Ni55NbCoWCrAlSiMoTi(C)-S powder Step S1: Preparation of solder slurry. Accurately weigh 93 parts of B-Ni55NbCoWCrAlSiMoTi(C)-S alloy powder (three-stage particle size distribution: 15% 74~150μm, 70% 48~74μm, 15% ≤48μm), 17 parts of the organic binder a prepared in Example 1, and 0.2 parts of nano-sized silica dispersion (30% solid content, anhydrous ethanol as dispersion medium, 20nm particle size). Place them in a vacuum mixer and heat under a vacuum degree lower than 1×10⁻⁶. -1 Under the condition of Pa, the mixture was stirred at 45 r / min for 2 hours to obtain a uniform paste-like solder mixture; then, it was pre-cured at 30℃ for 24 hours to obtain a solder slurry with preliminary strength. Step S2: Adhesive tape preparation. The solder slurry obtained in step S1 was transferred to a precision twin-roll mill, and by precisely adjusting the roll gap, it was repeatedly rolled 4 times at room temperature to produce a flexible adhesive tape solder with a thickness of 0.5 mm and a width of 50 mm; after cutting, single-sided silicone release paper was attached, and the packaged in coils was stored in a cool and dry place.

[0029] Example 5: Preparation of adhesive tape solder based on GHL-6-2 powder Step S1: Preparation of brazing filler metal slurry. Accurately weigh 94 parts of GHL-6-2 alloy powder (three-stage particle size distribution: 12% 74~150μm, 75% 48~74μm, 13% ≤48μm), 26 parts of organic binder a prepared in Example 2, and 0.1 parts of nano-sized titanium carbide particles (particle size 50nm, surface modified with silane coupling agent KH560). Place them in a vacuum mixer and heat under a vacuum degree lower than 1×10⁻⁶. -1Under the condition of Pa, the mixture was stirred at 35 r / min for 3 hours to obtain a uniform paste-like solder mixture; then, it was pre-cured at 28℃ for 36 hours to obtain a solder slurry with preliminary strength. Step S2: Preparation of adhesive tape. The solder slurry obtained in step S1 was transferred to a precision twin-roll mill, and rolled repeatedly 3 times at room temperature by precisely adjusting the roll gap to produce a flexible adhesive tape solder with a thickness of 1.0 mm and a width of 30 mm; after cutting, single-sided silicone release paper was attached, and the packaged in coils was stored in a cool and dry place.

[0030] Example 6: Preparation of adhesive solder based on HBCo43CrNiWBSi powder Step S1: Preparation of brazing filler metal slurry. Accurately weigh 94 parts of HBCo43CrNiWBSi alloy powder (three-stage particle size distribution: 18% 74~150μm, 65% 48~74μm, 17% ≤48μm), 6 parts of the organic binder a3 prepared in Example 3, and 0.3 parts of nano-sized titanium carbide particles (particle size 200nm, surface modified with silane coupling agent KH560). Place them in a vacuum mixer and heat under a vacuum degree lower than 1×10⁻⁶. -1 Under the condition of Pa, the mixture was stirred at 50 r / min for 1.5 hours to obtain a uniform paste-like solder mixture; then, it was pre-cured at 32℃ for 18 hours to obtain a solder slurry with preliminary strength. Step S2: Adhesive tape preparation. The solder slurry obtained in step S1 was transferred to a precision twin-roll mill, and by precisely adjusting the roll gap, it was repeatedly rolled 5 times at room temperature to produce a flexible adhesive tape solder with a thickness of 0.3 mm and a width of 80 mm; after cutting, single-sided silicone release paper was attached, and the packaged in coils was stored in a cool and dry place.

[0031] Example 7: Preparation of adhesive solder based on HBCo51CrNiSiW powder Step S1: Preparation of solder slurry. Accurately weigh 92 parts of HBCo51CrNiSiW alloy powder (three-stage particle size distribution: 20% 74~150μm, 60% 48~74μm, 20% ≤48μm), 18 parts of the organic binder a prepared in Example 1, and 0.2 parts of nano-sized titanium carbide particles (particle size 150nm, surface modified with silane coupling agent KH560). Place them in a vacuum mixer and heat under a vacuum degree lower than 1×10⁻⁶. -1Under the condition of Pa, the mixture was stirred at a speed of 40 r / min for 2.5 hours to obtain a uniform paste-like solder mixture; then, it was pre-cured at 25°C for 48 hours to obtain a solder slurry with preliminary strength. Step S2: Preparation of adhesive tape. The solder slurry obtained in step S1 was transferred to a precision twin-roll mill, and by precisely adjusting the roll gap, it was repeatedly rolled 4 times at room temperature to produce a flexible adhesive tape solder with a thickness of 1.5 mm and a width of 60 mm; after cutting, single-sided silicone release paper was attached, and the packaged in coils was stored in a cool and dry place.

[0032] Example 8: Application of adhesive brazing filler metal in GH3039 alloy lap welding Step S1: Take two GH3039 test plates with dimensions of 100×10×2mm, smooth their surfaces with sandpaper to remove oxide scale and impurities, then place them in acetone for ultrasonic cleaning for 8 minutes, and let them air dry naturally. Take the adhesive brazing filler metal prepared in Example 4, cut it into 10×10mm squares, and attach it to the surface of the part to be welded on one of the test plates (the lap length for lap welding is 10mm). Step S2: Align and assemble the two test plates with the adhesive brazing filler metal attached, place the whole assembly in a vacuum brazing furnace, close the furnace door, and evacuate the furnace to a vacuum state, controlling the vacuum degree at 5×10. -3 Step S3: Increase the temperature to 550℃ at a rate of 8℃ / min and hold for 12 minutes to allow the organic binder to fully decompose and volatilize. Step S4: Continue increasing the temperature to 900℃ at a rate of 8℃ / min and hold for 8 minutes. Then increase the temperature to 1240℃ (the melting temperature of B-Ni55NbCoWCrAlSiMoTi(C)-S powder) at a rate of 6℃ / min and hold for 12 minutes. Finally, cool to room temperature at a rate of 10℃ / min to complete the welding. The welded joint surface is bright, free of residual impurities, and exhibits good wetting.

[0033] Example 9: Application of adhesive brazing filler metal in GH3030 alloy lap welding Step S1: Take two GH3030 test plates with dimensions of 100×10×2mm, smooth their surfaces with sandpaper, place them in acetone and ultrasonically clean for 10 minutes, let them dry, then take the adhesive brazing filler metal prepared in Example 5, cut it into 10×10mm squares, and attach it to the surface of the part to be welded on the test plate (lap welding). Step S2: Place the assembled test plate in a vacuum brazing furnace and evacuate it to 8×10 -3Step S3: Continue heating at a rate of 10℃ / min to 500℃, hold for 15 min to allow the binder components to fully decompose. Step S4: Continue heating at a rate of 10℃ / min to 850℃, hold for 10 min, then heat at a rate of 5℃ / min to 1150℃ (melting temperature of GHL-6-2 powder), hold for 15 min; cool to room temperature at a rate of 10℃ / min to complete the welding. The welded joint has a uniform microstructure and excellent mechanical properties.

[0034] Example 10: Application of adhesive brazing filler metal in the repair of GH3039 alloy Step S1: Take a GH3039 test plate with dimensions of 100×10×2mm and minor surface defects. Sand the area around the defects with sandpaper, place it in acetone and ultrasonically clean for 5 minutes. After drying, take the adhesive brazing filler metal prepared in Example 6, cut it into a shape that matches the defect area, and attach it to the defect location. Step S2: Place the test plate in a vacuum brazing furnace and evacuate it to a vacuum level of 6×10. -3 Step S3: Continue heating at a rate of 7℃ / min to 580℃, hold for 10 minutes to allow the binder to fully evaporate. Step S4: Continue heating at a rate of 7℃ / min to 920℃, hold for 7 minutes, then heat at a rate of 7℃ / min to 1120℃ (the melting temperature of HBCo43CrNiWBSi powder), hold for 13 minutes; cool to room temperature at a rate of 10℃ / min to complete the repair. After repair, the defect is completely filled, the surface is smooth, and it is tightly bonded to the substrate.

[0035] Example 11: Application of adhesive brazing filler metal in DZ40M alloy welding Step S1: Take two DZ40M test plates with dimensions of 100×10×2mm, smooth their surfaces with sandpaper, place them in acetone and ultrasonically clean for 7 minutes, and let them dry. Then, take the adhesive brazing filler metal prepared in Example 7, cut it into 10×10mm squares, and attach it to the surface of the area to be soldered on the test plate. Step S2: Place the test plate in a vacuum brazing furnace and evacuate it to a vacuum level of 8×10. -3 Step S3: The temperature is increased to 600℃ at a rate of 9℃ / min and held for 11 minutes to allow for complete decomposition of the binder components. Step S4: The temperature is further increased to 950℃ at a rate of 9℃ / min and held for 5 minutes. Then, the temperature is increased to 1280℃ (the melting temperature of HBCo51CrNiSiW powder) at a rate of 8℃ / min and held for 10 minutes. The temperature is then cooled to room temperature at a rate of 10℃ / min to complete the welding. The welded joint exhibits good high-temperature resistance and meets service requirements.

[0036] Example 12: Preparation and application of hybrid alloy powder bonding brazing filler metal Step S1: Preparation of brazing filler metal slurry. Accurately weigh 46.5 parts of B-Ni55NbCoWCrAlSiMoTi(C)-S alloy powder, 46.5 parts of HBCo43CrNiWBSi alloy powder (three-stage particle size distribution after mixing: 16% 74~150μm, 68% 48~74μm, 16% ≤48μm), and 27 parts of the organic binder a prepared in Example 2. Place them in a vacuum mixer and heat under a vacuum degree lower than 1×10⁻⁶. -1 Under the condition of Pa, the mixture was stirred at a speed of 42 r / min for 2 hours to obtain a uniform paste-like brazing filler metal mixture; then, it was pre-cured at 30°C for 20 hours to obtain a brazing filler metal slurry with preliminary strength. Step S2: Adhesive tape preparation. The brazing filler metal slurry obtained in step S1 was transferred to a precision twin-roll mill and rolled repeatedly 4 times at room temperature to produce a flexible adhesive tape brazing filler metal with a thickness of 0.8 mm and a width of 40 mm; after cutting, single-sided silicone release paper was attached, and it was coiled, packaged, and stored. Step S3: Welding application. Two GH3039 test plates were taken, treated according to the pretreatment method of Example 8, the above adhesive tape brazing filler metal was attached, and placed in a vacuum brazing furnace, and the vacuum was evacuated to 5 × 10 -3 The temperature was increased to 560℃ at a rate of 8℃ / min and held for 12 minutes, then increased to 900℃ and held for 8 minutes, and finally increased to 1200℃ (the melting temperature of the mixed powder) and held for 14 minutes. The welding was then completed by cooling to room temperature. The welded joint combines the excellent properties of both alloy powders, exhibiting outstanding comprehensive mechanical properties.

[0037] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A nickel-based high-temperature alloy brazing adhesive tape, characterized in that, By weight percentage, the adhesive solder comprises 90%~95% alloy solder powder and 5%~10% organic binder, wherein the organic binder is a two-component system without diluent. The adhesive solder has a shelf life of more than 12 months and a residual carbon content of less than 0.05% after soldering. 0.5%~1.5% of nano-scale graphene oxide modifier is added to the organic binder. The graphene oxide modifier is surface-treated with silane coupling agent KH550 and has a sheet thickness of 1~5nm. 0.1%~0.3% of nano-scale titanium carbide particles with a particle size of 50~200nm are also added to the alloy solder powder and are surface-modified with silane coupling agent KH560.

2. The adhesive solder according to claim 1, characterized in that, The alloy solder powder is selected from one or more of B-Ni55NbCoWCrAlSiMoTi(C)-S, GHL-6-2, HBCo43CrNiWBSi, and HBCo51CrNiSiW. The alloy solder powder adopts a precise three-level particle size distribution, with 10%~20% of the powder having a particle size of 74μm~150μm, 60%~80% having a particle size of 48μm~74μm, and 10%~20% having a particle size no larger than 48μm. The alloy solder powder undergoes vacuum annealing treatment at a temperature of 800℃~900℃ for 2 hours to 4 hours to reduce the oxide film thickness on the powder surface to below 5nm. During the vacuum annealing process, a mixed protective gas of 5%~10% by volume of hydrogen and argon is introduced to further remove impurities adsorbed on the powder surface.

3. The adhesive solder according to claim 1, characterized in that, The organic binder is composed of component A and component B mixed in an equimolar ratio. Component A contains epoxy resin, compound tackifier, and reactive toughening agent, while component B contains a composite amine curing agent. After mixing components A and B, the mixture needs to be allowed to stand at 15℃~25℃ for 5min~10min to eliminate air bubbles generated during the mixing process. The viscosity of the mixed system is controlled at 5000mPa·s~15000mPa·s to meet the requirements of subsequent rolling processes. 0.2%~0.5% of nano-sized silica dispersion is also added to component A. The solid content of the dispersion is 30%~40%, the dispersion medium is anhydrous ethanol, and the nano-sized silica has a particle size of 20~50nm.

4. The adhesive solder according to claim 3, characterized in that, Component A, by mass percentage, comprises 50%–80% epoxy resin, 30%–40% compounding tackifier, and 10%–30% reactive toughening agent. The epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenolic type epoxy resin. The epoxy equivalent of the bisphenol A type epoxy resin is 180 g / eq–240 g / eq, the epoxy equivalent of the bisphenol F type epoxy resin is 160 g / eq–190 g / eq, and the epoxy equivalent of the phenolic type epoxy resin is 168 g / eq–185 g / eq. When different types of epoxy resins are compounded, the proportion of bisphenol A type epoxy resin is not less than 50% of the total compound. 0.3%–0.8% of hindered phenolic antioxidant 1010 is added to the epoxy resin to improve the storage stability of the adhesive.

5. The adhesive solder according to claim 4, characterized in that, The compound tackifier is selected from one or more of poly-α-pinene resin, poly-β-pinene resin, and α / β-pinene copolymer resin, combined with rosin ester. The rosin ester is selected from one or more of glycerol rosin ester, pentaerythritol rosin ester, polymerized rosin ester, and maleic rosin ester. The softening point of the polyterpene resin is 80℃~125℃. The mass ratio of polyterpene resin to rosin ester in the compound tackifier is 1:0.5~1:1.

5. The compound tackifier is subjected to vacuum dehydration treatment at 120℃~140℃ for 2 to 3 hours, and the moisture content is controlled below 0.1%.

6. The adhesive solder according to claim 4, characterized in that, The reactive toughening agent is selected from one or more of reactive liquid nitrile rubber and polyether polyol; the reactive liquid nitrile rubber is selected from one or more of carboxyl-terminated butadiene polymer, epoxy-terminated butadiene-acrylonitrile glycidyl ester polymer, epoxy-terminated butadiene-acrylonitrile resin adduct, methacrylate-terminated butadiene polymer, and butadiene-acrylonitrile polymer; the polyether polyol has a functionality of 2-3, a hydroxyl value of 20 mgKOH / g-280 mgKOH / g, an acid value of 0.05 mgKOH / g-0.15 mgKOH / g, and the proportion of propylene oxide units in the polyether polyol is not less than 60% of the total molecular structure. The reactivity index between the reactive toughening agent and the epoxy resin is controlled at 0.8-1.2 to ensure that the curing reaction is fully carried out.

7. The adhesive solder according to claim 3, characterized in that, Component B, by mass percentage, comprises 30%–80% polyamide, 5%–30% linear aliphatic polyamine, and 3%–15% cyclic aliphatic polyamine; the polyamide is selected from one or more of Versamid 140, Versamid 125, Aradur 450, and Aradur 115; the linear aliphatic polyamine is selected from one or more of triethylenetetramine, pentaethylenehexamine, and diethylenetriamine; the cyclic aliphatic polyamine is selected from one or more of isophorone diamine, 4,4'-diaminodicyclohexylmethane, and 1,4-cyclohexanediamine. During the preparation of component B, the heating temperature is controlled at 60°C–80°C, and the stirring speed is 80 rpm–120 rpm. 1%–3% of accelerator DMP-30 is added to component B to shorten the curing time and improve the degree of curing.

8. A method for preparing a nickel-based superalloy brazing adhesive tape as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Step S1. Preparation of organic binder: Epoxy resin, compound tackifier, reactive toughening agent, antioxidant, and nano-scale graphene oxide modifier are added to a reaction vessel and heated to 60℃~80℃ and stirred for 30min~60min to obtain component A; polyamide, linear aliphatic polyamine, cyclic aliphatic polyamine, and accelerator are added to a reaction vessel and heated to 60℃~80℃ and stirred for 30min~60min to obtain component B; components A and B are mixed in equal proportions and stirred at 30rpm~500rpm for 10min~30min, and allowed to stand for 5min~10min to obtain the organic binder; Step S2. Preparation of brazing filler metal slurry: Weigh the vacuum-annealed alloy brazing filler metal powder and the organic binder obtained in step S1 according to the specified ratio, place them in a vacuum mixer, and heat them under a vacuum degree lower than 1×10⁻⁶. -1 Under the condition of Pa, mix at a speed of 30 r / min to 60 r / min for 1 hour to 4 hours to obtain a paste-like brazing filler metal mixture; pre-cur at 25℃ to 35℃ for 12 hours to 48 hours to obtain a brazing filler metal slurry with preliminary strength. Step S3. Preparation of adhesive tape: Transfer the paste-like brazing filler metal mixture obtained in step S2 to a precision twin-roll mill and roll it repeatedly at room temperature 3 to 5 times. After each rolling, let it stand for 2 to 3 minutes to produce a flexible adhesive tape brazing filler metal with a thickness of 0.1 mm to 2.0 mm and a width of 10 mm to 100 mm. After cutting, attach single-sided silicone release paper, coil and package it, and store it in a cool and dry place. The relative humidity of the storage environment should be controlled at 30% to 60%. Before packaging, vacuum dry the adhesive tape brazing filler metal at 100℃ to 120℃ for 1 to 2 hours to remove residual trace moisture.

9. A brazing process for adhesive filler metal as described in any one of claims 1 to 7, characterized in that, Includes the following steps: Step S1. Grind the surface of the workpiece to be welded until smooth. Use acetone to ultrasonically clean the welding area of ​​the nickel-based high-temperature alloy component for 5 min to 10 min. After drying, attach the adhesive brazing filler to the welding area. The adhesion between the adhesive brazing filler and the welding area should not be less than 95%. After bonding, apply pressure of 0.1 MPa to 0.3 MPa for 10 min to 20 min to ensure tight contact at the interface. Step S2. Place the workpiece to be welded in a vacuum brazing furnace and evacuate it to a vacuum state with a vacuum degree of 1×10⁻⁶. -3 Pa ~ 1×10 -2 Pa, heated to 500℃~600℃ at a heating rate of 5℃ / min~10℃ / min, and held for 10min~15min; Step S3. Continue heating at a rate of 5℃ / min to 10℃ / min to 800℃ to 950℃, hold for 5 min to 10 min, then heat to the preset temperature at a rate of 5℃ / min to 10℃ / min and hold for 10 min to 15 min; cool to room temperature at a rate of 10℃ / min to complete the welding; the preset temperature is the melting temperature of the alloy solder powder in the adhesive solder, and the preset temperature fluctuation range does not exceed ±5℃. During the cooling process, a holding step of 5 min to 8 min is added in the 600℃ to 700℃ range to reduce thermal stress.

10. The application of the adhesive brazing filler metal as described in any one of claims 1 to 7 in the brazing or repair of nickel-based superalloy components for aero-engines and gas turbines, characterized in that, The brazing filler metal exhibits complete evaporation of organic binder with no residue within the temperature range of 350℃ to 550℃, has a wetting angle of less than 20° with the nickel-based superalloy base material, produces a uniform joint structure with low residual carbon content, and achieves a room temperature tensile strength of not less than 850 MPa. Its tensile strength retention rate at 800℃ is not less than 70%, making it suitable for connecting nickel-based superalloy components with gaps of 0.1mm to 1.0mm. The joint's corrosion resistance meets the requirement of no rust after 500 hours of neutral salt spray testing. The brazed joint's tensile strength retention rate at 800℃ is 5% to 8% higher than that of brazing filler metal without added nano-sized titanium carbide particles and nano-sized silica dispersion, and the joint hardness is increased by 10% to 15%.

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