CN115537596A - High-hardness corrosion-resistant nickel-aluminum bronze welding wire, preparation method thereof and application thereof in alloy cladding - Google Patents
High-hardness corrosion-resistant nickel-aluminum bronze welding wire, preparation method thereof and application thereof in alloy cladding Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/01—Alloys based on copper with aluminium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/20—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
Abstract
The invention discloses a high-hardness corrosion-resistant nickel-aluminum bronze welding wire which comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate; the welding wire matrix comprises Cu, ni, al, fe, mn and trace Ti, gd and As; the nano composite coating is prepared from coating liquid containing the following components: intermetallic compound powder, nano ceramic powder, nano conductive carbon black, nickel-based alloy powder, titanate accelerator and base liquid; the invention also discloses a preparation method of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire and application of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire in alloy cladding. The invention has the advantages that the welding wire has good strength and toughness by adjusting the components of the welding wire substrate, is convenient to machine into wires, ensures the surface quality of the welding wire through the nano composite coating, improves the wettability during cladding and the forming effect after cladding, and improves the surface hardness and the corrosion resistance of the alloy cladding layer by introducing the strengthening phase.
Description
Technical Field
The invention belongs to the technical field of alloy cladding, and particularly relates to a high-hardness corrosion-resistant nickel-aluminum bronze welding wire, a preparation method thereof and application thereof in alloy cladding.
Background
The hydraulic support is a main supporting device of a fully mechanized coal mining face of a coal mine and is necessary guarantee for safety production. The underground working condition is severe, and inevitable corrosion, strain, impact, collision and the like cause damage to the surface coating of the bracket and parts thereof, so that the integral service performance of the bracket is influenced, and the working face cannot be normally produced. Due to the factors of long support withdrawing and installing period, insufficient ground industrial field and the like, the maintenance work of the hydraulic support is always puzzled and restricts the production progress and the recovery work of a coal mine. The traditional repairing method is to adopt an electroplating iron repairing process, namely a traditional repairing technology for recovering the to-be-repaired piece to the use size under the condition of a low-temperature medium, and the metal ions in the plating solution are reduced into metal atoms by utilizing the principle of electrolytic ion replacement and are deposited on the surface of the metal to form a repairing layer with certain thickness and higher binding force, so that the aim of repairing the to-be-repaired piece is fulfilled. The mode has high repairing efficiency and low cost, but the environmental pollution is serious.
At present, aiming at the underground fully mechanized mining environment and the main damage form of the hydraulic support, the damaged part of the hydraulic support can be maintained, remanufactured and upgraded by alloy cladding. The alloy cladding mainly adopts the argon protection welding repair technology, utilizes a pulse power supply, protective gas and a special welding wire to finish repairing workpieces, and has the process characteristics of lowest control welding heat input, less melting of base metal, good arc stability, shallow melting depth, high cladding speed and the like. Wherein the welding wire material comprises aluminum bronze (such as ZQAl9-4, with Al 8.5-11.0%, fe 2.0-4.0%, and Cu in balance), tin bronze (such as ZQSn10-1, with Sn9.0-11.5%, P0.5-1.0%, and Cu in balance), etc. ZQAl9-4 has better strength, good pressure processability in a hot state, but poor solderability, and is easy to generate dealumination corrosion in an environmental medium, so that the service life of the material is low. While ZQSn10-1 has low strength and toughness, and greatly reduces the wear resistance under the condition of poor lubrication.
In order to improve the service performance of the copper alloy welding wire, research is focused on improving the alloy structure and realizing good mechanical property and corrosion resistance by adding a component with a strengthening effect in the alloy. The patent with the application number of CN201910942261.8 discloses a hydraulic upright post guide sleeve repairing and remanufacturing method, wherein related aluminum bronze welding wires comprise 82.8-88% of Cu + Ag, 2-4.5% of Fe, less than 0.2% of Sn, 10-11.5% of Al, less than 0.3% of Mn0.25% of Si; the welding wire component is mainly formed by adding Ag on the basis of an aluminum bronze alloy, so that the flowability, wettability and machining performance of the material are improved, but the segregation tendency is increased, and the content of Al in the component exceeds 10%, although the welding wire has higher strength and hardness due to the increase of the content of Al, the corrosion resistance of the alloy is adversely affected by the high content of Al, the gettering tendency of the alloy is also increased, the possibility of generating oxide inclusions is increased, and the hardness and the corrosion resistance of the material are not facilitated. Patent No. CN202210423895.4 discloses a copper alloy melting device for a hydraulic cylinder wall for a coal mine, wherein the chemical components of the related alloy copper welding wire are as follows: the welding wire belongs to a high manganese aluminum bronze welding wire, a certain amount of manganese is dissolved for solid solution strengthening, the mechanical property of the alloy is improved, the formation and the meshing of a gamma phase are inhibited by proper amounts of Fe and Ni, the rare earth element is combined to play a role in refining grains, the performance of the alloy is comprehensively improved, the hardness of the alloy is easy to guarantee, but the yield strength is faster than the tensile strength due to excessive fine crystal strengthening, so that the yield ratio is increased, the plasticity is reduced, the elongation is greatly reduced, and the production difficulty of the alloy copper welding wire with the chemical components is that the elongation is difficult to guarantee and the drawing forming is difficult.
Because the nickel-aluminum bronze alloy has excellent performances of stress corrosion cracking resistance, corrosion fatigue resistance, cavitation corrosion resistance, erosion resistance, marine organism pollution damage resistance and the like, the nickel-aluminum bronze welding wire attracts great attention in the alloy cladding field of parts such as blades for large-scale pumps, seawater pipes, hydraulic supports, steel rollers and the like. The nickel-aluminum bronze welding wire also has the problems that the machining performance and the service performance are difficult to improve simultaneously, and the defects on the surface of the welding wire in the production process can cause unstable wire feeding, large welding spatter and poor forming in the cladding process, so that the alloy layer formed by cladding on the surface has poor performance. How to improve the defects of the nickel-aluminum bronze welding wire is a problem to be solved urgently at present. Therefore, the development of the high-hardness and high-corrosion-resistance welding wire suitable for alloy cladding of the hydraulic support can promote the development of welding wire materials and has very important practical significance for alloy cladding additive application.
Disclosure of Invention
Based on the defects of the prior art, the invention provides a high-hardness corrosion-resistant nickel-aluminum bronze welding wire, which takes an alloy containing Cu, ni, al, fe, mn and trace Ti, gd and As As a welding wire substrate, and forms a nano composite coating outside the welding wire substrate through a coating liquid containing intermetallic compound powder, nano ceramic powder, nano conductive carbon black, nickel-based alloy powder and a titanate accelerator; the components of the welding wire matrix are adjusted, so that the welding wire matrix has good strength and toughness, is convenient to machine into wires, ensures the surface quality of the welding wire through the nano composite coating, improves the wettability during cladding and the forming effect after cladding, introduces a strengthening phase, and is beneficial to improving the surface hardness and corrosion resistance of the cladding layer.
The invention also discloses a preparation method of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire and application of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire in alloy cladding.
In order to achieve the purpose, the invention adopts the technical scheme that:
a high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate;
the welding wire base body comprises the following components in percentage by mass: 4.5 to 6.0 percent of Ni, 7.0 to 9.0 percent of Al, 2.2 to 4.0 percent of Fe, 1.0 to 2.0 percent of Mn, 0.2 to 0.35 percent of Ti, 0.02 to 0.05 percent of Gd, 0.02 to 0.04 percent of As, less than 0.03 percent of C and the balance of Cu;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: 5.4 to 7.2 percent of intermetallic compound powder, 1.8 to 3.6 percent of nano ceramic powder, 10 to 15 percent of nano conductive carbon black, 8 to 15 percent of nickel-based alloy powder, 1 to 3 percent of titanate accelerator and the balance of base liquid.
Preferably, the intermetallic compound powder is in powder form (Ti) 1-x Ta x ) 5 Si 3 ，(Ti 1-x Ta x ) 5 Si 3 Wherein x is 0.2 to 0.4;
the (Ti) 1-x Ta x ) 5 Si 3 The preparation method comprises the following steps: weighing Ti powder, ta powder and Si powder according to the molar ratio of the compounds, ball-milling for 4-6 h under a protective atmosphere, and carrying out cold isostatic pressing to form to obtain a block material; heating the block materials to be molten in a vacuum melting chamber, then cooling to 2100-2250 ℃, preserving heat for 25-50 min, preparing powder by adopting a gas atomization method, after the powder is collected, preserving heat and tempering at 400-500 ℃ for 2-4 h under a protective atmosphere, then cooling to room temperature, and screening to obtain the (Ti) 1-x Ta x ) 5 Si 3 (the grain diameter is less than or equal to 10 mu m);
wherein the protective atmosphere is argon; the ball-material ratio during ball milling is 8-15, absolute ethyl alcohol is used as a grinding aid, the ball milling speed is 300-400 r/min, and drying is carried out at 60-90 ℃ after ball milling.
Preferably, the nano ceramic powder is Si with the particle size of 15-30 nm 3 N 4 A powder; the nickel-based alloy powder is nickel-based self-fluxing alloy powder; the titanate accelerator is selected from n-butyl titanate; the base liquid is one or more than two of alcohol solvent, alcohol ether solvent, ester solvent and ketone solvent.
The welding wire substrate and the nano composite coating have the following functions:
the solubility of manganese (Mn) and aluminum (Al) in copper is high, the strength, the hardness and the corrosion resistance can be improved by proper amount of manganese and aluminum, and the plasticity of the alloy is reduced by excessive amount of manganese and aluminum; nickel (Ni) in the aluminum bronze is infinitely solid-dissolved, so that the structure segregation is reduced, the toughness, the corrosion resistance and the thermal stability of the alloy are improved, and the nickel and iron (Fe) can refine grains, improve the strength and refine the grains; the content of iron must be controlled below 4.0%, otherwise the alloy is embrittled, the toughness is reduced, and the corrosion resistance is reduced; titanium (Ti) can suppress the generation of pores and also improve arc stability in a high current region; gadolinium (Gd) can effectively reduce high-temperature rheological stress, reduce the grain size and improve the ductility of the alloy; arsenic (As) has high solid solubility in copper, and can eliminate eutectic structures on the grain boundary of copper alloy, thereby improving the plasticity of copper; titanium, gadolinium and arsenic are added in trace amounts, and are used for synergistically assisting in refining the structure and improving the toughness, and when the addition amount is increased, a high-melting point intermetallic compound which is excessively dispersed and distributed can be formed, and the compound can still improve the mechanical property as a second phase, but discontinuous precipitation at a grain boundary can influence the cold processing property, easily cause material fracture or cracking, and is not favorable for processing small-size wires.
(Ti 1-x Ta x ) 5 Si 3 And Si 3 N 4 The coating is wrapped on the welding wire substrate in the form of a surface nano composite coating, has a protective effect on the welding wire substrate, has a lubricating effect on the wire feeding in the processing process, reduces the surface defects of the welding wire, and is melted by electric arc (Ti) 1-x Ta x ) 5 Si 3 And Si 3 N 4 The existence of the hard phase in the alloy cladding layer can obviously improve the hardness of the materialDegree and abrasion resistance; the nickel-based self-fluxing alloy powder has low melting point, has a repairing effect on the surface of a welding wire matrix, plays a role in connecting the phases in cladding, and improves the compactness of the material; the titanium dioxide can cause shrinkage of anode spots and electric arc on the surface of a workpiece, and the surface tension of a molten pool changes in a gradient manner, so that the effects of refining molten drops and improving electric arc stability are achieved, splashing is reduced, and the deposition efficiency is improved; the nano conductive carbon black has good fluidity and high-temperature lubricity, is beneficial to the dispersion uniformity of coating liquid, ensures the conductivity and the wire feeding stability of the welding wire in the using process, and forms oxycarbide during cladding, thereby further protecting an alloy cladding layer and improving the quality of the cladding surface.
Wherein, the (Ti) is 1-x Ta x ) 5 Si 3 The preparation method adopts a method of combining mechanical ball milling and gas atomization, the ball milling enables the material to have larger surface energy and lattice distortion energy, and can promote the diffusion of atoms, the solid solution of alloy and the migration elimination of pores at lower temperature, so as to form solid solution in smelting and reduce the generation of complex phases; the gas atomization makes the material have low oxygen content, good powder sphericity and proper granularity, and the heat preservation tempering is carried out under the protective atmosphere, which is helpful for improving the structure and homogenizing the components.
Preferably, the mass ratio of Ni/Fe in the welding wire matrix is 1.5-2.0.
Preferably, the diameter of the welding wire substrate is 1.0-3.0 mm, and the nano composite coating accounts for 0.5-1% of the mass of the nickel-aluminum bronze welding wire.
The prior art finds that a kappa phase can appear in the structure of the Cu-Al-Ni-Fe quaternary alloy containing Al, ni and Fe, when the Ni content is larger than the Fe content, the kappa phase is precipitated in a layered manner, when the Fe content is larger than the Ni content, the kappa phase is in a blocky manner, and only when the Ni content is approximately equal to the Fe content, the kappa phase is in a uniformly dispersed fine particle shape. After the welding wire containing only the Cu-Al-Ni-Fe quaternary alloy is cladded, the hardness and the wear resistance of the material (alloy cladding layer) are difficult to ensure, other elements are required to be added for proper alloying so as to improve the mechanical property of the material, and lattice distortion and plasticity and toughness reduction are caused in the solid solution process of the other elements; the welding wire matrix contains other fine crystal elements, when the Ni content is slightly larger than the Fe content, the strength of the material is not obviously changed, the toughness of the material tends to be increased, and when the Ni/Fe is larger than 2.0, the hardness of the material is reduced. The mass percentage of the nano composite coating in the nickel-aluminum bronze welding wire is controlled to be 0.5-1%, too little of the nano composite coating can not play a role, and too much of the nano composite coating can deteriorate materials, so that the bonding force between an alloy cladding layer and a substrate to be clad is reduced.
The preparation method of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises the following steps of:
s1, preparing materials: preparing the welding wire substrate and the coating liquid according to the mass percentage of each component, and preparing the coating liquid;
s2, smelting: placing raw materials of a welding wire substrate in a vacuum melting chamber, heating to 1050-1150 ℃ by medium-frequency induction, melting for 40-60 min to obtain an alloy melt, and introducing argon into the alloy melt for 15-20 min in a heat preservation state to obtain copper alloy liquid;
s3, casting-hot rolling: heating the copper alloy liquid obtained in the step S2 to 1250-1350 ℃, performing horizontal continuous casting to form a copper alloy bar with the diameter of 30-50 mm, controlling the rolling temperature to be 420-480 ℃, performing hot continuous rolling for 2-3 times, wherein the total reducing ratio of the outer diameter of the hot continuous rolling is 60% -75%, and then pickling the surface to remove oil stains and impurities on the surface to obtain the copper alloy bar;
s4, solid solution-aging treatment: heating the copper alloy rod material to 870-950 ℃ in a vacuum furnace, preserving heat for 1-2 h, putting the copper alloy rod material into a quenching medium, cooling to below 60 ℃, and then air-cooling to room temperature; then heating to 400-480 ℃ in a vacuum furnace, preserving heat for 2-3 h, cooling to below 100 ℃ along with the furnace, and then air-cooling to room temperature to obtain a solid solution reinforced rod material;
s5, phosphating, cold drawing and intermediate annealing: straightening, pickling, carrying out surface phosphating treatment and coating lubricating oil on the solid solution strengthening rod obtained in the step S4, then carrying out multi-pass single-mode drawing and multi-mode drawing, and when the cold deformation amount in the single-mode drawing and multi-mode drawing processes reaches 60-75%, carrying out vacuum annealing at 550-620 ℃ for 20-30 min and then cooling along with a furnace; sizing and scraping after cold drawing to obtain a copper alloy wire;
s6, etching-coating: immersing the copper alloy wire obtained in the step S5 in an etchant for surface treatment for 20-40S, cleaning and drying, then mechanically coating or electrostatically spraying a coating solution on the surface of the copper alloy wire, and drying to obtain a coated welding wire;
and S7, carrying out vacuum heat treatment on the coating welding wire obtained in the S6 at the temperature of 380-420 ℃ for 20-30 min, cooling along with a furnace, and then coiling to obtain the nickel-aluminum bronze welding wire.
In the above method, the reduction ratio:
deformation amount:
in the formula of the reducing ratio and the deformation, D 0 Is the diameter (unit: mm) of the entry/entry die, D i The exit roll/exit die diameter (unit: mm).
Preferably, the coating solution in S1 is prepared by the following steps: mixing intermetallic compound powder, nano ceramic powder, nano conductive carbon black and nickel-based alloy powder under a protective atmosphere, and performing ball milling for 2-4 hours to obtain mixed powder; ultrasonically dispersing the mixed powder and the titanate accelerant in the base liquid to obtain a coating liquid;
wherein the protective atmosphere is a mixed gas of carbon dioxide and argon; the ball-milling process comprises the following steps of ball-milling at a ball-material ratio of 10-15, taking absolute ethyl alcohol as a grinding aid, ball-milling at a rotating speed of 300-500 r/min, and drying at 60-90 ℃.
Preferably, the etchant in S6 is a solution formed by mixing dilute sulfuric acid and citric acid, and H in the etchant 2 SO 4 The weight percentage of the citric acid is 2-4%, and the weight percentage of the citric acid is 3-5%.
After smelting and casting, the hot working is firstly carried out, the uniformity and the toughness of the structure are improved through the solid solution treatment, and then fine disperse phases are precipitated through the aging treatment, so that the internal structure of the rod is compact, the temperature and the duration are strictly controlled in the heat treatment process, the coarse structure is avoided, and the creep deformation and the cracking strength of the rod are improved; cold working is carried out, the surface is cleaned by acid pickling before the cold working, then a phosphating film is formed by phosphating treatment to improve the surface lubricity, cooling in the cold working process is realized by coating lubricating oil, a large amount of dislocation is introduced into a rod structure by cold drawing, the middle of the rod structure is raised to be close to the recrystallization temperature for vacuum annealing, and the dislocation is transferred within a small distance so as to facilitate the subsequent working; the surface of the formed wire is cleaned, the surface roughness is adjusted by weak etching to improve the adhesive force of the coating, then the coating liquid is coated on the surface, and finally the nano composite coating is stabilized by medium temperature heat treatment to realize the homogenization and stabilization of the components of the welding wire.
The application of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire in alloy cladding comprises the following steps: and repairing the surface defects of the hydraulic support cylinder body by cold arc cladding by using the high-hardness corrosion-resistant nickel-aluminum bronze welding wire as a cladding material.
Preferably, during cold arc cladding, the average arc voltage is 12-25V, the output pulse current is 30-90A, the output pulse time is 40-60 ms, the wire feeding speed is 2.0-3.0 m/min, the cladding linear speed is 0.6-1.2 m/min, the cladding thickness is 0.5-3 mm, and the protective gas is argon gas with the flow rate of 8-15L/min.
The nickel-aluminum bronze welding wire disclosed by the invention repairs the surface defects of the hydraulic support cylinder body through cold arc cladding, the formed alloy cladding layer is good in combination condition with a matrix to be clad, the wear resistance and the corrosion resistance are good, the hardness is greater than 460HV, the neutral salt spray corrosion (NSS) resistance is greater than 1000h, and no rust spot appears in a copper accelerated acetate spray test (CASS) for 120 h.
Detailed Description
In order to make the technical purpose, technical scheme and beneficial effects of the invention clearer, the technical scheme of the invention is further described with reference to specific examples, which are intended to explain the invention and are not to be construed as limiting the invention, and the raw materials used in the examples are all common commercial products, and the specific technology or conditions are not noted, according to the technology or conditions described in the literature in the field or according to the product specification.
Example 1
A high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate, wherein the nano composite coating accounts for 0.8 percent of the mass of the nickel-aluminum bronze welding wire;
the welding wire base body comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of Al, 2.8% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =1.857;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: (Ti) 0.75 Ta 0.25 ) 5 Si 3 5.8% of powder and nano Si 3 N 4 2.7% of powder, 12.5% of nano conductive carbon black, 12% of Ni60A powder, 2% of n-butyl titanate and the balance of isopropanol.
Wherein, the (Ti) is 0.75 Ta 0.25 ) 5 Si 3 The preparation method comprises the following steps: weighing Ti powder, ta powder and Si powder according to the compound molar ratio, ball-milling for 5h in an argon atmosphere (the ball-material ratio during ball-milling is 10, absolute ethyl alcohol is used as a grinding aid, the ball-milling rotation speed is 400r/min, drying is carried out at 80 ℃ after ball-milling), and carrying out cold isostatic pressing and forming to obtain a block material; heating the block materials to be molten in a vacuum melting chamber (the vacuum degree is less than 0.1 Pa), then cooling to 2180 ℃ and preserving heat for 40min, preparing powder by a gas atomization method (argon powder spraying with the pressure of 4MPa is adopted), after the powder is collected, preserving heat and tempering for 3h at 450 ℃ in an argon atmosphere, then cooling to room temperature, and screening to obtain the material.
The preparation method of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises the following steps:
s1, preparing materials: preparing the welding wire substrate and the coating liquid according to the mass percentage of each component, and preparing the coating liquid;
wherein, the raw material of the welding wire matrix can adopt pure metal or intermediate alloy; the coating solution is prepared by adopting the following steps: in the presence of carbon dioxide and argonUnder the mixed atmosphere of (a) and (b), will be (Ti) 0.75 Ta 0.25 ) 5 Si 3 Powder, nano Si 3 N 4 Mixing powder (the particle size is about 20 nm), nano conductive carbon black and Ni60A powder, performing ball milling for 4 hours (the ball-material ratio is 12:1 during ball milling, absolute ethyl alcohol is used as a grinding aid, the ball milling speed is 400r/min, and drying is performed at 70 ℃ after ball milling) to obtain mixed powder; ultrasonically dispersing the mixed powder and n-butyl titanate in isopropanol to obtain a coating liquid;
s2, smelting: placing raw materials of a welding wire substrate in a vacuum melting chamber, heating to 1100 ℃ by medium-frequency induction, melting for 45min to obtain an alloy melt, and introducing argon into the alloy melt for 15min in a heat preservation state to obtain a copper alloy liquid;
s3, casting-hot rolling: heating the copper alloy liquid obtained in the step S2 to 1300 ℃, performing horizontal continuous casting to form a copper alloy bar with the diameter of 40mm, controlling the rolling temperature to be 450 ℃, performing hot continuous rolling for 3 times, wherein the total external diameter reduction rate of the hot continuous rolling is 75%, the rolling speed of the hot continuous rolling is 2m/S, and then pickling the surface to remove oil stains and impurities on the surface to obtain the copper alloy bar with the diameter of 10 mm;
s4, solid solution-aging treatment: heating the copper alloy rod material to 910 ℃ along with the furnace in a vacuum furnace, preserving the heat for 1.5h, cooling the copper alloy rod material to be lower than 60 ℃ in a quenching medium, and then cooling the copper alloy rod material to room temperature; then heating to 440 ℃ in a vacuum furnace, preserving heat for 2h, cooling to less than 100 ℃ along with the furnace, and then air-cooling to room temperature to obtain a solid solution reinforced rod material;
s5, phosphating, cold drawing and intermediate annealing: after straightening, pickling, surface phosphating and lubricating oil coating are carried out on the solid solution reinforced rod obtained in the step S4, single-mode drawing is carried out, the diameter reduction rate of each pass is 17%, the drawing speed is 1m/S, then multi-mode drawing is carried out, the diameter reduction rate of each pass is 10%, the drawing speed is 2m/S, when the cold deformation in the single-mode drawing and multi-mode drawing processes reaches 60-75%, vacuum annealing is carried out for 30min at the temperature of 560 ℃ and furnace cooling is carried out, and the vacuum annealing treatment is not carried out when the multi-mode drawing is finished; after cold drawing, sizing and scraping (the scraping speed is 8m/s, the diameter is reduced by 0.02 mm) to obtain a copper alloy wire with the diameter of 1 mm;
wherein the acid washing adopts a solution containing 100g/L H 2 SO 4 、40g/L H 2 O 2 Soaking 40g/L ethanol and 0.2g/L aqueous solution of benzotriazole at room temperature for 30s; the surface phosphating treatment adopts common commercial zinc-manganese phosphating solution (AIR-XMA 50) to be soaked for 5min at room temperature, and the weight of a phosphating film on a unit area after the surface phosphating treatment is about 5g/m 2 ；
The cold drawing and intermediate annealing processes are controlled as follows:
single-mode drawing: φ 10mm → φ 8.30mm → φ 6.89mm → φ 5.72mm → interannealing → φ 4.75mm → φ 3.94mm → φ 3.27mm → interannealing;
drawing in a multi-mode: phi 3.27mm to phi 2.94mm to phi 2.65mm to phi 2.38mm to phi 2.14mm to phi 1.93mm; intermediate annealing; phi 1.93mm to phi 1.74mm to phi 1.56mm to phi 1.40mm to phi 1.26mm to phi 1.13mm to phi 1.02mm;
s6, etching-coating: immersing the copper alloy wire obtained in S5 in an etchant (containing 3% H) 2 SO 4 And 4% citric acid aqueous solution), cleaning, drying, mechanically coating the coating liquid on the surface of the copper alloy wire, and drying to obtain a coated welding wire;
and S7, carrying out vacuum heat treatment on the coating welding wire obtained in the S6 at 400 ℃ for 30min, cooling along with the furnace, and then coiling to obtain the nickel-aluminum bronze welding wire.
Example 2
A high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate, wherein the nano composite coating accounts for 0.8 percent of the mass of the nickel-aluminum bronze welding wire;
the welding wire base body comprises the following components in percentage by mass: 5.6% of Ni, 8.1% of Al, 2.8% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =2.0;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: (Ti) 0.75 Ta 0.25 ) 5 Si 3 5.8% of powder and nano Si 3 N 4 2.7% of powder, 12.5% of nano conductive carbon black, 12% of Ni60A powder, 2% of n-butyl titanate and the balance of isopropanol.
The difference of example 2 compared to example 1 is that: the content of Ni in the welding wire matrix is changed, and Ni/Fe is changed accordingly.
Example 3
A high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate, wherein the nano composite coating accounts for 0.8 percent of the mass of the nickel-aluminum bronze welding wire;
the welding wire base body comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of Al, 3.47% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =1.5;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: (Ti) 0.75 Ta 0.25 ) 5 Si 3 5.8% of powder and nano Si 3 N 4 2.7% of powder, 12.5% of nano conductive carbon black, 12% of Ni60A powder, 2% of n-butyl titanate and the balance of isopropanol.
Example 3 differs from example 1 in that: the content of Fe in the welding wire matrix is changed, and Ni/Fe is changed accordingly.
Example 4
A high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate, wherein the nano composite coating accounts for 0.5 percent of the mass of the nickel-aluminum bronze welding wire;
the welding wire base body comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of Al, 2.8% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =1.857;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: (Ti) 0.75 Ta 0.25 ) 5 Si 3 5.8% of powder and nano Si 3 N 4 2.7% of powder, 12.5% of nano conductive carbon black, 12% of Ni60A powder, 2% of n-butyl titanate and the balance of isopropanol.
Example 4 differs from example 1 in that: the mass percentage of the nano composite coating layer in the nickel-aluminum bronze welding wire is reduced.
Example 5
A high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate, wherein the nano composite coating accounts for 1.0 percent of the mass of the nickel-aluminum bronze welding wire;
the welding wire base body comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of Al, 2.8% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =1.857;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: (Ti) 0.75 Ta 0.25 ) 5 Si 3 5.8% of powder and nano Si 3 N 4 2.7% of powder, 12.5% of nano conductive carbon black, 12% of Ni60A powder, 2% of n-butyl titanate and the balance of isopropanol.
Example 5 differs from example 1 in that: the mass percentage of the nano composite coating layer in the nickel-aluminum bronze welding wire is increased.
Comparative example 1
A nickel-aluminum bronze welding wire (without a nano composite coating) comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of AlC, 5.2% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =1.0.
The difference of comparative example 1 compared to the wire base of example 1 is that: the content of Fe in the welding wire matrix is increased, and Ni/Fe is changed along with the increase of the content of Fe in the welding wire matrix.
Comparative example 2
A nickel-aluminum bronze welding wire (without a nano composite coating) comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of AlC, 2.0% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =2.6.
The difference between comparative example 2 and the wire base of example 1 is that: the content of Fe in the welding wire matrix is reduced, and Ni/Fe is changed along with the reduction of the content of Fe in the welding wire matrix.
Comparative example 3
A nickel-aluminum bronze welding wire comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate, wherein the nano composite coating accounts for 2% of the mass of the nickel-aluminum bronze welding wire;
the welding wire base body comprises the following components in percentage by mass: 5.2% of Ni, 8.1% of Al, 2.8% of Fe, 1.37% of Mn, 0.28% of Ti, 0.03% of Gd, 0.03% of As, less than 0.03% of C and the balance of Cu; wherein Ni/Fe =1.857;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: (Ti) 0.75 Ta 0.25 ) 5 Si 3 5.8% of powder and nano Si 3 N 4 2.7% of powder, 12.5% of nano conductive carbon black, 12% of Ni60A powder, 2% of n-butyl titanate and the balance of isopropanol.
Comparative example 3 differs from example 1 in that: the mass percentage of the nano composite coating layer in the nickel-aluminum bronze welding wire is increased.
The nickel aluminum bronze welding wires according to examples 2 to 5 and comparative example 3 were manufactured according to the method of example 1, and the nickel aluminum bronze welding wires according to comparative examples 1 and 2 were manufactured according to the method of example 1 except for S6. The nickel-aluminum bronze welding wires prepared in examples 1 to 5 and comparative examples 1 to 3 were used as cladding materials, and the surface defects of the hydraulic bracket cylinder were repaired by cold arc cladding using a pulse gas shield arc welding machine. During cold arc cladding, the average arc voltage is 20V, the output pulse current is 60A, the output pulse time is 50ms, the wire feeding speed is 3m/min, the cladding linear speed is 1m/min, and the shielding gas adopts argon with the flow of 10L/min. No preheating is needed before welding, and natural air cooling is carried out after welding.
In order to detect the service performance of the nickel-aluminum bronze welding wire, according to the cold arc cladding parameters, cladding the nickel-aluminum bronze welding wire on a 30CrMnSi steel substrate (the surface is polished and cleaned), testing the bonding strength, the surface average hardness, the elongation and the frictional wear loss of the cladding layer (a frictional wear testing machine is adopted, the testing parameters are room temperature, the rotating speed is 150r/min, the working load is 50N, the time is 10 min), continuously cladding for 5h, and testing the aperture wear rate of the conductive nozzle (the
In the formula D 0 For the aperture value of the nozzle before use, D max The maximum value of the aperture of the contact tip after use), the results are shown in table 1.
TABLE 1 service Properties of the Nickel-aluminum bronze welding wire according to examples 1 to 5 and comparative examples 1 to 3
As can be seen from Table 1, in order to achieve both toughness and hardness, ni/Fe should be 1.5-2.0, the relative content of Fe is increased, the toughness is reduced, and the toughness is not improved any more after the content of Fe is reduced to a certain degree, but rather the hardness is not improved. The mass percentage of the nano composite coating in the nickel-aluminum bronze welding wire is controlled to be 0.5-1%, too little of the nano composite coating can not play a role, and too much of the nano composite coating can deteriorate materials, so that the binding force between an alloy cladding layer and a substrate to be clad is reduced.
The corrosion resistance of the cladding layers formed by the nickel-aluminum bronze welding wires of examples 1 and comparative examples 1 to 3 was measured by a salt spray tester under the conditions shown in table 2.
TABLE 2 Corrosion resistance test conditions
It was found that the flux layer formed by the nickel aluminum bronze wire described in example 1 showed no corrosion spots after 1000 hours of neutral salt spray test and 120 hours of accelerated acetic acid salt spray test, the flux layer formed by the nickel aluminum bronze wire described in comparative examples 1 and 2 showed 2 or more corrosion spots after 120 hours of accelerated acetic acid salt spray test, and the flux layer formed by the nickel aluminum bronze wire described in comparative example 3 showed 1 corrosion spot after 120 hours of accelerated acetic acid salt spray test.
In conclusion, the nickel-aluminum bronze welding wire disclosed by the invention repairs the surface defects of the hydraulic support cylinder body through cold arc cladding, the formed alloy cladding layer is well combined with a matrix to be clad, the cladding layer does not crack when subjected to a bending test according to EN ISO 7438-2020 standard, the cladding layer is compact and uniform in tissue, and has no defects of shrinkage cavity, crack, peeling and the like, and the nickel-aluminum bronze welding wire has high hardness and good wear resistance and corrosion resistance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A high-hardness corrosion-resistant nickel-aluminum bronze welding wire is characterized in that: comprises a welding wire substrate and a nano composite coating on the surface of the welding wire substrate;
the welding wire base body comprises the following components in percentage by mass: 4.5 to 6.0 percent of Ni, 7.0 to 9.0 percent of Al, 2.2 to 4.0 percent of Fe, 1.0 to 2.0 percent of Mn, 0.2 to 0.35 percent of Ti, 0.02 to 0.05 percent of Gd, 0.02 to 0.04 percent of As, less than 0.03 percent of C and the balance of Cu;
the nano composite coating is prepared from a coating liquid, wherein the coating liquid comprises the following components in percentage by mass: 5.4 to 7.2 percent of intermetallic compound powder, 1.8 to 3.6 percent of nano ceramic powder, 10 to 15 percent of nano conductive carbon black, 8 to 15 percent of nickel-based alloy powder, 1 to 3 percent of titanate accelerator, and the balance of base liquid.
2. The high hardness corrosion resistant nickel aluminum bronze welding wire according to claim 1, wherein: the intermetallic compound powder is in the form of powder (Ti) 1-x Ta x ) 5 Si 3 ，(Ti 1-x Ta x ) 5 Si 3 Wherein x is 0.2 to 0.4;
the (Ti) is 1-x Ta x ) 5 Si 3 The preparation method comprises the following steps: weighing Ti powder according to the molar ratio of the compoundsCarrying out ball milling on Ta powder and Si powder for 4-6 h under a protective atmosphere, and carrying out cold isostatic pressing for forming to obtain a block material; heating the block materials to be molten in a vacuum melting chamber, then cooling to 2100-2250 ℃, preserving heat for 25-50 min, preparing powder by adopting a gas atomization method, collecting the powder, then preserving heat and tempering at 400-500 ℃ for 2-4 h under a protective atmosphere, then cooling to room temperature, and screening to obtain the (Ti) 1-x Ta x ) 5 Si 3 ；
Wherein the protective atmosphere is argon; the ball-material ratio during ball milling is 8-15, absolute ethyl alcohol is used as a grinding aid, the ball milling speed is 300-400 r/min, and drying is carried out at 60-90 ℃ after ball milling.
3. The high hardness corrosion resistant nickel aluminum bronze welding wire according to claim 1, wherein: the nano ceramic powder is Si with the grain diameter of 15-30 nm 3 N 4 A powder; the nickel-based alloy powder is nickel-based self-fluxing alloy powder; the titanate accelerator is selected from n-butyl titanate; the base solution is one or more than two of alcohol solvent, alcohol ether solvent, ester solvent and ketone solvent.
4. The high-hardness corrosion-resistant nickel aluminum bronze welding wire according to claim 1, wherein: the mass ratio of Ni to Fe in the welding wire matrix is 1.5-2.0.
5. The high-hardness corrosion-resistant nickel aluminum bronze welding wire according to claim 1, wherein: the diameter of the welding wire substrate is 1.0-3.0 mm, and the mass percentage of the nano composite coating layer in the nickel-aluminum bronze welding wire is 0.5-1%.
6. The method for preparing a high-hardness corrosion-resistant nickel aluminum bronze welding wire according to any one of claims 1 to 5, comprising the steps of:
s1, preparing materials: preparing the welding wire substrate and the coating liquid according to the mass percentage of each component, and preparing the coating liquid;
s2, smelting: placing raw materials of a welding wire substrate in a vacuum melting chamber, carrying out medium-frequency induction heating to 1050-1150 ℃, smelting for 40-60 min to obtain an alloy melt, and introducing argon into the alloy melt for 15-20 min under a heat preservation state to obtain copper alloy liquid;
s3, casting-hot rolling: heating the copper alloy liquid obtained in the step S2 to 1250-1350 ℃, performing horizontal continuous casting to form a copper alloy bar with the diameter of 30-50 mm, controlling the rolling temperature to be 420-480 ℃, performing hot continuous rolling for 2-3 times, and performing acid pickling on the surface to remove oil stains and impurities on the surface to obtain the copper alloy bar;
s4, solid solution-aging treatment: heating the copper alloy rod material to 870-950 ℃ in a vacuum furnace, preserving heat for 1-2 h, putting the copper alloy rod material into a quenching medium, cooling to below 60 ℃, and then air-cooling to room temperature; then heating to 400-480 ℃ in a vacuum furnace, preserving heat for 2-3 h, cooling to below 100 ℃ along with the furnace, and then air-cooling to room temperature to obtain a solid solution reinforced rod material;
s5, phosphating, cold drawing and intermediate annealing: straightening, pickling, carrying out surface phosphating treatment and coating lubricating oil on the solid solution strengthening rod obtained in the step S4, then carrying out multi-pass single-mode drawing and multi-mode drawing, and when the cold deformation amount in the single-mode drawing and multi-mode drawing processes reaches 60-75%, carrying out vacuum annealing at 550-620 ℃ for 20-30 min and then cooling along with a furnace; sizing and scraping after cold drawing to obtain a copper alloy wire;
s6, etching-coating: immersing the copper alloy wire obtained in the step S5 in an etchant for surface treatment for 20-40S, cleaning and drying, then mechanically coating or electrostatically spraying a coating solution on the surface of the copper alloy wire, and drying to obtain a coated welding wire;
and S7, carrying out vacuum heat treatment on the coating welding wire obtained in the step S6 at the temperature of 380-420 ℃ for 20-30 min, cooling along with the furnace, and then coiling to obtain the nickel-aluminum bronze welding wire.
7. The method for preparing the high-hardness corrosion-resistant nickel-aluminum bronze welding wire according to claim 6, wherein the coating solution in S1 is prepared by the following steps: under the protective atmosphere, mixing intermetallic compound powder, nano ceramic powder, nano conductive carbon black and nickel-based alloy powder, and performing ball milling for 2-4 h to obtain mixed powder; ultrasonically dispersing the mixed powder and the titanate accelerant in the base liquid to obtain a coating liquid;
wherein the protective atmosphere is a mixed gas of carbon dioxide and argon; the ball-material ratio during ball milling is 10-15, absolute ethyl alcohol is used as a grinding aid, the ball milling speed is 300-500 r/min, and drying is carried out at 60-90 ℃ after ball milling.
8. The method for preparing a high-hardness corrosion-resistant nickel aluminum bronze welding wire according to claim 6, wherein the etchant in S6 is a solution formed by mixing dilute sulfuric acid and citric acid, and H in the etchant 2 SO 4 The weight percentage of the citric acid is 2-4%, and the weight percentage of the citric acid is 3-5%.
9. The application of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire in alloy cladding as recited in any one of claims 1 to 5, wherein the high-hardness corrosion-resistant nickel-aluminum bronze welding wire comprises the following components in percentage by weight: and repairing the surface defects of the hydraulic support cylinder body by cold arc cladding by using the high-hardness corrosion-resistant nickel-aluminum bronze welding wire as a cladding material.
10. The application of the high-hardness corrosion-resistant nickel-aluminum bronze welding wire in alloy cladding according to claim 9, wherein the high-hardness corrosion-resistant nickel-aluminum bronze welding wire is characterized in that: during cold arc cladding, the average arc voltage is 12-25V, the output pulse current is 20-90A, the output pulse time is 40-60 ms, the wire feeding speed is 2.0-3.0 m/min, the cladding linear speed is 0.6-1.2 m/min, the cladding thickness is 0.5-3 mm, and argon with the flow rate of 8-15L/min is adopted as the protective gas.
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