CN110977248B - Wear-resistant flux-cored composition, wear-resistant welding wire, and preparation method and application thereof - Google Patents
Wear-resistant flux-cored composition, wear-resistant welding wire, and preparation method and application thereof Download PDFInfo
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- CN110977248B CN110977248B CN201911285219.XA CN201911285219A CN110977248B CN 110977248 B CN110977248 B CN 110977248B CN 201911285219 A CN201911285219 A CN 201911285219A CN 110977248 B CN110977248 B CN 110977248B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/3601—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0227—Rods, wires
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
- B23K35/368—Selection of non-metallic compositions of core materials either alone or conjoint with selection of soldering or welding materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/38—Selection of media, e.g. special atmospheres for surrounding the working area
- B23K35/383—Selection of media, e.g. special atmospheres for surrounding the working area mainly containing noble gases or nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
- B23K35/406—Filled tubular wire or rods
Abstract
The invention relates to a wear-resistant flux-cored composition, a wear-resistant welding wire, and a preparation method and application thereof. The wear-resistant flux core composition comprises a wear-resistant material and the balance of a filling material; the wear-resistant material accounts for 0.6-10 wt% of the wear-resistant flux core composition; the wear resistant material comprises diamond particles; the filling material comprises transition metal oxide powder and nickel-based alloy powder; the transition metal oxide powder accounts for 12 wt.% to 65 wt.% of the filler material. The wear-resistant flux core composition takes diamond particles as a wear-resistant reinforcing material, and forms a wear-resistant coating when used for welding or braze coating; the transition metal oxide is used as a filling material, so that the heat damage of the diamond is reduced, the brazing activity of the diamond is improved, and the linear expansion coefficient of cladding metal is reduced.
Description
Technical Field
The invention relates to the field of wear-resistant materials, in particular to a wear-resistant flux-cored composition, a wear-resistant welding wire, and a preparation method and application thereof.
Background
The hardfacing is a process of depositing materials with wear resistance on the surface of a workpiece by a welding method, and aims at not realizing the connection between the workpieces but obtaining a deposited metal layer with good wear resistance on the surface of the workpiece so as to prolong the service life of a weldment, save the manufacturing and maintenance cost, shorten the time for repairing and replacing key parts and reduce the loss of machine halt and production halt, thereby improving the production efficiency and reducing the production cost.
Carbides (such as tungsten carbide, chromium carbide, titanium carbide and the like) are often adopted in the surfacing metals as hard phases so as to improve the wear resistance of the surfacing metals. However, diamond, the hardest material currently known, is rarely used in hardfacing. The reason for this is that the diamond has poor thermal stability under high temperature conditions, and the arc temperature is extremely high during the overlay welding process, which is the most important reason for limiting the application of diamond in the field of hardfacing. As can be seen from the phase diagram of carbon, diamond is metastable at normal temperature and pressure. Therefore, the diamond is easily oxidized and graphitized at high temperature, thereby causing thermal damage to the diamond, which seriously affects the wear resistance of the overlay metal.
The brazing technology is widely applied at home and abroad as a manufacturing method of a diamond coating, brazing alloy powder, a powdery brazing material of diamond particles or a paste brazing material consisting of the brazing alloy powder, the diamond particles and a binder is adopted, the heating temperature is slightly lower than that of overlaying welding, the brazing alloy is melted to form a capillary action in the brazing heating process, the diamond particles are tightly wrapped by the alloy, and the diamond particles and the brazing alloy are metallurgically combined to form the wear-resistant diamond coating. But the prior art adopts furnace heating to braze the diamond coating, has low production efficiency and long required period, and cannot meet the requirement of rapidly replacing the diamond coating abrasion-resistant parts of industrial equipment in the in-service process.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a wear-resistant flux-cored composition and a wear-resistant welding wire thereof. The wear-resistant flux core composition takes diamond particles as a wear-resistant and reinforcing material, and forms a wear-resistant coating on the surface of a workpiece when the wear-resistant flux core composition is used for welding or braze coating; the transition metal oxide with a specific dosage is used as a filling material, so that the heat damage of the diamond particles is reduced, the brazing activity of the diamond particles is improved, and meanwhile, the linear expansion coefficient of the cladding metal is reduced, so that the linear expansion coefficients of the cladding metal and the diamond particles are matched, and the diamond particles are prevented from generating cracks under the action of welding thermal stress. On the basis, the sheath of the wear-resistant welding wire is transited to the surface of the workpiece through molten drops, is soft, can form a stress buffer layer between the diamond coating and the workpiece, and avoids the diamond coating formed on the surface of the workpiece from cracking.
The invention also provides a preparation method of the wear-resistant welding wire, which is simple and efficient, has strong continuity, controllable cost and short period, and is beneficial to large-scale industrial popularization.
The invention also provides application of the wear-resistant flux-cored composition and the wear-resistant welding wire in the aspect of wear-resistant brazing filler metal coating materials. When the wear-resistant flux-cored wire is used for wear-resistant brazing materials, the wear-resistant flux-cored composition and the wear-resistant welding wire can realize on-line continuous brazing, the brazing efficiency is greatly improved, and the adaptability is strong under the complex working condition environment of industrial equipment in the working process.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the abrasion resistant flux core composition comprises an abrasion resistant material and a filler material;
the wear-resistant material accounts for 0.6-10 wt% of the wear-resistant flux core composition; the wear resistant material comprises diamond particles;
the filling material comprises transition metal oxide powder and nickel-based alloy powder, wherein the proportion of the transition metal oxide powder is 12-65 wt.%.
Optionally, the transition metal oxide is selected from at least one of metal oxides of group VB or group VIB elements.
Optionally, the transition metal oxide powder comprises niobium oxide powder and molybdenum oxide powder; the mass ratio of the two is 6-25: 6-40.
Optionally, the transition metal oxide powder has a particle size of 140 mesh to 1000 mesh.
Alternatively, the niobium oxide powder and the molybdenum oxide powder may have a particle size selected from a range between 140 mesh, 150 mesh, 180 mesh, 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 550 mesh, 600 mesh, 650 mesh, 700 mesh, 750 mesh, 800 mesh, 850 mesh, 900 mesh, 950 mesh, and 1000 mesh, any point value.
Optionally, the diamond particles are surface activated diamond particles.
Optionally, the diamond particles have a particle size of 140 mesh to 600 mesh.
Alternatively, the diamond particles may have a particle size selected from a range between 140 mesh, 150 mesh, 180 mesh, 200 mesh, 250 mesh, 300 mesh, 350 mesh, 400 mesh, 450 mesh, 500 mesh, 550 mesh, and 600 mesh, any point value.
Optionally, the nickel-based alloy powder is selected from BNi73CrFeSiB(C)、BNi74CrFeSiB、BNi82CrSiBFe、BNi78CrSiBCuMoNb or BNi66At least one of MnSiCu.
Optionally, the nickel-based alloy powder is spherical or nearly spherical with a particle size of 45-350 μm.
According to the invention, the wear-resistant flux core composition takes diamond particles as a wear-resistant and reinforcing material, and takes transition metal oxide as a filling material, especially niobium oxide and molybdenum oxide, when the wear-resistant flux core composition is used for welding or braze coating, a salt film on the surface of diamond absorbs heat of an electric arc for decomposition, and generated ammonia gas can reduce oxygen partial pressure in an argon atmosphere and improve the atmosphere protection effect in the braze coating process; the generated molybdenum oxide and niobium oxide react with diamond to form a metal film of molybdenum and niobium, and the metal film is attached to the surface of the diamond layer, so that the heat damage of the diamond particles at high temperature can be reduced, and the brazing activity of the diamond particles can be improved. Moreover, niobium and molybdenum generated by reducing molybdenum oxide and niobium oxide by carbon are dissolved in the cladding metal, so that the linear expansion coefficient of the cladding metal can be reduced, the linear expansion coefficients of the cladding metal and the diamond particles are matched, the welding thermal stress of the diamond particles is reduced, and the diamond particles are prevented from generating cracks under the action of the welding thermal stress. In addition, unreacted niobium oxide and molybdenum oxide are melted and attached to the surface of the brazing coating, so that the coating is slowly cooled, the oxidation of the diamond coating is prevented, and the diamond coating is prevented from cracking due to the excessively high cooling speed.
As an embodiment of the present invention, the wear resistant flux core composition comprises surface activated diamond particles 0.6 wt.% to 10 wt.%, niobium oxide 6 wt.% to 25 wt.%, molybdenum oxide 6 wt.% to 40 wt.%, and the balance nickel based alloy powder.
In accordance with another object of the present invention, a wear resistant welding wire is provided; the wear resistant welding wire comprises, in mass fraction, 60 wt.% to 80 wt.% of a core and 20 wt.% to 40 wt.% of a sheath;
the drug core is selected from any of the abrasion resistant drug core compositions;
the material of the outer skin is selected from at least one of nickel, copper, silver, iron and their respective alloys.
Optionally, the outer skin is made of nickel.
Optionally, the diameter of the wear-resistant welding wire is 0.8mm to 2.0 mm.
Optionally, the diameter of the wear resistant welding wire may be independently selected from 0.8mm, 0.9mm, 1mm, 1.2mm, 1.5mm, 1.8mm, 2mm, and a diameter selected from a range between any of the foregoing.
Optionally, the thickness of the skin is 0.1mm to 0.3 mm.
Optionally, the thickness of the skin may be independently selected from 0.1mm, 0.15mm, 0.2mm, 0.25mm, 0.3mm, and a thickness selected from a range between any of the foregoing.
When the pure nickel sheath is used for welding or braze coating, the pure nickel sheath is arcing to generate a large amount of heat, and the pure nickel sheath and the flux core powder are melted and attached to the surface of a workpiece to form the wear-resistant diamond coating. Under the action of electric arc, the pure nickel sheath is transited to the surface of the workpiece through molten drops, is soft, can form a stress buffer layer between the diamond coating and the workpiece, and avoids the diamond coating from cracking.
According to another object of the present invention, there is provided a method for preparing the above-mentioned wear-resistant welding wire, the method comprising the steps of:
a1) uniformly mixing the uniformly mixed filling material and the diamond particles to obtain the wear-resistant flux core composition;
b1) feeding the wear-resistant flux-cored composition obtained in the step a1) into a groove formed by a sheath material, and forming a wear-resistant welding wire after closing and multi-step drawing.
Optionally, in the step a1), the filling material is mixed by a ball mill, the rotation speed of the ball mill is 200 r/min-250 r/min, and the ball milling time is 0.5 h-2 h.
Optionally, the ball milling pot of the ball mill is made of ceramic materials.
Optionally, the mass ratio of the filling material to the grinding balls in the ball mill is 1: 1-2; the grinding balls are high-chromium cast iron grinding balls, and the diameter of the grinding balls is 5-20 mm.
Optionally, in the step a1), the filler and the diamond particles are mixed by a mixer, wherein the rotation speed of the mixer is 30 r/min-60 r/min, and the mixing time is 0.5 h-1 h.
Optionally, the groove in step b1) is U-shaped or arc-shaped.
Optionally, the diamond particles in step a1) are surface activated diamond particles. Optionally, the surface activation method of diamond particles comprises:
a2) placing the diamond particles in an alkali liquor at the temperature of 80-90 ℃ for ultrasonic treatment, washing until the pH value is neutral, drying, then placing in an acid liquor for boiling treatment, washing until the pH value is neutral, and drying again;
b2) soaking the diamond particles treated in the step a2) in a solution containing transition metal ions at 60-70 ℃, and drying.
Optionally, in the step a2), the alkali solution is a sodium hydroxide solution with a concentration of 5gL to 10g/L, and the acid solution is a nitric acid solution with a concentration of 10 wt.% to 30 wt.%; the drying temperature is 60-80 ℃.
Optionally, in the step a2), the frequency of the ultrasonic treatment is 20kHz to 40kHz, and the time is 20min to 30 min; the boiling treatment time is 10 min-30 min.
Alternatively, in step b2), the solution containing transition metal ions comprises an ammonium molybdate solution and an ammonium niobium oxalate solution.
Optionally, the concentration of the ammonium molybdate solution is 25 g/L-80 g/L, and the concentration of the ammonium niobium oxalate solution is 35 g/L-60 g/L; the soaking time is 30-40 min; the drying temperature is 60-80 ℃.
As an embodiment of the present invention, the surface activation method of diamond particles includes:
(1) putting diamond particles into a sodium hydroxide solution with the concentration of 5 g/L-10 g/L and the temperature of 80-90 ℃, ultrasonically vibrating at 20 kHz-40 kHz for 20-30 min, cleaning with deionized water until the pH value is 7, and drying at 60-80 ℃;
(2) putting the dried diamond particles into a nitric acid solution with the mass fraction of 10-30% to boil for 10-30 min, washing the diamond particles by deionized water until the pH value is 7, and drying the diamond particles at the temperature of 60-80 ℃;
(3) soaking the dried diamond particles in a mixed solution of ammonium molybdate and ammonium niobium oxalate for 30-40 min, wherein the concentration of the ammonium molybdate solution is 25-80 g/L, the concentration of the ammonium niobium oxalate solution is 35-60 g/L, and the temperature of the mixed solution is 60-70 ℃;
(4) and fishing out the diamond particles from the mixed solution, and drying at 60-80 ℃ to obtain the diamond particles with activated surfaces.
As an embodiment of the present invention, a method for preparing the wear-resistant welding wire includes:
(1) putting niobium oxide, molybdenum oxide and nickel-based alloy powder into a ball mill according to the proportion, uniformly mixing, wherein the ball mill tank is made of ceramic, the grinding balls are made of high-chromium cast iron grinding balls with the diameter of 5-20 mm, the powder ball ratio is 1: 2-1: 1, the rotating speed of the ball mill is 200-250 r/min, and the ball milling time is 0.5-2.0 h;
(2) uniformly mixing the diamond particles with the surface activated and the uniformly mixed mixture of the niobium oxide, the molybdenum oxide and the nickel-based alloy powder by a V-shaped mixer according to the proportion, wherein the rotating speed is 30-60 r/min, and the mixing time is 0.5-1.0 h;
(3) after multiple rolling, the cross section of the pure nickel strip is in a U shape or an arc shape, the flux-cored powder mixture formed in the previous step is sent into a groove with the U shape or the arc shape of the cross section, and the wear-resistant flux-cored wire and the diamond brazing material are formed through closing and multiple drawing.
According to another object of the invention, there is provided the use of any of the above-mentioned wear resistant flux cored compositions and/or wear resistant welding wires in wear resistant brazing filler metal coating materials.
When the alloy is used as a wear-resistant brazing coating material, the protective gas is argon, and the dew point is lower than minus 54 ℃.
Alternatively, on-line continuous braze coating can be realized by taking the wear-resistant flux-cored composition and/or the wear-resistant welding wire as braze coating materials and taking electric arcs as braze coating heat sources:
a salt film on the surface of the diamond absorbs the heat of the electric arc for decomposition, the generated ammonia reduces the oxygen partial pressure of the argon atmosphere, and the atmosphere protection effect in the braze coating process is improved; the generated molybdenum oxide and niobium oxide react with the diamond to form a molybdenum and niobium metal film which is attached to the surface of the diamond, so that the heat damage of the diamond particles at high temperature can be reduced, and the brazing activity of the diamond particles is improved; niobium and molybdenum generated by reducing molybdenum oxide and niobium oxide by carbon are dissolved in the cladding metal, so that the linear expansion coefficient of the cladding metal can be reduced, the linear expansion coefficients of the cladding metal and the diamond particles are more matched, the welding thermal stress of the diamond particles is reduced, and the diamond particles are prevented from generating cracks under the action of the welding thermal stress; unreacted niobium oxide and molybdenum oxide are melted and attached to the surface of the brazing coating, so that the coating is slowly cooled, the oxidation of the diamond coating is prevented, and the diamond coating is prevented from cracking due to the excessively high cooling speed; the online continuous braze welding improves the braze welding efficiency and is suitable for the complex working condition environment of the industrial equipment in the in-service process; under the action of electric arc, the pure nickel alloy sheath is transited to the surface of the workpiece through molten drops, the pure nickel alloy sheath is soft, a stress buffer layer between the diamond coating and the workpiece is formed, and the diamond coating is prevented from cracking.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the wear-resistant flux-cored composition and the wear-resistant welding wire thereof, diamond particles are used as wear-resistant and reinforcing materials, and transition metal oxides with specific dosage are used as filling materials, so that the outer skin of the wear-resistant welding wire is transited to the surface of a workpiece through molten drops, is soft, can form a stress buffer layer between a diamond coating and the workpiece, and avoids cracking of the diamond coating formed on the surface of the workpiece.
(2) The preparation method of the wear-resistant welding wire provided by the invention is simple, efficient, high in continuity, controllable in cost, short in period and beneficial to large-scale industrial popularization.
(3) The invention also provides application of the wear-resistant flux-cored composition and the wear-resistant welding wire in the aspect of wear-resistant brazing coating materials, and when the wear-resistant flux-cored composition and the wear-resistant welding wire are used for the wear-resistant brazing coating materials, on-line continuous brazing coating can be realized, the brazing coating efficiency is greatly improved, and the adaptability is strong in complex working condition environments of industrial equipment in the service process.
Drawings
FIG. 1 is a schematic cross-sectional view of a wear-resistant welding wire in accordance with one embodiment of the present invention; wherein, 1 is pure nickel crust, 2 is abrasion-proof drug core;
FIG. 2 is an SEM surface topography of a braze coating formed by using the wear-resistant welding wire for braze coating in one embodiment of the invention.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. Unless otherwise specified, the raw materials in the examples of the present application were purchased commercially, and those who did not specify specific conditions in the examples were conducted under conventional conditions or conditions recommended by the manufacturer.
As an embodiment of the invention, as shown in fig. 1, the wear-resistant welding wire of the invention comprises a pure nickel sheath (1) and a wear-resistant flux core (2), wherein the mass ratio of the pure nickel sheath (1) is 20-40%, and the balance is the wear-resistant flux core (2), and the wear-resistant flux core (2) comprises the following components: 0.5-5.5 percent of diamond particles with activated surfaces, 5-15 percent of niobium oxide, 5-25 percent of molybdenum oxide and the balance of nickel-based alloy powder.
In one embodiment of the invention, the thickness of the pure nickel sheath (1) in the wear-resistant welding wire is 0.1-0.3 mm, and the diameter of the welding wire is 0.8-2.0 mm.
In the wear-resistant welding wire, the molybdenum oxide and the niobium oxide in the wear-resistant flux core (2) are powdery, and the granularity is 140-1000 meshes.
As an embodiment of the invention, the nickel-based powder in the wear-resistant flux core (2) is BNi73CrFeSiB(C)、BNi74CrFeSiB、BNi82CrSiBFe、BNi78CrSiBCuMoNb or BNi66One or more of MnSiCu with the granularity of 45-350 microns is spherical or nearly spherical.
EXAMPLE 1 preparation of a wear resistant welding wire
#1 wear-resistant welding wire
The wear-resistant flux core composition comprises the following components: 1.5 wt.% of diamond particles with activated surfaces, 5 wt.% of niobium oxide, 5 wt.% of molybdenum oxide and the balance of nickel-based alloy powder.
Outer skin: pure nickel.
Surface activation method of diamond particles:
(1) alkali liquor treatment of diamond particles:
selecting 5g/L sodium hydroxide solution at 90 ℃ from alkali liquor, and placing diamond particles in the alkali liquor for ultrasonic treatment; the ultrasonic conditions are as follows: ultrasonic vibration at 30kHz for 25 min;
washing with deionized water until pH is neutral, and drying at 70 deg.C;
(2) acid liquor treatment of diamond particles:
selecting a nitric acid solution with the mass fraction of 20% from the acid solution, placing the diamond particles obtained in the step (1) in the acid solution, boiling for 20min, cleaning with deionized water until the pH is neutral, and drying at 70 ℃;
(3) putting the diamond particles obtained in the step (2) into a mixed solution of ammonium molybdate and ammonium niobium oxalate at the temperature of 60 ℃, and soaking for 40 min;
wherein the concentration of the ammonium molybdate solution is 40g/L, and the concentration of the ammonium niobium oxalate solution is 60 g/L;
(4) and fishing out the diamond particles from the mixed solution, and drying at 70 ℃ to obtain the diamond particles with activated surfaces.
Mixing the materials of the wear-resistant flux core composition:
(1) putting niobium oxide, molybdenum oxide and nickel-based alloy powder into a ball mill according to the proportion, uniformly mixing, wherein the ball mill tank is made of ceramic, the grinding balls are made of high-chromium cast iron grinding balls with the diameter of 10mm, the powder ball proportion is 1:2, the rotating speed of the ball mill is 200r/min, and the ball milling time is 1 h;
(2) according to the proportion, a V-shaped mixer is adopted to uniformly mix diamond particles with activated surfaces and the uniformly mixed mixture of niobium oxide, molybdenum oxide and nickel-based alloy powder, the rotating speed is 60r/min, and the mixing time is 0.5 h.
Selecting a cold-rolled pure nickel strip with the width of 14mm and the thickness of 0.2mm, rolling the cold-rolled pure nickel strip into a U-shaped or arc-shaped cross section through multiple passes, feeding the wear-resistant flux-cored composition material into a U-shaped or arc-shaped groove with the cross section, forming an O-shaped cross section through a closed opening, wrapping the flux-cored powder in the groove, and drawing and reducing the diameter of the flux-cored powder by the conventional method one by one to obtain a wear-resistant welding wire with the diameter of 1.6mm, which is marked as 1#A wear-resistant welding wire. Wherein, the weight ratio of the pure nickel sheath is 32%.
A schematic cross-sectional view of a wear-resistant welding wire is shown in fig. 1.
# #2-5 wear-resistant welding wire
2#～5#Preparation method of wear-resistant welding wire and 1#The wear-resistant welding wires are substantially the same, with the differences listed in table 1:
TABLE 12#～5#Wear-resistant welding wire and 1#Different parameters of wear-resistant welding wire
Obtained 2#The diameter of the wear-resistant welding wire is phi 1.8mm, and the weight ratio of the pure nickel sheath is 28%.
Obtained 3#The diameter of the wear-resistant welding wire is phi 1.8mm, and the weight ratio of the pure nickel sheath is 34%.
Obtained 4#The diameter of the wear-resistant welding wire is phi 2mm, and the weight proportion of the pure nickel sheath is 37%.
Obtained 5#The diameter of the wear-resistant welding wire is phi 2mm, and the weight percentage of the pure nickel sheath is 39%.
In this example for the preparation of 1#～5#Wear resistance of wear-resistant welding wireThe 50-mesh passing rate of the abrasive core composition reaches 100 percent, and the weight percentage of the powder with the granularity larger than 120 meshes is less than 30 percent.
Experimental example 1 surface morphology of braze coating layer of wear-resistant welding wire and braze coating application
The PhenomXL type Scanning Electron Microscope (SEM) is used for representing the surface morphology of the braze coating, and the result is shown in figure 2, the surface of the coating obtained by braze coating is uniform and has no cracks, the diamond particles are embedded into cladding metal, and the cladding metal has good wettability to the diamond particles and has no cracks.
As 1 prepared in example 1#～5#The wear-resistant welding wire is used for surfacing on the surface of a Q235 steel plate with the thickness of 10mm, the surfacing protective atmosphere is argon, the dew point is-55 ℃, and the surfacing process parameters are as follows: the welding polarity is direct current reverse connection, the welding current is 300A-480A, the welding voltage is 23V-35V, and the welding lap joint amount is 50%.
To be compared with 1 in example 1#～5#The diamond powder with the same amount of wear-resistant welding wire and treatment method and the nickel-based alloy powder with the same amount are directly coated with a Q235 steel plate with the thickness of 10mm in an argon shielded furnace, and the coating thickness is 0.5mm, which is taken as a comparative example D1#～D5#。
And (3) wear resistance test: the subject was 1 prepared as in example 1#～5#A wear-resistant welding wire for a sample formed by surface welding of a Q235 steel plate having a thickness of 10mm, and a comparative example D1#～D5#The formed sample was braze-coated. The dimensions of the test specimen were 57 mm. times.25.5 mm. times.10.5 mm.
The abrasion resistance test conditions included: the test load is 20N, the abrasive is 120-type brown corundum, the rotating speed of the rubber wheel is 100r/min, the sand flow is 100g/min, and the abrasion time is 15 min; wherein the abrasion of the diamond coating is expressed by weight loss, and 5 groups of samples were prepared for each example and comparative example, and the average value and standard deviation were respectively obtained. The test results are shown in table 2.
TABLE 2 abrasion resistance test results
As can be seen from the results of the wear-resistant tests in Table 2, the wear weight loss values of the diamond coating samples prepared from the wear-resistant flux-cored composition and the wear-resistant welding wire provided by the invention are obviously lower than the wear loss weight values of the comparative examples, which indicates that the wear resistance of the diamond coating samples prepared from the wear-resistant flux-cored composition and the wear-resistant welding wire provided by the invention is higher than that of the diamond coating samples prepared by the traditional brazing method. The wear-resistant flux-cored composition and the wear-resistant welding wire provided by the invention have longer service life, and compared with the traditional diamond coating preparation method, the production efficiency is greatly improved by adopting the wear-resistant flux-cored composition and the wear-resistant welding wire provided by the invention for braze coating. In addition, the wear-resistant flux-cored composition and the wear-resistant welding wire provided by the invention can also be suitable for the complex working condition environment of in-service process industrial equipment, which can not be overcome by the traditional diamond coating preparation method.
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 (22)
1. A wear resistant flux core composition, wherein the wear resistant flux core composition comprises a wear resistant material and a filler material;
the wear-resistant material accounts for 0.6-10 wt% of the wear-resistant flux core composition; the wear resistant material comprises diamond particles;
the filling material comprises transition metal oxide powder and nickel-based alloy powder; the transition metal oxide powder accounts for 12-65 wt.% of the filler material;
the transition metal oxide is selected from at least one of metal oxides of elements in VB group or VIB group;
the transition metal oxide powder includes niobium oxide powder and molybdenum oxide powder.
2. The wear-resistant flux core composition of claim 1, wherein the mass ratio of the niobium oxide powder to the molybdenum oxide powder is (6-25): (6-40).
3. The abrasion resistant flux core composition of claim 2, wherein the niobium oxide powder and the molybdenum oxide powder have a particle size of 140 mesh to 1000 mesh.
4. The abrasion resistant flux core composition of claim 1, wherein the diamond particles have a particle size of 140 mesh to 600 mesh.
5. The abrasion resistant core composition of claim 4 wherein the diamond particles are surface activated diamond particles.
6. The abrasion resistant flux core composition as claimed in claim 1, wherein said nickel based alloy powder is selected from BNi73CrFeSiB(C)、BNi74CrFeSiB、BNi82CrSiBFe、BNi78CrSiBCuMoNb or BNi66At least one of MnSiCu.
7. The abrasion resistant flux core composition according to claim 6, wherein the nickel based alloy powder is spherical or near spherical with a particle size of 45 μm to 350 μm.
8. A wear resistant welding wire, characterized in that the wear resistant welding wire comprises, in mass fraction, 60 wt.% to 80 wt.% of a core and 20 wt.% to 40 wt.% of a sheath;
the core is selected from the abrasion resistant core composition of claim 1;
the material of the outer skin is selected from at least one of nickel, copper, silver, iron and their respective alloys.
9. The wear-resistant welding wire as claimed in claim 8, wherein the outer layer is made of nickel.
10. The wear-resistant welding wire according to claim 8, wherein the diameter of the wear-resistant welding wire is 0.8mm to 2.0 mm.
11. The wear resistant welding wire of claim 10 wherein the sheath has a thickness of 0.1mm to 0.3 mm.
12. The method of preparing the wear resistant welding wire of any one of claims 8 to 11, characterized in that the method comprises the steps of:
a1) uniformly mixing the uniformly mixed filling material and the diamond particles to obtain the wear-resistant flux core composition;
b1) feeding the wear-resistant flux-cored composition obtained in the step a1) into a groove formed by a sheath material, and forming a wear-resistant welding wire after closing and multi-step drawing.
13. The method of claim 12, wherein the cross-section of the groove in step b1) is U-shaped or curved.
14. The method according to claim 12, wherein the diamond particles in step a1) are surface activated diamond particles;
the method of surface activation comprises:
a2) placing diamond particles in alkali liquor at the temperature of 80-90 ℃ for ultrasonic treatment, washing until the pH =7, drying, then placing in acid liquor for boiling treatment, washing until the pH =7, and drying again;
b2) soaking the diamond particles treated in the step a2) in a solution containing transition metal ions at the temperature of 60-70 ℃, and drying.
15. The method as claimed in claim 14, wherein in the step a2), the alkali solution is sodium hydroxide solution with a concentration of 5 gL-10 g/L, and the acid solution is nitric acid solution with a concentration of 10 wt.% to 30 wt.%; the drying temperature is 60-80 ℃.
16. The method according to claim 14, wherein in the step a2), the ultrasonic treatment is carried out at a frequency of 20 kHz-40 kHz for a time of 20 min-30 min; the boiling treatment time is 10-30 min.
17. The method according to claim 14, wherein in step b2), the solution containing transition metal ions comprises ammonium molybdate solution and ammonium niobium oxalate solution; the concentration of the ammonium molybdate solution is 25-80 g/L, and the concentration of the ammonium niobium oxalate solution is 35-60 g/L; the soaking time is 30-40 min; the drying temperature is 60-80 ℃.
18. The method as claimed in claim 12, wherein in the step a1), the filling material is mixed by a ball mill, the rotation speed of the ball mill is 200 r/min-250 r/min, and the ball milling time is 0.5 h-2 h.
19. The method according to claim 18, wherein the mass ratio of the filler material to the grinding balls in the ball mill is 1: 1-2; the grinding balls are high-chromium cast iron grinding balls, and the diameter of the grinding balls is 5 mm-20 mm.
20. The method according to claim 18, wherein in step a1), the filler material and the diamond particles are mixed by a mixer at a rotation speed of 30r/min to 60r/min for a mixing time of 0.5h to 1 h.
21. Use of the wear resistant flux cored composition of any one of claims 1 to 7 and the wear resistant welding wire of any one of claims 8 to 11 in wear resistant brazing filler metal.
22. Use according to claim 21, characterised in that, when used as a wear resistant braze material, the shielding gas is argon and the dew point is below-54 ℃.
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