A flux cored wire dedicated to the deposition of copper on a steel substrate

Abstract

The application discloses a flux-cored wire for depositing copper on a steel base, which comprises a hollow rectangular copper alloy shell and an internal protective agent flux core. The copper alloy shell wrapping the flux core has a rectangular cross section, and the chemical composition of the copper alloy welding wire comprises 0.05-0.5% of Pb, 0.01-0.5% of MoS2, 0.01-0.5% of Nd, 0.01-0.1% of C, 1-2% of In, and the balance of Cu in percentage of mass. The chemical composition of the flux core comprises 10-12% of borax, 5% of ZnCl2, and the balance of corrosion inhibitor carboxymethyl cellulose wrapped hydrochloric acid. The copper alloy flux-cored wire containing Pb and In has good lubricating properties after forming, excellent bonding strength with the steel base and good forming performance. The flux-cored wire is used for depositing copper alloy on the steel base to realize high-efficiency and high-quality forming, and is suitable for depositing and adding materials on the surface of a stainless steel, a high-strength steel and the like, and the deposited and added material has consistent mechanical properties and high quality.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of additive manufacturing in metal material processing engineering, and relates to a flux-cored wire specially used for cladding copper on a steel base. BACKGROUND

[0002] Copper alloy is widely used in industry due to its excellent plasticity and electrical conductivity, but its inherent low structural strength and high price limit its use; steel can be used in many occasions in engineering due to its high strength and low price. Therefore, copper and steel can be combined according to the use requirements to comprehensively utilize the excellent performance of the two metals. The connection of dissimilar metals is complex, and the strength of the connection limits the use of the composite metal structure, and the metal additive manufacturing can effectively manufacture the dissimilar metal composite structure.

[0003] After searching the existing reports on copper-steel dissimilar metal additive manufacturing, the copper-steel dissimilar metal additive manufacturing generally uses explosive welding or mechanical connection to form a composite plate, and cannot directly form a part with a specific shape. The dissimilar metal additive manufacturing through the mechanical connection and the plate-shaped composite material means that the geometry of the additive product is limited, and the organization is uncontrollable and the quality cannot be guaranteed. SUMMARY

[0004] The purpose of the present application is to provide a flux-cored wire specially used for cladding copper on a steel base, which has the function of being suitable for cladding copper alloy on a steel base and is suitable for repairing, surface treatment and additive manufacturing of metal materials.

[0005] The technical scheme for achieving the purpose of the present application is as follows:

[0006] A flux-cored wire specially used for cladding copper on a steel base, the chemical composition of the copper alloy metal shell includes 0.05% to 0.5% of Pb, 0.01% to 0.5% of MoS2, 0.01% to 0.5% of Nd, 0.01% to 0.1% of C, 1% to 2% of In, and the balance is Cu. The chemical composition of the flux core includes 10% to 12% of borax (Na2B4O7·10H2O), 5% of ZnCl2, and the balance is hydrochloric acid wrapped with corrosion inhibitor (carboxymethyl cellulose) particles.

[0007] Using commercially available Cu, lead ingot, molybdenum disulfide, metal Nd, graphite and metal In as raw materials, the rod (wire) material can be obtained by adopting a conventional smelting method according to the designed component ratio, adding the "covering agent" and "degassing agent" determined by optimization screening during smelting, and horizontal continuous casting. The wire material is obtained by annealing and skinning and drawing. After cleaning and coiling, the welding wire for automatic welding is obtained. The straight wire can also be obtained by straightening and cutting.

[0008] The product can adopt induction cladding additive, plasma additive, laser additive and composite heat source additive method, and is used for automatic or semi-automatic additive of steel base body and cladded copper alloy.

[0009] Compared with the prior art, the present application has the following advantages:

[0010] The strip provided by the present application is used for cladding additive, and the steel base body does not need to be pre-treated before additive, and the operation of removing the oxide film is not needed, the oxide film on the steel surface is removed and the wettability of the liquid copper is improved by the core protective agent in the additive process, the copper and the steel are effectively combined, the pre-treatment energy consumption is saved, and the manufacturing efficiency is improved.

[0011] It is found and proved that the trace elements In and Nd have the "anti-infiltration" ability, the problem of Fe infiltration to the copper side to form intermetallic compounds in the copper-steel dissimilar metal welding process is solved, the third phase can be formed at the copper-steel interface to block the Fe atom infiltration, so that the copper-steel combination interface quality is excellent, and there is no crack and pore. When the induction cladding additive, plasma additive, laser additive and composite heat source additive method are used for additive manufacturing of copper-steel composite structure, the additive part has no defects such as pores and cracks.

[0012] It is found that the addition amount (mass percentage) of Pb, MoS2, Nd and C in the copper alloy core strip of the present application must be controlled in the range of 0.01% to 0.5%. Within the above component range, the copper alloy core strip of the present application has the best anti-intermetallic compound formation performance, and the mechanical properties of the additive part can meet the requirements. In the process of the present application, through analysis of test data of 15 groups of 150 alloy formulations, it is found that when the component ratio deviates by 5% to 200%, the crack generation tendency in the additive process is increased by more than 60%, the mechanical properties of the component in the plasma additive method are also greatly reduced (decrease amplitude is 10% to 40%), and the crack occurrence rate and the number of cracks of the additive part are increased by 50% to 100%.

[0013] It is found that In and Nd are both interfacial active elements in the copper alloy, and are free in the grain boundary. During smelting and additive, they are oxidized on one hand, and combined with Fe atoms on the other hand, so that the free Fe is greatly reduced, and the function of "fixing Fe" is achieved, so that the harm of brittle phase caused by intermetallic compound formation is eliminated. Therefore, while In and Nd are added, Pb and MoS2 are added in equal amount, which can significantly improve the lubricity of the cladded copper alloy, reduce the friction under the working condition of the copper alloy, so that the copper-steel alloy component in the cladded state can reduce the friction force with the friction pair, and the purpose of prolonging the service life of the component is achieved. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1The schematic diagram of the cross section structure of the strip of the application.

[0015] Figure 2 The contrastive diagram of the copper steel interface after the addition of the application and the ordinary copper alloy addition interface, (a) the application (b) ordinary copper alloy. DETAILED DESCRIPTION

[0016] The application will be further described below in combination with the drawings and examples

[0017] The technical scheme of the application specifically comprises the following and solves the following key problems:

[0018] 1) By adding trace elements In and Nd, the copper alloy in the deposited state is enhanced in the ability to resist penetration, the problem of Fe penetration to the copper side to form intermetallic compounds in the copper steel dissimilar metal welding process is solved, the third phase can be formed at the copper steel interface to block the penetration of Fe atoms, thereby ensuring that the copper steel bonding interface is of excellent quality, free of cracks and pores. When the copper steel composite structure is manufactured by induction deposition, plasma deposition, laser deposition and composite heat source deposition methods, the deposited part is free of defects such as pores and cracks.

[0019] 2) After 15 groups of 150 alloy formula test researches, it is found that the addition of trace amounts of Pb, MoS2 and C in the conventional copper alloy can significantly improve the lubricity of the deposited copper alloy, reduce the friction under the working condition of the copper alloy, so that the copper steel alloy component in the deposited state can reduce the friction force with the friction pair, and the purpose of prolonging the service life of the component is achieved.

[0020] 3) It is found through tests that the addition amount (mass percentage) of Pb, MoS2, Nd and C of the flux cored strip for depositing copper on the steel substrate of the application must be controlled in the range of 0.01% to 0.5%. Within the above component range, the strip containing In and Nd of the application has the highest lubricity, the best intermetallic compound generation resistance of the deposited material, and the best mechanical properties of the deposited material component.

[0021] The application will be further described below in combination with the drawings and examples

[0022] The structure of the strip of the application is specifically: a hollow structure rectangular copper alloy shell and an internal protective agent flux core, the copper alloy shell wrapping the flux core, and the cross section of the copper alloy shell is rectangular.

[0023] The strip is internally hollow rectangular structure, wherein the height h of the hollow rectangular structure is determined by the following formula: h = ηv / v0·H, wherein v is the deposition speed, v0 is the standard deposition speed, the value of which is 2 m / min, η is the cross section proportion coefficient, the value of which is 0.1-0.3, and H is the height of the rectangular cross section outside.

[0024] The distance from the core to the bottom surface section is m = β·IU / v, wherein β is an energy coefficient, which affects the thickness of the copper material on the ground, and is 0.0001-0.00015; I is the additive current, U is the additive voltage, and V is the additive speed.

[0025] The rectangular width d of the cross-section of the strip is determined by the following formula: d = θ·W·v / v0, wherein W is the cross-sectional outer width, v is the additive speed, v0 is the standard additive speed, and θ is a shape adjustment coefficient, and is 0.5-0.9. Embodiment

[0026] An In and Nd-containing core wire strip dedicated to depositing copper on a steel substrate, the chemical composition of the strip includes, by mass percentage: 0.01% of In, 0.01% of Nd, 0.01% of C, 0.01% of MoS2, 0.05% of Pb, 5% of Sn, and the balance of Cu; the chemical composition of the core wire includes 11% of borax (Na2B4O7·10H2O), 5% of ZnCl2, and the balance of hydrochloric acid wrapped by corrosion inhibitor (carboxymethyl cellulose) particles. The strip has excellent processability. A rectangular strip with a width of 10 mm and a thickness of 5 mm is used, the additive substrate is a 20 mm thick 50SiMnVB test plate, the additive current is 260 A, the additive arc voltage is 26 V, the argon gas flow is 22 L / min (liters / minute), the plasma welding gun is used for additive, the additive part is subjected to X-ray detection, and the requirements of GB / T3323-2005 "Metal Fusion Welding Welded Joints Radiography" for grade I welded joints are met, and the copper-steel interface shear strength is 180 MPa±10 MPa. Embodiment

[0027] An In and Nd-containing core wire strip dedicated to depositing copper on a steel substrate, the chemical composition of the strip includes, by mass percentage: 0.01% of In, 0.01% of Nd, 0.01% of C, 0.01% of MoS2, 0.05% of Pb, 5% of Sn, and the balance of Cu; the chemical composition of the core wire includes 11% of borax (Na2B4O7·10H2O), 5% of ZnCl2, and the balance of hydrochloric acid wrapped by corrosion inhibitor (carboxymethyl cellulose) particles. The strip has excellent processability. A rectangular strip with a width of 10 mm and a thickness of 5 mm is used, the additive substrate is a 20 mm thick 50SiMnVB test plate, the additive current is 260 A, the additive arc voltage is 26 V, the argon gas flow is 22 L / min (liters / minute), the plasma welding gun is used for additive, the additive part is subjected to X-ray detection, and the requirements of GB / T3323-2005 "Metal Fusion Welding Welded Joints Radiography" for grade I welded joints are met, and the copper-steel interface shear strength is 180 MPa±10 MPa. Embodiment

[0028] An In and Nd containing flux cored wire for copper deposition on steel substrate, the chemical composition of the wire includes 0.01% of In, 0.01% of Nd, 0.01% of C, 0.01% of MoS2, 0.05% of Pb, 5% of Sn, and the balance of Cu; the chemical composition of the flux includes 11% of borax (Na2B4O7·10H2O), 5% of ZnCl2, and the balance of hydrochloric acid coated with corrosion inhibitor (carboxymethyl cellulose) particles. The wire has excellent processability. Rectangular wire with a width of 10 mm and a thickness of 5 mm is used, the deposition substrate is a 20 mm 30CrMnSi test plate, the laser power is 5 kW, the deposition speed is 2 m / min, and the argon gas flow rate is 22 L / min (liters / min). Laser deposition is used, the weld is subjected to X-ray detection, and the requirements of GB / T3323-2005 "Metal Fusion Welding Welded Joints Radiography" for Grade I welded joints are met, and the copper-steel interface shear strength of the deposition component is 200 MPa ± 20 MPa.

[0029] Comparative Example 1

[0030] An In and Nd containing flux cored wire for copper deposition on steel substrate, the chemical composition of the wire includes 0.01% of In, 0.01% of Nd, 0.01% of C, 0.01% of MoS2, 0.05% of Pb, 5% of Sn, and the balance of Cu; the chemical composition of the flux includes 11% of borax (Na2B4O7·10H2O), 5% of ZnCl2, and the balance of hydrochloric acid coated with corrosion inhibitor (carboxymethyl cellulose) particles. The wire has excellent processability. Rectangular wire with a width of 10 mm and a thickness of 5 mm is used, the deposition substrate is a 20 mm 30CrMnSi test plate, the laser power is 5 kW, the deposition speed is 2 m / min, and the argon gas flow rate is 22 L / min (liters / min). Laser deposition is used, the weld is subjected to X-ray detection, and the requirements of GB / T3323-2005 "Metal Fusion Welding Welded Joints Radiography" for Grade I welded joints are met, and the copper-steel interface shear strength of the deposition component is 200 MPa ± 20 MPa.

[0031] Comparative Example 2

[0032] An In and Nd containing flux cored wire for copper deposition on steel substrate, the chemical composition of the wire includes 0.25% In, 0.05% Nd, 0.15% C, 0.2% MoS2, 0.15% Pb, 7% Sn, and the balance Cu, the chemical composition of the flux includes 11% borax (Na2B4O7·10H2O), 5% ZnCl2, and the balance corrosion inhibitor (carboxymethyl cellulose) coated hydrochloric acid. The wire has excellent processability. Rectangular wire with a width of 10 mm and a thickness of 5 mm is used, the deposition substrate is 20 mm thick 45CrMnSi, the deposition current is 280 A, the deposition arc voltage is 24 V, and the argon gas flow rate is 22 L / min (liters / minute), plasma deposition is used, the weld is subjected to X-ray detection, and the requirements of GB / T3323-2005 "Metal Fusion Welding Welded Joints Radiography" for Grade I welded joints are met, and the tensile strength of the weld is 170 MPa±15 MPa.

[0033] Comparative Example 3

[0034] An In and Nd containing flux cored wire for copper deposition on steel substrate, the chemical composition of the wire includes 0.05% In, 0.1% Nd, 0.15% C, 0.05% MoS2, 0.15% Pb, 5% Sn, and the balance Cu, the chemical composition of the flux includes 11% borax (Na2B4O7·10H2O), 5% ZnCl2, and the balance corrosion inhibitor (carboxymethyl cellulose) coated hydrochloric acid. The wire has excellent processability. Rectangular wire with a width of 10 mm and a thickness of 5 mm is used, the deposition substrate is 20 mm thick 45CrMnSi, the deposition current is 280 A, the deposition arc voltage is 24 V, and the argon gas flow rate is 22 L / min (liters / minute), plasma deposition is used, the weld is subjected to X-ray detection, and the requirements of GB / T3323-2005 "Metal Fusion Welding Welded Joints Radiography" for Grade I welded joints are met, and the tensile strength of the weld is 170 MPa±15 MPa.

Claims

1. A flux-cored strip specifically for depositing copper onto a steel substrate, characterized in that, The strip structure is as follows: a hollow copper alloy metal shell and an internal core. The copper alloy metal shell encasing the core has a rectangular cross-section. The chemical composition of the copper alloy metal shell, by mass percentage, includes 0.05%–0.5% Pb, 0.01%–0.5% MoS2, 0.01%–0.5% Nd, 0.01%–0.1% C, 1%–2% In, and the balance is Cu. The chemical composition of the core, by mass percentage, includes 10%–12% borax Na2B4O7·10H2O, 5% ZnCl2, and the balance is hydrochloric acid encapsulated with carboxymethyl cellulose corrosion inhibitor.

2. The flux-cored strip for depositing copper on a steel substrate according to claim 1, characterized in that, The strip has a hollow rectangular structure inside, and the height h of the hollow rectangle is determined by the following formula: h=ηv / v0·H, where v is the additive speed, v0 is the standard additive speed with a value of 2m / min, η is the cross-sectional ratio coefficient with a value of 0.1-0.3, and H is the external height of the rectangular cross-section of the strip.

3. The flux-cored tape for depositing copper on a steel substrate according to claim 1, characterized in that, The width d of the strip cross-section core rectangle is determined by the following formula: d = θ·W·v / v0, where W is the outer width of the cross-section, v is the additive speed, v0 is the standard additive speed, and θ is the shape adjustment coefficient, which is taken as 0.5-0.9.

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