CN107498210A - A kind of Cu sills being modified for red copper surface and preparation and welding method - Google Patents

A kind of Cu sills being modified for red copper surface and preparation and welding method Download PDF

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Publication number
CN107498210A
CN107498210A CN201710700484.4A CN201710700484A CN107498210A CN 107498210 A CN107498210 A CN 107498210A CN 201710700484 A CN201710700484 A CN 201710700484A CN 107498210 A CN107498210 A CN 107498210A
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China
Prior art keywords
cloth
copper base
copper
brazing
base brazing
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CN201710700484.4A
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Chinese (zh)
Inventor
许祥平
何力
黄晓龙
康昊杰
邹家生
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JIANGSU YANGMING SHIP-EQUIPMENT MANUFACTURING TECHNOLOGY Co Ltd
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JIANGSU YANGMING SHIP-EQUIPMENT MANUFACTURING TECHNOLOGY Co Ltd
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Priority to CN201710700484.4A priority Critical patent/CN107498210A/en
Publication of CN107498210A publication Critical patent/CN107498210A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/30Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302Cu as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • B23K1/008Soldering within a furnace
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K1/00Soldering, e.g. brazing, or unsoldering
    • B23K1/20Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
    • B23K1/206Cleaning
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40Making wire or rods for soldering or welding
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C9/00Alloys based on copper
    • C22C9/05Alloys based on copper with manganese as the next major constituent

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention discloses a kind of Cu sills being modified for red copper surface, including the copper base brazing cloth being connected with red copper surface and the WC hardware cloths being connected with copper base brazing cloth, the elemental composition of the copper base brazing cloth by weight percentage to include:Mn30%~35%, Ni4%~6%, Sn0.5%~1.5%, Zn0.5%~1.0%, Si0.1%~0.3%, La0.1%~0.2%, polytetrafluoroethylene (PTFE) 0.01~0.03%, surplus Cu;The elemental composition of the WC hardware cloths by weight percentage includes:WC50%~80%, surplus are the copper base brazing cloth.The present invention avoids generating brittle intermetallic compound in coating and matrix conversion zone by the fusing point toward addition trace alloying element in copper base solder and rare earth element improvement copper base solder, wetability and seam-filling ability.Copper base solder is rolled into the problem of adhesive tape shape is advantageous to overcome workpiece size complex-shaped simultaneously, coordinates the soldering processes of high vacuum to advantageously reduce the generation of brittle metal compound, reduces residual stress.

Description

A kind of Cu sills being modified for red copper surface and preparation and welding method
Technical field
The present invention relates to the Cu sills being modified for red copper surface and preparation and welding method, belongs to soldering field.
Background technology
Fine copper has excellent conduction, thermal conductivity and corrosion resistance and processing forming, electric power, electrician, metallurgy and The industrial circles such as machinery are widely used (such as electron tube, lead frame, electrified rail, blast-furnace tuyere and continuous casting crystallining Device etc.).But the case hardness and wearability of fine copper are poor to cause some brass wares too early because of surface abrasion or plastic deformation Failure, service life substantially reduces, so as to limit the application of fine copper.Realize that the effective surface modification of fine copper is led to expanding its application Domain is significant and is worth.
Surface carried out to fine copper be modified mainly have a thermal spraying, built-up welding, plating, the methods of laser cladding.But these methods are all In the presence of the limitation of itself, such as to prepare composite coating operating environment poor for thermal spraying, it is difficult to the larger coating of thickness is prepared, and Coating and matrix are mechanical bond, and bond strength is low.Field of welding temperature is difficult to control when built-up welding prepares composite coating, matrix material Larger residual stress inside be present and be easily deformed, heap postwelding coating surface is coarse, increases machining procedure.It is prepared by plating Coating layer thickness it is relatively thin, protective effect is poor.Laser melting coating one-time investment cost is high, and it is higher when preparing composite coating Energy density can cause the scaling loss of alloying element, change the tissue of hard phase and Binder Phase, to composite coating surface Hardness and wearability produce certain influence.Fine copper is combined with the excellent properties of hard coat, could turn into preferable Structural material.Preparation for coating needs to consider the difference such as linear expansion coefficient, thermal conductivity of coating and matrix.Because fine copper melts Point is higher, and thermal conductivity is good, easily produces larger residual stress in cooling so that the bond strength of coating and matrix is relatively low. Therefore it is to solve the above problems and practical implementation problem to develop a kind of new surface metalation material, preparation method and technique Key.
The content of the invention
Goal of the invention:In order to overcome the deficiencies in the prior art, the present invention provides a kind of red copper surface that is used for and is modified Cu sills and preparation and welding method, can effectively improve the wearability and hardness of red copper surface, adjustment coating layer thickness simultaneously carries The bond strength of high coating and matrix.
Technical scheme:To achieve the above object, the of the invention Cu sills for being used for red copper surface and being modified, including with red copper The copper base brazing cloth of surface connection and the WC hardware cloths being connected with copper base brazing cloth, the copper base brazing cloth is by weight percentage The elemental composition of meter includes:Mn30%~35%, Ni4%~6%, Sn0.5%~1.5%, Zn0.5%~1.0%, Si0.1%~0.3%, La0.1%~0.2%, polytetrafluoroethylene (PTFE) 0.01~0.03%, surplus Cu;The WC hardware cloths are pressed The elemental composition of percentage by weight meter includes:WC50%~80%, surplus are the copper base brazing cloth.
Preferably, the copper base brazing cloth and WC hardware cloths are flexible adhesive tape shape, thickness is 0.5~2.0mm.
Preferably, the WC is nickel bag WC, nickel bag WC particle size is 30~45 μm.
A kind of above-mentioned Cu sills for being used for red copper surface and being modified, comprise the following steps:
A, the preparation of copper base brazing cloth
(1) Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder are weighed by mass percentage, and are mixed It is even;
(2) obtained mixed metal powder particle is rolled in automatic roll equipment, control bonding cloth preliminary first Thickness in 3.0~5.0mm or so, roll is carried out again to bonding cloth, adjusts the spacing between roller, control and is highly 0.5~2.0mm, bonding one normal pressure of cloth is given, 2~3 repetition rolls are carried out, between surface of metal particles and metallic particles Bonding agent produce squeezing action, bonding agent forms threadiness under squeezing action;To copper base brazing cloth tow sides carry out 5~ 6 repetition rolls, metallic fiber form a crisscross three-dimensional spider net type structure, and bonding is inlayed or be wrapped in metallic particles In agent, scattered alloying metal powder is set to form the entirety connected each other, the metallic particles in each section of threadiness uniformly divides Cloth, roll form flexible copper base brazing cloth;
B, the preparation of WC hardware cloths
(1) weigh WC powder, Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder by mass percentage, and by its It is well mixed;
(2) obtained mixed metal powder particle is being pricked into rod equipment progress roll automatically, control bonding cloth preliminary first Thickness in 3.0~5.0mm or so, carry out roll again to WC hardware cloths, adjust the spacing between roller, control and be highly 0.5~2.0mm, give WC hardware cloths one normal pressure, carry out 2~3 repetition rolls, to surface of metal particles and metallic particles it Between bonding agent produce squeezing action, bonding agent forms threadiness under squeezing action;To WC hardware cloths tow sides carry out 5~ 6 repetition rolls, metallic fiber form a crisscross three-dimensional spider net type structure, and bonding is inlayed or be wrapped in metallic particles In agent, scattered alloying metal powder is set to form the entirety connected each other, the metallic particles in each section of threadiness uniformly divides Cloth, roll form flexible WC hardware cloths.
A kind of above-mentioned soldering processes for being used for the Cu sills that red copper surface is modified, comprise the following steps:
(1) preparatory stage:First fine copper surface to be brazed is cleared up, removes the impurity, greasy dirt and oxide-film on surface, It is placed in acetone, using ultrasonic wave cleaning 10-15min, according to the shape on fine copper surface, cutting corresponding flexible copper base brazing Cloth and WC hardware cloths;
(2) installation step:Fine copper matrix is placed on it is following, by flexible the copper base brazing cloth and WC hardware cloths that cut by The order of fine copper/copper base brazing cloth/WC hardware cloths is put into soldering oven;
(3) soldering processes:The sample assembled is integrally placed at vacuum not less than 1.5 × 10-3Pa vacuum brazing is set In standby, 300~350 DEG C are warming up to 8~10 DEG C/min speed first, 20~25min is incubated, with 5~8 DEG C/min speed 550~600 DEG C are warming up to, is incubated 20~25min, then 800~850 DEG C are continuously heating to 5~8 DEG C/min speed, insulation 20~30min, then 1030~1080 DEG C of brazing temperature is warming up to 5~8 DEG C/min speed, 20~30min is incubated, then with 5 ~8 DEG C/min speed is cooled to 600~650 DEG C, is incubated 20~30min, finally cools to room temperature with the furnace.
In the present invention, it is the mechanical mixture of WC particle and above-mentioned copper base brazing cloth powder before the rolling of described WC hardware cloths Thing.The quality purity that the quality purity of the alloy powder Mn is 99.50%~99.90%, Ni is 99.50%~99.90%, The quality purity that the quality purity that Sn quality purity is 99.50%~99.90%, Si is 99.50%~99.90%, La is 99.50%~99.90%, Cu quality purity are 99.50%~99.90%.By toward adding microalloy in copper base solder Element and rare earth element improve the fusing point of copper base solder, wetability and seam-filling ability, while avoid in coating and matrix conversion zone Generate brittle intermetallic compound.Copper base solder is rolled into adhesive tape shape simultaneously to be advantageous to overcome workpiece size complex-shaped Problem, coordinate the soldering processes of high vacuum to advantageously reduce the generation of brittle metal compound, reduce residual stress.
Beneficial effect:Compared with prior art, possessed advantage and beneficial effect are mainly reflected in following the present invention Several respects:
(1) using the present invention be used for red copper surface be modified welding procedure, by vacuum brazing connection be not in pollution, Uneven heating and problems of crack.Coat inside and coating and matrix junction stress concentration are small, and coating surface shaping is smooth It is attractive in appearance.
(2) copper-based material that red copper surface of the invention is modified, is made flexible fiber shape under the repeat-rolling of roll Metal cloth material.The copper base brazing cloth of adhesive tape shape and the alloy material composition of WC hardware cloths are uniform, and powder is fine and close, can be cut to It is variously-shaped, it is strong to adapt to workpiece ability.
(3) the copper base brazing cloth and fine copper matching that red copper surface of the invention is modified are good, with appropriate fusing point, well Wetability, seam-filling ability and environment friendly, while decrease the copper-based solder brazing of tradition and easily generate frangible compounds Problem.Mn advantageously reduces solder fusing point, improves solder fluidity, the influence also having had to solder heat resistance and wetability, but When CuMn reaches eutectic point, fusing point is still higher, therefore also to control Mn content.Ni be advantageous to improve solder mobility and Intensity, but Ni can improve the fusing point of solder, therefore to control Ni content.The fusing point of solder can be reduced by adding Sn and Zn, and Zn is also The toughness of solder can be increased.But excessive Sn can generate brittlement phase, and Zn is volatile, coating can be made to produce stomata, and it is poisonous, because This content to Sn, Zn will be also controlled.Zn volatilization can be reduced by adding appropriate Si, but excessive Si can be generated Silica is not easy to remove.Adding micro rare earth element can be with crystal grain thinning.The present invention passes through reasonable to each alloying element Maximum effect has been given play to it is made.
(4) a kind of new copper-based material (including copper base brazing cloth and WC hardware cloths) for being used for red copper surface and being modified of the present invention It is easy to implement quick and preparation method and welding procedure are easily understood, it is easy to utilize.
Embodiment
Embodiment 1:
The fine copper matrix surface in 50 × 50 × 8mm is selected to prepare WC hard coat of the thickness for 0.5mm, copper base brazing cloth Middle alloy powder each element mass ratio is:Mn30.0%, Ni4.0%, Sn0.5%, Zn0.5%, Si0.1%, La0.1%, gather Tetrafluoroethene 0.1%, surplus Cu.WC hardware cloths are made up of the element of following percentage by weight:WC50%, surplus are copper-based pricker Weld cloth.
Manufacturing process steps:
1st, red copper surface be modified copper-based material in copper base brazing cloth preparation process:
(1) Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder are weighed by above mass percent, and is mixed Close uniform;
(2) obtained mixed metal powder particle is rolled in automatic roll equipment, control bonding cloth preliminary first Thickness in 3mm or so.Roll is carried out again to bonding cloth, adjusts the spacing between roller, it is 0.5mm to control height, is given One normal pressure of cloth is bonded, carries out 2~3 repetition rolls, the bonding agent between surface of metal particles and metallic particles is produced Squeezing action, bonding agent form threadiness under squeezing action;5~6 repetition rolls are carried out to copper base brazing cloth tow sides, Metallic fiber forms a crisscross three-dimensional spider net type structure, and metallic particles is inlayed or is wrapped in bonding agent, makes to disperse Alloying metal powder form the entirety connected each other, the metallic particles in each section of threadiness is uniformly distributed, and roll is formed Flexible copper base brazing cloth.
2nd, red copper surface be modified copper-based material in WC hardware cloths preparation process:
(1) weigh WC powder, Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder by mass percentage, and by its It is well mixed;
(2) obtained mixed metal powder particle is being pricked into rod equipment progress roll automatically, control bonding cloth preliminary first Thickness in 3mm.Roll is carried out again to bonding cloth, adjusts the spacing between roller, it is 0.5mm to control height, to bonding One normal pressure of cloth, 2~3 repetition rolls are carried out, extruding is produced to the bonding agent between surface of metal particles and metallic particles Effect, bonding agent form threadiness under squeezing action;WC hardware cloths tow sides are carried out with 5~6 repetition rolls, metal is fine Dimension forms a crisscross three-dimensional spider net type structure, and metallic particles is inlayed or is wrapped in bonding agent, makes scattered alloy Metal powder forms the entirety connected each other, and the metallic particles in each section of threadiness is uniformly distributed, and roll forms flexible WC Hardware cloth.
High temperature brazing processing step is:
1st, the preparatory stage:Brazing equipment uses WZB-20 vacuum brazing furnaces, before weldering, grinds fine copper surface with sand paper, uses wine Seminal plasma is put into ultrasonic cleaner after washing, and adds acetone, cleans 15min.Then with cleaning cloth wiped clean and air drying. Correspondingly sized copper base brazing cloth and WC hardware cloths are cut out according to workpiece size.
2nd, installation step:Fine copper matrix is placed on it is following, by flexible the copper base brazing cloth and WC hardware cloths that cut by The order of fine copper/copper base brazing cloth/WC hardware cloths is put into soldering oven.
3rd, the soldering connection stage:The sample assembled is integrally placed at vacuum not less than 1.5 × 10-3Pa vacuum brazing In equipment, 300 DEG C are warming up to 8 DEG C/min speed first, is incubated 20min, 550 DEG C is warming up to 5 DEG C/min speed, protects Warm 20min, then 800 DEG C are continuously heating to 5 DEG C/min speed, 20min is incubated, then pricker is warming up to 5 DEG C/min speed 1030 DEG C of temperature is welded, is incubated 20min, then 600 DEG C are cooled to 5 DEG C/min speed, 20min is incubated, finally cools to the furnace Room temperature.
As a result:The fine copper face coat shaping that vacuum brazing obtains is preferable, and metallographic observation finds coating and matrix junction Fine and close interface cohesion is formed, alloying component is evenly distributed, and joint bending stiffness reaches as high as 216MPa, and coating surface Rockwell is hard Degree is up to 63.6HRC.
Embodiment 2:
The fine copper matrix surface in 50 × 50 × 8mm is selected to prepare WC hard coat of the thickness for 1mm, in copper base brazing cloth Alloy powder each element mass ratio is:Mn32.0%, Ni5.0%, Sn1.0%, Zn0.8%, Si0.2%, La0.15%, poly- four PVF 0.02%, surplus Cu.WC hardware cloths are made up of the element of following percentage by weight:WC60%, surplus are copper-based pricker Weld cloth.
Manufacturing process steps:
1st, red copper surface be modified copper-based material in copper base brazing cloth preparation process:
(1) Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder are weighed by above mass percent, and is mixed Close uniform;
(2) obtained mixed metal powder particle is rolled in automatic roll equipment, control bonding cloth preliminary first Thickness in 4mm or so.Roll is carried out again to bonding cloth, adjusts the spacing between roller, it is 1.0mm to control height, is given One normal pressure of cloth is bonded, carries out 2~3 repetition rolls, the bonding agent between surface of metal particles and metallic particles is produced Squeezing action, bonding agent form threadiness under squeezing action;5~6 repetition rolls are carried out to copper base brazing cloth tow sides, Metallic fiber forms a crisscross three-dimensional spider net type structure, and metallic particles is inlayed or is wrapped in bonding agent, makes to disperse Alloying metal powder form the entirety connected each other, the metallic particles in each section of threadiness is uniformly distributed, and roll is formed Flexible copper base brazing cloth.
2nd, red copper surface be modified copper-based material in WC hardware cloths preparation process:
(1) weigh WC powder, Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder by mass percentage, and by its It is well mixed;
(2) obtained mixed metal powder particle is being pricked into rod equipment progress roll automatically, control bonding cloth preliminary first Thickness in 4mm.Roll is carried out again to bonding cloth, adjusts the spacing between roller, it is 1mm to control height, gives bonding cloth One normal pressure, 2~3 repetition rolls are carried out, producing extruding to the bonding agent between surface of metal particles and metallic particles makees With bonding agent forms threadiness under squeezing action;5~6 repetition rolls, metallic fiber are carried out to WC hardware cloths tow sides A crisscross three-dimensional spider net type structure is formed, metallic particles is inlayed or is wrapped in bonding agent, makes scattered alloy gold Belong to powder and form the entirety connected each other, the metallic particles in each section of threadiness is uniformly distributed, and roll forms flexible WC gold Belong to cloth.
High temperature brazing processing step is:
1st, the preparatory stage:Brazing equipment uses WZB-20 vacuum brazing furnaces, before weldering, grinds fine copper surface with sand paper, uses wine Seminal plasma is put into ultrasonic cleaner after washing, and adds acetone, cleans 15min.Then with cleaning cloth wiped clean and air drying. Correspondingly sized copper base brazing cloth and WC hardware cloths are cut out according to workpiece size.
2nd, installation step:Fine copper matrix is placed on it is following, by flexible the copper base brazing cloth and WC hardware cloths that cut by The order of fine copper/copper base brazing cloth/WC hardware cloths is put into soldering oven.
3rd, the soldering connection stage:The sample assembled is integrally placed at vacuum not less than 1.5 × 10-3Pa vacuum brazing In equipment, 330 DEG C are warming up to 9 DEG C/min speed first, is incubated 23min, 580 DEG C is warming up to 6 DEG C/min speed, protects Warm 23min, then 830 DEG C are continuously heating to 6 DEG C/min speed, 25min is incubated, then pricker is warming up to 6 DEG C/min speed 1050 DEG C of temperature is welded, is incubated 25min, then 630 DEG C are cooled to 6 DEG C/min speed, 25min is incubated, finally cools to the furnace Room temperature.
As a result:The fine copper face coat shaping that vacuum brazing obtains is preferable, and metallographic observation finds coating and matrix junction Fine and close interface cohesion is formed, alloying component is evenly distributed, and joint bending stiffness reaches as high as 211MPa, and coating surface Rockwell is hard Degree is up to 64.2HRC.
Embodiment 3:
The fine copper matrix surface in 50 × 50 × 8mm is selected to prepare WC hard coat of the thickness for 2mm, in copper base brazing cloth Alloy powder each element mass ratio is:Mn35.0%, Ni6.0%, Sn1.5%, Zn1.0%, Si0.3%, La0.2%, poly- four PVF 0.03%, surplus Cu.WC hardware cloths are made up of the element of following percentage by weight:WC80%, surplus are copper-based pricker Weld cloth.
Manufacturing process steps:
1st, red copper surface be modified copper-based material in copper base brazing cloth preparation process:
(1) Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder are weighed by above mass percent, and is mixed Close uniform;
(2) obtained mixed metal powder particle is rolled in automatic roll equipment, control bonding cloth preliminary first Thickness in 5mm or so.Roll is carried out again to bonding cloth, adjusts the spacing between roller, it is 2.0mm to control height, is given One normal pressure of cloth is bonded, carries out 2~3 repetition rolls, the bonding agent between surface of metal particles and metallic particles is produced Squeezing action, bonding agent form threadiness under squeezing action;5~6 repetition rolls are carried out to copper base brazing cloth tow sides, Metallic fiber forms a crisscross three-dimensional spider net type structure, and metallic particles is inlayed or is wrapped in bonding agent, makes to disperse Alloying metal powder form the entirety connected each other, the metallic particles in each section of threadiness is uniformly distributed, and roll is formed Flexible copper base brazing cloth.
2nd, red copper surface be modified copper-based material in WC hardware cloths preparation process:
(1) weigh WC powder, Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder by mass percentage, and by its It is well mixed;
(2) obtained mixed metal powder particle is being pricked into rod equipment progress roll automatically, control bonding cloth preliminary first Thickness in 5.0mm.Roll is carried out again to bonding cloth, adjusts the spacing between roller, it is 2.0mm to control height, to viscous One normal pressure of cloth is connect, carries out 2~3 repetition rolls, the bonding agent between surface of metal particles and metallic particles is produced and squeezed Pressure acts on, and bonding agent forms threadiness under squeezing action;5~6 repetition rolls, metal are carried out to WC hardware cloths tow sides Fiber forms a crisscross three-dimensional spider net type structure, and metallic particles is inlayed or is wrapped in bonding agent, makes scattered conjunction Golden metal powder forms the entirety connected each other, and the metallic particles in each section of threadiness is uniformly distributed, and roll forms flexibility WC hardware cloths.
High temperature brazing processing step is:
1st, the preparatory stage:Brazing equipment uses WZB-20 vacuum brazing furnaces, before weldering, grinds fine copper surface with sand paper, uses wine Seminal plasma is put into ultrasonic cleaner after washing, and adds acetone, cleans 15min.Then with cleaning cloth wiped clean and air drying. Correspondingly sized copper base brazing cloth and WC hardware cloths are cut out according to workpiece size.
2nd, installation step:Fine copper matrix is placed on it is following, by flexible the copper base brazing cloth and WC hardware cloths that cut by The order of fine copper/copper base brazing cloth/WC hardware cloths is put into soldering oven.
3rd, the soldering connection stage:The sample assembled is integrally placed at vacuum not less than 1.5 × 10-3Pa vacuum brazing In equipment, 350 DEG C are warming up to 10 DEG C/min speed first, 25min is incubated, 600 DEG C is warming up to 8 DEG C/min speed, 25min is incubated, then 850 DEG C are continuously heating to 8 DEG C/min speed, is incubated 30min, then 8 DEG C/min speed is warming up to pricker 1080 DEG C of temperature is welded, is incubated 30min, then 650 DEG C are cooled to 8 DEG C/min speed, 30min is incubated, finally cools to the furnace Room temperature.
As a result:The fine copper face coat shaping that vacuum brazing obtains is preferable, and metallographic observation finds coating and matrix junction Fine and close interface cohesion is formed, alloying component is evenly distributed, and joint bending stiffness reaches as high as 203MPa, and coating surface Rockwell is hard Degree is up to 66.6HRC
Comparative example
Compared with embodiment 1~3, only the composition of solder is different, and solder is as shown in table 1:
Table 1
Coating surface shaping is smooth as made from embodiment 1-3, and coating forms uniform conversion zone with matrix junction, even Border face is obvious, and hard alloy WC particle is evenly distributed, and coating abrasion performance is good, and surface rockwell hardness is up to 66.6HRC, coating It is good with substrate combinating strength, up to 252MPa.
Described above is only the preferred embodiment of the present invention, it should be pointed out that:For the ordinary skill people of the art For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should It is considered as protection scope of the present invention.

Claims (5)

  1. A kind of 1. Cu sills being modified for red copper surface, it is characterised in that:Including the copper base brazing being connected with red copper surface Cloth and the WC hardware cloths being connected with copper base brazing cloth, the elemental composition of the copper base brazing cloth by weight percentage include: Mn30%~35%, Ni4%~6%, Sn0.5%~1.5%, Zn0.5%~1.0%, Si0.1%~0.3%, La0.1% ~0.2%, polytetrafluoroethylene (PTFE) 0.01~0.03%, surplus Cu;The elemental composition of the WC hardware cloths by weight percentage Including:WC50%~80%, surplus are the copper base brazing cloth.
  2. 2. the Cu sills according to claim 1 being modified for red copper surface, it is characterised in that:The copper base brazing cloth It is flexible adhesive tape shape with WC hardware cloths, thickness is 0.5~2.0mm.
  3. 3. the Cu sills according to claim 1 being modified for red copper surface, it is characterised in that:The WC is nickel bag WC, nickel bag WC particle size are 30~45 μm.
  4. A kind of 4. Cu sills for being used for red copper surface and being modified as described in any one of claims 1 to 3, it is characterised in that bag Include following steps:
    A, the preparation of copper base brazing cloth
    (1) Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder are weighed by mass percentage, and are mixed uniformly;
    (2) obtained mixed metal powder particle is rolled in automatic roll equipment, the thickness of control bonding cloth preliminary first Degree carries out roll again in 3.0~5.0mm or so, to bonding cloth, adjusts the spacing between roller, control height be 0.5~ 2.0mm, bonding one normal pressure of cloth is given, carries out 2~3 repetition rolls, to viscous between surface of metal particles and metallic particles Connect agent and produce squeezing action, bonding agent forms threadiness under squeezing action;Copper base brazing cloth tow sides are carried out 5~6 times Roll is repeated, metallic fiber forms a crisscross three-dimensional spider net type structure, and bonding agent is inlayed or be wrapped in metallic particles In, scattered alloying metal powder is formed the entirety connected each other, the metallic particles in each section of threadiness is uniformly distributed, Roll forms flexible copper base brazing cloth;
    B, the preparation of WC hardware cloths
    (1) WC powder, Cu, Mn, Ni, Zn, Sn, Si, La and polytetrafluorethylepowder powder are weighed by mass percentage, and are mixed Uniformly;
    (2) obtained mixed metal powder particle is being pricked into rod equipment progress roll, the thickness of control bonding cloth preliminary first automatically Spend in 3.0~5.0mm or so, carry out roll again to WC hardware cloths, adjust the spacing between roller, it is 0.5 to control height ~2.0mm, give WC hardware cloths one normal pressure, 2~3 repetition rolls are carried out, between surface of metal particles and metallic particles Bonding agent produce squeezing action, bonding agent forms threadiness under squeezing action;5~6 are carried out to WC hardware cloths tow sides Secondary to repeat roll, metallic fiber forms a crisscross three-dimensional spider net type structure, and bonding is inlayed or be wrapped in metallic particles In agent, scattered alloying metal powder is set to form the entirety connected each other, the metallic particles in each section of threadiness uniformly divides Cloth, roll form flexible WC hardware cloths.
  5. 5. a kind of soldering processes for being used for the Cu sills that red copper surface is modified as described in claims 1 to 3, its feature exists In comprising the following steps:
    (1) preparatory stage:First fine copper surface to be brazed is cleared up, removes the impurity, greasy dirt and oxide-film on surface, juxtaposition Using ultrasonic wave cleaning 10-15min in acetone, according to the shape on fine copper surface, cut corresponding flexible copper base brazing cloth and WC hardware cloths;
    (2) installation step:Fine copper matrix is placed on it is following, by flexible the copper base brazing cloth and WC hardware cloths that cut by pure The order of copper/copper base brazing cloth/WC hardware cloths is put into soldering oven;
    (3) soldering processes:The sample assembled is integrally placed at vacuum not less than 1.5 × 10-3In Pa vacuum brazing equipment, 300~350 DEG C are warming up to 8~10 DEG C/min speed first, is incubated 20~25min, is heated up with 5~8 DEG C/min speed To 550~600 DEG C, 20~25min is incubated, then 800~850 DEG C are continuously heating to 5~8 DEG C/min speed, insulation 20~ 30min, then 1030~1080 DEG C of brazing temperature is warming up to 5~8 DEG C/min speed, 20~30min is incubated, then with 5~8 DEG C/min speed is cooled to 600~650 DEG C, 20~30min is incubated, finally cools to room temperature with the furnace.
CN201710700484.4A 2017-08-16 2017-08-16 A kind of Cu sills being modified for red copper surface and preparation and welding method Pending CN107498210A (en)

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CN109128577A (en) * 2018-10-30 2019-01-04 西南交通大学 A kind of solder and preparation method thereof of Mn-Cu alloy and the soldering of Fe-Cr based alloy
CN109576697A (en) * 2018-11-23 2019-04-05 江苏科技大学 A kind of Al-based coating and preparation method, using the Al alloy composite and preparation method of coating preparation
CN109594073A (en) * 2018-12-12 2019-04-09 江苏阳明船舶装备制造技术有限公司 Copper alloy surface wear-resistant coating and preparation method are prepared with CuMnCo
CN109622973A (en) * 2018-11-22 2019-04-16 淮北市菲美得环保科技有限公司 A kind of preparation process of wearability stainless steel alloy coating
CN109622938A (en) * 2018-12-12 2019-04-16 江苏阳明船舶装备制造技术有限公司 It is a kind of to prepare copper alloy surface wear-resistant coating and preparation method with AgCuTi
CN109622939A (en) * 2018-12-12 2019-04-16 江苏阳明船舶装备制造技术有限公司 Copper alloy surface wear-resistant coating and preparation method are prepared with CuMnNi
CN110465715A (en) * 2019-08-15 2019-11-19 南昌大学 A kind of preparation process based on tinbase solder joint under the conditions of metastable state
CN111575611A (en) * 2020-06-19 2020-08-25 南京尚吉增材制造研究院有限公司 SiC fiber-WC-Ni hard alloy composite material and preparation method thereof

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CN109128577A (en) * 2018-10-30 2019-01-04 西南交通大学 A kind of solder and preparation method thereof of Mn-Cu alloy and the soldering of Fe-Cr based alloy
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CN109622973A (en) * 2018-11-22 2019-04-16 淮北市菲美得环保科技有限公司 A kind of preparation process of wearability stainless steel alloy coating
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CN110465715A (en) * 2019-08-15 2019-11-19 南昌大学 A kind of preparation process based on tinbase solder joint under the conditions of metastable state
CN111575611A (en) * 2020-06-19 2020-08-25 南京尚吉增材制造研究院有限公司 SiC fiber-WC-Ni hard alloy composite material and preparation method thereof
CN111575611B (en) * 2020-06-19 2021-11-05 南京尚吉增材制造研究院有限公司 SiC fiber-WC-Ni hard alloy composite material and preparation method thereof

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