CN106077936A - A kind of cobalt base superalloy and the diffusion connection method of graphite - Google Patents
A kind of cobalt base superalloy and the diffusion connection method of graphite Download PDFInfo
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- CN106077936A CN106077936A CN201610455497.5A CN201610455497A CN106077936A CN 106077936 A CN106077936 A CN 106077936A CN 201610455497 A CN201610455497 A CN 201610455497A CN 106077936 A CN106077936 A CN 106077936A
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- Prior art keywords
- graphite
- diffusion
- temperature
- base superalloy
- cobalt base
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Classifications
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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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
-
- 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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/14—Preventing or minimising gas access, or using protective gases or vacuum during welding
-
- 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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/16—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating with interposition of special material to facilitate connection of the parts, e.g. material for absorbing or producing gas
-
- 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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/22—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating taking account of the properties of the materials to be welded
- B23K20/233—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating taking account of the properties of the materials to be welded without ferrous layer
-
- 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
- B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
- B23K20/24—Preliminary treatment
Abstract
The invention discloses the diffusion connection method of a kind of cobalt base superalloy and graphite, mainly between cobalt base superalloy and graphite contact interface to be connected, add Ti Cu intermediate alloy, carried out diffusion in vacuum connection, technological parameter is: the heating rate of heating process is 2 DEG C～8 DEG C/min, at 420 DEG C and 600 DEG C of each temperature retention times 10min～15min；Connect temperature 720 DEG C～800 DEG C, temperature retention time 60min～120min, connection pressure 3MPa～10MPa, vacuum are 1.33 × 10‑5～1.33 × 10‑4Pa；Temperature-fall period: from connecting temperature to 600 DEG C of rate of temperature fall 3 DEG C～5 DEG C/min；Less than 600 DEG C rate of temperature fall 5 DEG C～10 DEG C/min.This invention can promote the interface diffusion bond of cobalt base superalloy and graphite material, has concise in technology, it is simple to the advantages such as popularization and application.
Description
Technical field
The present invention relates to the diffusion of the connection of metal material and Inorganic Non-metallic Materials, particularly high temperature alloy and graphite even
Connect, belong to welding technology field.
Background technology
Cobalt base superalloy is containing cobalt amount 40～65% high temperature alloy.There is under the high temperature of 730～1100 DEG C good resisting
Oxidisability, heat and corrosion resisting and combination property, be suitable to make aero-jet engine, industry gas turbine, Vessel personnel leaf
Sheet, diesel nozzeles etc., be the critical material of national defense industry hot-end component use.
Graphite is a kind of novel high-strength material, has the spies such as the corrosion resistance of excellence, high temperature resistant and higher compressive resistance
Point, is widely used in the industrial circles such as petrochemical industry, electric power, metallurgy, such as reactor, electromotor, electrode, brush etc..Graphite also may be used
As nuclear reactor neutron moderator and rocket nozzle, guided missile nose cone, aerospace equipment parts, heat-barrier material, radioprotective material
Material etc..The chemical composition of graphite is pure carbon, and atomic number is 6, and fusing point is 3727 DEG C.The key property of graphite is at high temperature
In there is stable and higher intensity, more stable from room temperature to 2500 DEG C intensity, also have the trend increased.Graphite also has well
Heat conductivity and electric conductivity.
Cobalt base superalloy has vast potential for future development with the defense and commercial industry field that is connected to of graphite.The highest
Temperature alloy is to be badly in need of solving the technical problem that with being reliably connected of graphite.
Connection currently for cobalt base superalloy Yu graphite has following several method: one is to use to be mechanically connected；Two are
Use binding agent (including organic binder bond and inorganic binder).It is low all to there is Joint Reliability in both methods of attachment, application
The problem that scope is limited.If welding method can be used reliably to be coupled together with graphite by high temperature alloy, will significantly advance height
Temperature alloy and the graphite material application in defense and commercial industry field.
High temperature alloy and graphite are carried out the connection of foreign material, the composite structural member made, metal can be given full play to
Material and the respective performance advantage of Inorganic Non-metallic Materials, it is greatly improved service life of composite construction and equipment.But due to
Graphite plasticity is poor, linear expansion coefficient is little, and particularly high temperature alloy is widely different with the thermophysical property of graphite, thus high temperature alloy with
The welding of graphite is extremely difficult.
Cobalt base superalloy welds with graphite, is primarily present both sides problem.One be due to cobalt base superalloy with
Relatively big (α high temperature alloy=11.8 × 10 of linear expansion coefficient gap between graphite-6K～16.2 × 10-6K, α graphite=4 × 10-6
～6 × 10-6K), the two difference about 3 times, weldment causes crackle occur due to thermal stress difference in cooling procedure.Two be by
Much lower compared with graphite-phase ratio in high temperature alloy fusing point, under the conditions of normal weld, interface is difficult to be formed effectively combination.Therefore, high temperature
Alloy and graphite can produce the biggest thermal stress in weld heating and cooling procedure, are easily generated crackle, even at linkage interface
Cause joint breaking, hinder the popularization and application of high temperature alloy and graphite composite structure.
Summary of the invention
It is an object of the invention to, for the deficiencies in the prior art, propose the diffusion connection side of a kind of high temperature alloy and graphite
Method, uses this technology can obtain the Diffusion Bonded Joint of the good high temperature alloy of interface cohesion and graphite, meet high temperature alloy with
Graphite composite structure use requirement in occasion heat-resisting, corrosion-resistant.
To achieve these goals, the technical solution used in the present invention is: to be connected of high temperature alloy and graphite it
Between add Ti-Cu alloy-layer, realize high temperature alloy and graphite by controlling temperature, pressure and diffusion time etc. under vacuum
Be reliably connected.The processing step used is as follows:
(1) before welding, cobalt base superalloy is carried out pretreatment at joining of graphite: by the table to be connected of high temperature alloy Yu graphite
Face is through machining and (or) chemical treatment；
(2) placing Ti-Cu alloy at cobalt base superalloy with graphite pending connection position, with 502 binding agent adhesion Cu paper tinsels, titanium valve is uniform
Lay, and the workpiece to be welded adding intermediate layer stacked and assembles, high temperature alloy under, graphite is upper.
(3) part to be connected to the high temperature alloy assembled and graphite is positioned in the vacuum chamber that diffusion is connected equipment, with resistance to
Upper and lower pressure head prepared by hot material compresses the workpiece treating that diffusion connects, it is desirable to whole combination weldment is flat with the contact surface of pressure head
OK；
(4) diffusion connecting process parameter is: the heating rate of heating process is 2 DEG C～8 DEG C/min, near 420 DEG C and 600 DEG C
One insulation platform, temperature retention time 10min～15min are respectively set；Connect temperature 720 DEG C～800 DEG C, temperature retention time 60min～
120min, connection pressure 3MPa～10MPa, vacuum are 1.33 × 10-5～1.33 × 10-4Pa；
(5) slow cooling, from connecting temperature to 600 DEG C of rate of temperature fall 3 DEG C～5 DEG C/min；Less than 600 DEG C rate of temperature fall 5 DEG C～
10℃/min；Treat that vacuum chamber temperature slowly cools to less than 80 DEG C, fire door can be opened and take out connected piece.
The Ti-Cu intermediate layer that the present invention uses is the pure titanium powder+Cu paper tinsel that purity is more than 99.6%, and the granularity of Ti powder is 200
Mesh～300 mesh, Cu paper tinsel thickness is 10 μm～50 μm.The chemical composition (by percentage to the quality) of Copper Foil is: C 0.05%～
0.10%, Fe 0.15%～0.25%, Si 0.05～1.0%, remaining for Cu.Add Ti-Cu intermediate alloy and may advantageously facilitate high temperature conjunction
Gold and the diffusion bond of graphite interface.
The invention has the beneficial effects as follows:
The cobalt base superalloy of present invention proposition and the diffusion connection method of graphite, there is the diffusion reaction life of Ti Yu C in interface
Become the new thing phases such as TiC and promote the diffusion bond of high temperature alloy and graphite interface.
It is 900 DEG C (even 1000 that conventional metal material (such as carbon steel, rustless steel etc.) is connected temperature with the diffusion of graphite
DEG C) more than, during only eutectic penetrates into graphite hole, firm joint could be formed.Expand with graphite with conventional metal material
Scattered weldering is compared, and the high temperature alloy that the present invention proposes is connected temperature with the diffusion connecting process of graphite than the reduction of conventional Pervasion Weld Technology
130 DEG C～280 DEG C, having significant energy-saving effect, Diffusion Bonding Joint is stable and reliable for performance, it is simple to popularization and application.
The present invention has technique and is simple and convenient to operate, it is simple to the advantages such as popularization and application, is particularly suited for high temperature alloy and stone
The connection of ink composite construction.The shear strength of jointing disclosure satisfy that high temperature alloy and graphite diffusion plumb joint is heat-resisting, corrosion resistant
The use requirement of erosion property occasion.
Detailed description of the invention
Embodiment 1
Cobalt base superalloy and a length of 100mm, the width that a length of 100mm, width are 40mm, thickness is 20mm be 40mm,
Thickness is that the diffusion of the graphite sheet of 40mm connects, and joint face is 100mm × 40mm contact surface.Processing step is as follows:
(1) mechanical grinding processing cobalt base superalloy and to be connected of graphite, by surface to be connected to high temperature alloy and graphite nothing
Water-ethanol wiping, to remove greasy dirt and the foreign material on surface；With the hydrochloric acid solution of concentration 10% by the oxidation of to be connected for high temperature alloy
Film is removed.
(2) it is more than the titanium valve+Cu paper tinsel of 99.6% as intermediate layer, titanium valve granularity 280 mesh, copper thickness 30 μm, Cu by purity
The chemical composition (by percentage to the quality) of paper tinsel is: C 0.06%, Fe 0.18%, Si 0.8%, remaining for Cu.
(3) Ti-Cu intermediate alloy is positioned between rectangular-shaped high temperature alloy and to be connected of graphite, uses 502 binding agents
Adhesion Cu paper tinsel, titanium valve lays uniformly, stacked by workpiece and assemble, cobalt base superalloy under, graphite sheet is upper.
(4) workpiece assembled is positioned over diffusion connection equipment vacuum chamber in, and use, push-down head compress；Requirement
Whole combination weldment is parallel with the contact surface of pressure head.
(5) heating process arranges two insulation platforms, 3 DEG C/min of heating rate before 420 DEG C, 420 DEG C～the 600 DEG C speed that heat up
5 DEG C/min of rate, 600 DEG C to connecting 4 DEG C/min of temperature ramp, platform temperature retention time 10min.
(6) diffusion connecting process parameter is: connects temperature 780 DEG C, temperature retention time 60min, connect pressure 4MPa, vacuum
It is 1.33 × 10-5Pa。
(7) slow cooling, from connection temperature to 5 DEG C/min of 600 DEG C of rate of temperature fall；Less than 600 DEG C rate of temperature fall 8 DEG C/
min。
(8) treat that vacuum chamber temperature slowly cools to less than 80 DEG C, fire door can be opened and take out workpiece.
After testing, rectangular-shaped high temperature alloy is well combined with graphite diffusion linkage interface, Diffusion Bonding Joint shear strength
Shear strength higher than graphite.Disclosure satisfy that high temperature alloy and joining of graphite joint is heat-resisting, the use requirement of corrosion resistance occasion.
Embodiment 2
A diameter of 80mm, thickness are that the discoid cobalt base superalloy of 20mm connects with the diffusion of the graphite disk shape plate of comparable size
Connecing, joint face is the circular contact face of diameter 80mm.Processing step is as follows:
(1) respectively cobalt base superalloy is become to meet the discoid of dimensional requirement with machining graphite with method for turning.Machinery
Grinding high temperature alloy and to be connected of graphite, with dehydrated alcohol wiping high temperature alloy and graphite surface to be connected, remove table
The greasy dirt in face and foreign material；With the hydrochloric acid solution of concentration 10%, the oxide-film of to be connected for high temperature alloy is removed.
(2) it is more than the titanium valve+Cu paper tinsel of 99.6% as intermediate layer, titanium valve granularity 300 mesh, copper thickness 30 μm, Cu by purity
The chemical composition (by percentage to the quality) of paper tinsel is: C 0.06%, Fe 0.18%, Si 0.8%, remaining for Cu.
(3) Ti-Cu intermediate alloy is positioned between discoid high temperature alloy and to be connected of graphite, uses 502 binding agents
Adhesion Cu paper tinsel, titanium valve lays uniformly, stacked by workpiece and assemble, high temperature alloy under, graphite disk plate is upper.
(4) the discoid workpiece assembled is positioned over diffusion connection equipment vacuum chamber in, and use, push-down head pressure
Tightly；Require that whole combination weldment is parallel with the contact surface of pressure head.
(5) heating process arranges two insulation platforms, 3 DEG C/min of heating rate before 400 DEG C, 400 DEG C～the 600 DEG C speed that heat up
6 DEG C/min of rate, 600 DEG C to connecting 5 DEG C/min of temperature ramp, platform temperature retention time 10min.
(6) diffusion connecting process parameter is: connects temperature 730 DEG C, temperature retention time 80min, connect pressure 3MPa, vacuum
It is 1.33 × 10-5Pa。
(7) slow cooling, from connection temperature to 5 DEG C/min of 600 DEG C of rate of temperature fall；Less than 600 DEG C rate of temperature fall 8 DEG C/
min。
After testing, discoid high temperature alloy is well combined with graphite diffusion linkage interface, Diffusion Bonding Joint shear strength
Shear strength higher than graphite.Disclosure satisfy that high temperature alloy and joining of graphite joint is heat-resisting, the use requirement of corrosion resistance occasion.
Claims (5)
1. a cobalt base superalloy and the diffusion connection method of graphite, it is characterised in that comprise the following steps:
(1) before weldering, cobalt base superalloy is carried out machining at joining of graphite, and pending connection position is carried out pretreatment；
(2) in the middle of cobalt-base alloys with graphite part to be connected, Ti-Cu intermediate alloy is added to promote its interface diffusion bond；
(3) workpiece to be connected stacked assemble, be placed in the vacuum chamber of diffusion connection equipment, high temperature alloy under, carry out true
Empty diffusion connects；
(4) diffusion connecting process parameter is:
Heating process: heating rate is 2 DEG C～8 DEG C/min, is respectively incubated 10min～15min when 420 DEG C and 600 DEG C；
Connect temperature 720 DEG C～800 DEG C, temperature retention time 60min～120min, connection pressure 3MPa～10MPa, vacuum are
1.33×10-5～1.33 × 10-4Pa；
Temperature-fall period: from connecting temperature to 600 DEG C of rate of temperature fall 3 DEG C～5 DEG C/min；Less than 600 DEG C rate of temperature fall 5 DEG C～10
℃/min；
(5) treat that vacuum chamber temperature slowly cools to less than 80 DEG C, fire door can be opened and take out connected piece.
Cobalt base superalloy the most according to claim 1 and the diffusion connection method of graphite, it is characterised in that: described step
(1) machining in is milling machine or grinding machine processing, and pretreatment is use dehydrated alcohol wiping and incites somebody to action with the hydrochloric acid solution of concentration 10%
The oxide-film that high temperature alloy is to be connected is removed.
Cobalt base superalloy the most according to claim 1 and the diffusion connection method of graphite, it is characterised in that: described step
(2) the Ti-Cu intermediate alloy in is the pure titanium powder+Cu paper tinsel that purity is more than 99.6%, and the chemical composition of Copper Foil is (with percent mass
Than meter) be: C 0.05%～0.10%, Fe 0.15%～0.25%, Si 0.05～1.0%, remaining for Cu.
Cobalt base superalloy the most according to claim 1 and the diffusion connection method of graphite, it is characterised in that described step
(3) in, concrete processing method is: use, push-down head compresses the workpiece treating that diffusion connects, it is desirable to whole combination weldment is with upper and lower
The contact surface of pressure head is parallel.
Cobalt base superalloy the most according to claim 1 and the diffusion connection method of graphite, it is characterised in that: described step
(2) granularity of Ti powder described in the Ti-Cu intermediate alloy in is 200 mesh～300 mesh, and Cu paper tinsel thickness is 10 μm～50 μm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111496414A (en) * | 2020-04-01 | 2020-08-07 | 武汉工程大学 | Graphite and copper joint and preparation method thereof |
| CN115255703A (en) * | 2022-08-31 | 2022-11-01 | 武汉工程大学 | Graphite-molybdenum joint and preparation method thereof |
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