CN103252572A - Transient liquid phase diffusion bonding process of molybdenum copper alloy and stainless steel - Google Patents
Transient liquid phase diffusion bonding process of molybdenum copper alloy and stainless steel Download PDFInfo
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- CN103252572A CN103252572A CN2013101731245A CN201310173124A CN103252572A CN 103252572 A CN103252572 A CN 103252572A CN 2013101731245 A CN2013101731245 A CN 2013101731245A CN 201310173124 A CN201310173124 A CN 201310173124A CN 103252572 A CN103252572 A CN 103252572A
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Abstract
The invention discloses a transient liquid phase diffusion bonding process of molybdenum copper alloy and stainless steel. The transient liquid phase diffusion bonding process comprises the following steps that (1) before welding, the surfaces to be welded of the molybdenum copper alloy and the stainless steel are cleaned, wiped and blown to be dry until the surfaces to be welded show metallic luster; (2) a composite middle layer is added between contacting surfaces to be welded of the molybdenum copper alloy and the stainless steel, and then a workpiece to be welded is put in a vacuum chamber and is pressed tightly through an upper pressing head and a lower pressing head; (3) when the vacuum chamber is vacuumized until the vacuum degree reaches 10-4 Pa, transient liquid phase diffusion welding is carried out on the assembled workpiece made of the molybdenum copper alloy and the stainless steel; (4) cooling is carried out after welding, and the welding workpiece made of the molybdenum copper alloy and the stainless steel is taken out. The transient liquid phase diffusion bonding process of the molybdenum copper alloy and the stainless steel completely achieves diffusion bonding between the molybdenum copper alloy and the stainless steel, can obtain a diffusion bonding connector made of the molybdenum copper alloy and the stainless steel with the shearing strength reaching 120 M Pa, can meet the use requirements of a composite structure made of the molybdenum copper alloy and the stainless steel, and has the advantages of being low in cost, simple, convenient, high in applicability, convenient to popularize and apply and the like.
Description
Technical field
The present invention relates to a kind ofly for molybdenum-copper and stainless diffusion method of attachment, relate in particular to the diffusion of a kind of transient liquid phase and connect molybdenum-copper and stainless method, belong to the welding technology field of foreign material.
Background technology
Along with the increase of reinforcement, volume miniaturization and the power of electronic device function, require more and more high to high-temperature behavior and the heat dispersion of electronics seal, sealing materials.Molybdenum-copper has favorable conductive, heat conductivility and more stable thermal coefficient of expansion, and suitable mechanical strength, can use under higher temperature, is paid much attention to as the electronics seal, sealing materials.
When molybdenum-copper and stainless steel welding, because both thermophysical property differs bigger, as adopting fusion welding method, the joint is easy to generate weld crack, therefore, need take technological measures such as weld preheating, postheating to prevent the generation of joint crackle.And molybdenum-copper is responsive to gaseous impurity, easily produces pore during welding, and when joint cooled off fast, interstitial impurity also can form segregation at crystal boundary.Therefore, molybdenum-copper and the more employing of stainless welding are welded under vacuum environment or gas shield condition.
Both at home and abroad mainly adopt argon tungsten-arc welding and Vacuum Soldering Technology about molybdenum-copper and stainless welding.When adopting the argon arc welding of tungsten welding, adopt the Cr25-Ni13 alloy welding wire as packing material, earlier molybdenum-copper one side is carried out preheating before the welding, can obtain obdurability austenite and δ-ferrite duplex structure weld seam preferably by the input of control sweating heat then.But have small amount of Fe-Mo intermetallic compound in the fusion area of molybdenum-copper one side, the aggregation limited of these intermetallic compounds the high temperature of molybdenum-copper and stainless joint use.The solder that vacuum brazing molybdenum-copper and stainless steel adopt mainly contains Ag-Cu-Ti active solder and Ni-based amorphous brazing filler metal, and these two kinds of solder costs are higher, therefore its range of application is very restricted.
Summary of the invention
At above-mentioned prior art, the objective of the invention is to overcome the deficiencies in the prior art part, propose a kind of transient liquid phase diffusion and connect molybdenum-copper and stainless method, to realize that molybdenum-copper is connected with stainless diffusion, improve welding quality, reduce production costs, enlarge the range of application of molybdenum-copper and stainless steel weldment.
The present invention is achieved by the following technical solutions:
Molybdenum-copper and stainless transient liquid phase diffusion connecting process may further comprise the steps:
(1) preweld cleaning molybdenum-copper and stainless welding surface, and wipe away clean, dry up, until exposing metallic luster;
(2) between molybdenum-copper and stainless steel contact-making surface to be welded, add composite interlayer, then workpiece to be welded placed vacuum chamber, and use, push-down head compresses;
(3) vacuum for the treatment of vacuum chamber is evacuated to 10
-4During Pa, molybdenum-copper and the stainless steel work-piece that assembles carried out instant liquid-phase diffusion welding, technological parameter is: 1010～1080 ℃ of heating-up temperatures, firing rate are 25～40 ℃/min, temperature retention time 25～40min, and pressure 6～10MPa, vacuum is 10
-4～10
-5Pa;
(4) molybdenum-copper and stainless steel welding work pieces are taken out in postwelding cooling.
In the described step (1), the method for preweld cleaning molybdenum-copper and stainless welding surface is that mechanical chipping is or/and soak cleaning.Mechanical chipping refers to make its surface roughness reach Ra1.6～6.4 μ m with abrasive paper for metallograph polishing molybdenum-copper and stainless welding surface, after the polishing, with alcohol with surface of the work wiped clean to be welded, dry up.It is that the hydrochloric acid of 10% sulfuric acid solution or 10%～15% or 75%～100% alcohol are treated welder's part surface and cleaned pickling time 5～10min that soak cleaning refers to adopt percent by volume; After the pickling, clear water flushing, with alcohol with surface of the work wiped clean to be welded, dry up.
In the described step (2), composite interlayer is made up of Copper Foil and titanium foil, or formed by Copper Foil and titanium valve, they are molybdenum-copper-titanium foil+Copper Foil+titanium foil-stainless steel with the order, or: molybdenum-copper-titanium valve+Copper Foil+titanium valve-stainless mode folds up between molybdenum-copper and stainless steel work-piece.
Further, described Copper Foil purity is greater than 99%.
Further, the thickness of described titanium foil is 10～20 μ m, and the thickness of Copper Foil is 80～140 μ m.
Further, be coated with the niobium powder on the described titanium foil, the addition of niobium powder is 20%～40% of titanium foil quality.
Further, the granularity of described titanium valve is greater than 200 orders.
Further, be added with the niobium powder in the described titanium valve, in the mixed-powder, the mass ratio of niobium powder and titanium valve is 1:3～1:2.
Further, the addition of described titanium valve is 10%～25% of Copper Foil quality.
Described step (4) is specially: cool off by the water circulation weld vacuum chamber, when treating that vacuum chamber is cooled to below 100 ℃, stops water circulation cooling, after vacuum chamber cools off 6～10h naturally, takes out molybdenum-copper and stainless steel welding work pieces.
Molybdenum-copper of the present invention and stainless transient liquid phase diffusion connecting process, the titanium foil that contains niobium that adopts and Copper Foil (or Copper Foil+titanium, niobium mixed powder) composite interlayer, fusing point is lower, can be fused into liquid metal at a lower temperature in the welding process, wetting molybdenum-copper and stainless contact surface, improve molybdenum-copper and stainless interface wettability, promote the rapid diffusion of atom between the two and diffusion reaction takes place; Through the temperature retention time of setting, diffusion reaction is sustainable to carry out, and has accelerated the diffusion of molybdenum-copper between stainless steel and has been combined in addition.
The transient liquid phase diffusion that the present invention proposes connects molybdenum-copper and stainless method, be to contain the titanium foil of niobium and Copper Foil (or Copper Foil+titanium, niobium mixed powder) composite interlayer by activity, activation molybdenum-copper and stainless contact surface to be welded in welding process realize that molybdenum-copper is connected with stainless diffusion.The activation temperature scope that contains the titanium foil of niobium and Copper Foil (or Copper Foil+titanium, niobium mixed powder) is lower than stainless softening temperature.When diffusion connected, priming reaction at first took place in composite interlayer, decomposited Ti, Nb, Cu isoreactivity atom and was diffused into molybdenum-copper and stainless contact surface rapidly.This activation process activates the atom of molybdenum-copper and stainless steel contact surface on the one hand, and active atomic Ti, Nb, Cu and molybdenum-copper/stainless steel atom generation diffusion reaction at the interface generates new phase structure on the other hand.The new phase structure of diffusion reaction that active atomic Ti, Nb, Cu form between molybdenum-copper/stainless steel interface is conducive to promote that molybdenum-copper/stainless steel interface forms good diffusion combination, improves the bond strength performance of molybdenum-copper/stainless steel diffusion welding (DW) joint.
Before the weldering activity being contained the titanium foil of niobium and Copper Foil (or Copper Foil+titanium, niobium mixed powder) folds up between molybdenum-copper and stainless steel part, and in the diffusion connection procedure, exert pressure, can reduce the microcosmic gap between molybdenum-copper, composite interlayer and the stainless steel, increase the contact area in molybdenum-copper and stainless steel and intermediate layer, promote the atom diffusion at the interface of Ti, Nb, Cu and molybdenum-copper/stainless steel, be conducive to diffusion reaction, improve the bond strength of linkage interface.
Adopt interpolation composite interlayer transient liquid phase of the present invention diffusion to connect molybdenum-copper and stainless method, under the effect of the titanium foil that contains niobium and Copper Foil (or Copper Foil+titanium, niobium mixed powder), realized that fully molybdenum-copper is connected with stainless diffusion.And, connect parameter in conjunction with the instant liquid-phase diffusion welding that provides in the inventive method, can obtain molybdenum-copper and stainless diffusion jointing that shear strength reaches 120MPa, can satisfy the instructions for use of molybdenum-copper and the compound structure of stainless steel.Molybdenum-copper of the present invention and stainless method of attachment have advantages such as cost is low, technology is simple and convenient, and applicability is strong, easy to utilize.The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
The molybdenum-copper plate of embodiment 1:40mm * 40mm * 3mm is connected with the transient liquid phase diffusion of the 1Cr18Ni9Ti austenite stainless steel plate of 40mm * 40mm * 3mm.
Concrete processing step is as follows:
(1) the molybdenum-copper welding surface is polished with abrasive paper for metallograph, make its surface roughness reach Ra2.5 μ m, will carry out wiping with alcohol then, dry up.In addition the surperficial hydrochloric acid with 15% of 1Cr18Ni9Ti stainless steel substrates is carried out pickling 8min, clear water is cleaned, and dries up; With the abrasive paper for metallograph stainless welding surface of polishing, make its surface roughness reach Ra2.5 μ m, again with alcohol with surperficial wiped clean, dry up.
(2) between molybdenum-copper and the stainless contact-making surface to be welded of 1Cr18Ni9Ti, folding up thickness successively with molybdenum-copper-titanium foil (containing the niobium powder)+Copper Foil+titanium foil (containing the niobium powder)-stainless order of 1Cr18Ni9Ti is that 20 μ m titanium foils (weight is 0.15g), thickness are that 110 μ m Copper Foils and thickness are 20 μ m titanium foils (weight is 0.15g), form composite interlayer, wherein the single face at the both sides titanium foil evenly applies niobium powder 0.06g respectively, and the surface that will scribble the niobium powder contacts with Copper Foil, uses at last, push-down head compresses and treat weldment.
(3) molybdenum-copper that will accompany composite interlayer places the vacuum chamber of vacuum diffusion welding equipment to carry out the liquid phase diffusion with 1Cr18Ni9Ti stainless steel sub-assembly to be connected, technological parameter is: firing rate is 30 ℃/min, 1050 ℃ of heating-up temperatures, temperature retention time 35min, pressure 7MPa, vacuum is 4.5 * 10
-5Pa.
(4) after to be welded the finishing, vacuum chamber when being cooled to below 100 ℃, stops water circulation cooling by water circulation cooling, after vacuum chamber cools off 7h naturally, takes out workpiece, obtains molybdenum-copper and 1Cr18Ni9Ti stainless steel diffusion welding (DW) joint.Through the shearing test test, the shear strength at this molybdenum-copper and 1Cr18Ni9Ti stainless joint interface reaches 120MPa.
The molybdenum-copper plate of embodiment 2:40mm * 40mm * 2.5mm is connected with the transient liquid phase diffusion of the 1Cr17Mo ferrite stainless steel of 40mm * 40mm * 2.5mm.
Concrete processing step is as follows:
(1) the molybdenum-copper welding surface is polished with abrasive paper for metallograph, make its surface roughness reach Ra4.0 μ m, will carry out wiping with alcohol then, dry up.In addition 1Cr17Mo ferrite stainless steel welding surface is carried out pickling 10min with 10% sulfuric acid, clear water is cleaned, and dries up, and with the polish welding surface of steel of abrasive paper for metallograph, makes its surface roughness reach Ra5.2 μ m then; Again with alcohol with surperficial wiped clean, dry up.
(2) between molybdenum-copper and 1Cr17Mo stainless steel contact-making surface to be welded, folding up thickness successively with molybdenum-copper-titanium foil (containing the niobium powder)+Copper Foil+titanium foil (containing the niobium powder)-stainless order of 1Cr17Mo is that 10 μ m titanium foils (weight is 0.075g), thickness are that 120 μ m Copper Foils and thickness are 10 μ m titanium foils (weight is 0.075g), form composite interlayer, wherein the single face at the both sides titanium foil evenly applies niobium powder 0.03g respectively, and the surface that will scribble the niobium powder contacts with Copper Foil, uses at last, push-down head compresses.
(3) molybdenum-copper that will accompany composite interlayer places the vacuum chamber of vacuum diffusion welding equipment to carry out the transient liquid phase diffusion with 1Cr17Mo stainless steel sub-assembly to be connected weldering, technological parameter is: firing rate is 35 ℃/min, 1080 ℃ of heating-up temperatures, temperature retention time 30min, pressure 10MPa, vacuum is 2.5 * 10
-4Pa.
(4) treat that insulation is finished after, vacuum chamber when being cooled to below 100 ℃, stops water circulation cooling by water circulation cooling, after vacuum chamber cool off 6h naturally, taking-up workpiece, acquisition molybdenum-copper and 1Cr17Mo stainless steel diffusion welding (DW) joint.Through the shearing test test, the shear strength at this molybdenum-copper and 1Cr17Mo stainless joint interface reaches 126MPa.
Claims (10)
1. molybdenum-copper and stainless transient liquid phase diffusion connecting process is characterized in that: may further comprise the steps:
(1) preweld cleaning molybdenum-copper and stainless welding surface, and wipe away clean, dry up, until exposing metallic luster;
(2) between molybdenum-copper and stainless steel contact-making surface to be welded, add composite interlayer, then workpiece to be welded placed vacuum chamber, and use, push-down head compresses;
(3) vacuum for the treatment of vacuum chamber is evacuated to 10
-4During Pa, molybdenum-copper and the stainless steel work-piece that assembles carried out instant liquid-phase diffusion welding, technological parameter is: 1010～1080 ℃ of heating-up temperatures, firing rate are 25～40 ℃/min, temperature retention time 25～40min, and pressure 6～10MPa, vacuum is 10
-4～10
-5Pa;
(4) molybdenum-copper and stainless steel welding work pieces are taken out in postwelding cooling.
2. molybdenum-copper according to claim 1 and stainless transient liquid phase diffusion connecting process, it is characterized in that: in the described step (1), the method for preweld cleaning molybdenum-copper and stainless welding surface is that mechanical chipping is or/and soak cleaning; Mechanical chipping is: with abrasive paper for metallograph polishing molybdenum-copper and stainless welding surface, make its surface roughness reach Ra1.6～6.4 μ m, after the polishing, with alcohol with surface of the work wiped clean to be welded, dry up; Soak cleaning is: adopting percent by volume is that the hydrochloric acid of 10% sulfuric acid solution or 10%～15% or 75%～100% alcohol are treated welder's part surface and cleaned pickling time 5～10min; After the pickling, clear water flushing, with alcohol with surface of the work wiped clean to be welded, dry up.
3. molybdenum-copper according to claim 1 and stainless transient liquid phase diffusion connecting process, it is characterized in that: in the described step (2), composite interlayer is made up of Copper Foil and titanium foil, or formed by Copper Foil and titanium valve, they are molybdenum-copper-titanium foil+Copper Foil+titanium foil-stainless steel with the order, or: molybdenum-copper-titanium valve+Copper Foil+titanium valve-stainless mode folds up between molybdenum-copper and stainless steel work-piece.
4. molybdenum-copper according to claim 3 and stainless transient liquid phase diffusion connecting process, it is characterized in that: described Copper Foil purity is greater than 99%.
5. molybdenum-copper according to claim 3 and stainless transient liquid phase diffusion connecting process, it is characterized in that: the thickness of described titanium foil is 10～20 μ m, the thickness of Copper Foil is 80～140 μ m.
6. molybdenum-copper according to claim 3 and stainless transient liquid phase diffusion connecting process, it is characterized in that: be coated with the niobium powder on the described titanium foil, the addition of niobium powder is 20%～40% of titanium foil quality.
7. molybdenum-copper according to claim 3 and stainless transient liquid phase diffusion connecting process, it is characterized in that: the granularity of described titanium valve is greater than 200 orders.
8. molybdenum-copper according to claim 3 and stainless transient liquid phase diffusion connecting process, it is characterized in that: be added with the niobium powder in the described titanium valve, in the mixed-powder, the mass ratio of niobium powder and titanium valve is 1:3～1:2.
9. molybdenum-copper according to claim 3 and stainless transient liquid phase diffusion connecting process, it is characterized in that: the addition of described titanium valve is 10%～25% of Copper Foil quality.
10. molybdenum-copper according to claim 1 and stainless transient liquid phase diffusion connecting process, it is characterized in that: described step (4) is specially: cool off by the water circulation weld vacuum chamber, when treating that vacuum chamber is cooled to below 100 ℃, stop water circulation cooling, after vacuum chamber cools off 6～10h naturally, take out molybdenum-copper and stainless steel welding work pieces.
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