CN101176946A - Method for vacuum scattering intermetallic compound for coupling TiAL - Google Patents
Method for vacuum scattering intermetallic compound for coupling TiAL Download PDFInfo
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- CN101176946A CN101176946A CNA2007101446861A CN200710144686A CN101176946A CN 101176946 A CN101176946 A CN 101176946A CN A2007101446861 A CNA2007101446861 A CN A2007101446861A CN 200710144686 A CN200710144686 A CN 200710144686A CN 101176946 A CN101176946 A CN 101176946A
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Abstract
The invention relates to a TiAl-intermetallic-compound vacuum diffusing connection method, belonging to the TiAl-intermetallic-compound welding field, which overcomes the technical drawbacks of high temperature of diffusing connection and high pressure of diffusing connection in the prior TiAl-intermetallic-compound diffusing connection technology. The invention adopts hydrogenated titanium or titanium alloy chaff as the interface layer of diffusing connection. Ti3Al+TiAl dual phase (Alpha2+Gamma) organ can be formed under the temperature of diffusing connection titanium, which facilitates the formation of high-intensity connector lug of TiAl-intermetallic-compound diffusing connection. And hydrogen makes the flow stress of thermal deformation of titanium or titanium alloy decrease and the thermal plasticity increase, so that hydrogenated titanium or titanium alloy is prone to deform under high temperature. Meanwhile,, the self-diffusing capacity of hydrogen in titanium or titanium alloy and the diffusing capacity of solute are enhanced, more particularly, in Beta phase the capacities are more enhanced, so that hydrogen can accelerate the diffusing of the alloy elements, reduce the atomic combination energy and the diffusing activation energy, promote the diffusing coordinated deformation capacity, and the reliable diffusing connection of connector lug of TiAl-intermetallic-compound can be realized under comparatively low temperature.
Description
Technical field
The invention belongs to the TiAl intermetallic compound jointing field, be applicable to the TiAl intermetallic compound and with being connected of other foreign material.
Background technology
The TiAl intermetallic compound has that density is little (to be about 3.8g/cm
3), advantage such as specific strength height, good rigidly, good high-temperature mechanical property and non-oxidizability, be considered to a kind of Aeronautics and Astronautics desirable, that be rich in development prospect, military affairs and civilian new type high temperature structural material.The TiAl intermetallic compound is used on engineering, makes member, must run into Welding Problems, comprise himself welding and with the welding of other material.Chinese scholars has all been carried out relevant research to the interconnection technique of TiAl intermetallic compound, from present document and report, mainly comprise method for welding such as solid welding method such as fusion welding method such as argon arc welding, electron beam welding, laser weld and diffusion welding (DW), friction welding, the welding of self propagating high temperature synthetic reaction and vacuum brazing, induction brazing, infrared brazing.The weldability of melting welding shows, there are two in the connection of TiAl intermetallic compound than distinct issues: the one, the hot tearing trend is arranged; The 2nd, the weld metal zone is different with the matrix that obtains through technologies such as overheated mechanical treatments, shows lower mechanical property.At present, the research of melting welding also is confined to how to obtain not have the integrity of welded joint of crackle.Though friction welding (FW) can realize TiAl intermetallic compound self and with being connected of other material, joint form is restricted, and can not connect complex-shaped member and hollow internal weld seams; Being added in to a certain extent of friction welding (FW) intermediate layer can improve strength of joint, but a plurality of interfaces are arranged on joint, this just makes joint quality be difficult to control more, and research does not for many years solve the internal problem that exists fully, for example, upset force causes MATRIX CRACKING easily, and therefore this method still can't obtain practical application.For the TiAl intermetallic compound of low ductility, Chinese scholars generally believes that diffusion connects and soldering is comparatively effective interconnection technique.But TiAl intermetallic compound self and be connected with the diffusion of other material shows, joint interface fragility is mutually more, the strength of joint dispersiveness is bigger, and the general used pressure of connection that spreads is bigger, and temperature is higher, the transformation temperature that usually surpasses TiAl intermetallic compound mother metal, make thickization of TiAl intermetallic compound mother metal crystal grain, degradation is simultaneously because diffusion connects the long cost that increased of thermal cycle time, thereby up to the present, this method still can't obtain practical application.In sum, though Chinese scholars has been carried out corresponding research work aspect the interconnection technique of TiAl intermetallic compound, but because TiAl intermetallic compound its special crystal structure and physical and chemical performance, even adopt the diffusion method of attachment yet can't realize its effectively reliable connection fully, this mainly is because there are two big difficult points in the reliable connection of TiAl intermetallic compound: 1, the high temeperature chemistry Stability Analysis of Structures of TiAl intermetallic compound, very high interface energy is arranged during connection, the control of Interface Microstructure is difficult, is difficult to form the combination of control excellent metallurgical when therefore connecting; 2, the TiAl intermetallic compound has low ductility, thermal coefficient of expansion and most of metal material are variant, when the TiAl intermetallic compound is connected with other dissimilar metal, the thermodynamics of both sides, interface does not match, therefore after cooling down, the connection temperature can produce bigger thermal stress, the fracture strength of joint is reduced, even cracking.Because the existence of the problems referred to above is arranged, therefore to realize very difficulty of the reliable metallurgical binding of TiAl intermetallic compound, can't obtain reliable the connection with conventional welding material with process, this has almost become the biggest obstacle that the TiAl intermetallic compound is used.
Summary of the invention
Diffusion connects the temperature height in the existing TiAl intermetallic compound diffusion interconnection technique, diffusion connects the big technical deficiency of pressure, the invention provides a kind of method of vacuum scattering intermetallic compound for coupling TiAL in order to solve.The method of vacuum scattering intermetallic compound for coupling TiAL of the present invention realizes by following step: one, diffusion is cleared up the mother metal surface before connecting; Two, the diffusion intermediate layer is placed on the joint face of mother metal to be welded uniformly; Diffusion connects the intermediate layer for putting hydrogen titanium or titanium alloy paillon foil, and diffusion connects thickness 30～100 μ m in intermediate layer; Three, the weldment that will clamp places in the vacuum diffusion welding machine and heats, and is 1.33 * 10 in vacuum
-3～4.0 * 10
-3Spread connection under the Pa vacuum condition; Four, welding finishes to remove pressure when the back weldment is cooled to 100 ℃ under former vacuum condition, when cooling to room temperature, takes out weldment.
The described hydrogen content of putting the hydrogen titanium is 0.2～0.5wt%.
Principle is as follows: adopt the titanium of hydrogen content 0.2～0.5wt% (weight) or titanium alloy paillon foil to connect the intermediate layer as diffusion, utilize titanium to connect can react with the TiAl intermetallic compound under the temperature in diffusion and form Ti
3Al+TiAl two-phase (α 2+ γ) tissue, and the intensity of α 2+ γ duplex structure is much higher than intermetallic compound TiAl mother metal, therefore helps forming high-intensity TiAl intermetallic compound diffusion jointing.Simultaneously because hydrogen causes the decline of titanium or titanium alloy thermal deformation flow stress, thermoplastic increase is put the hydrogen titanium or titanium alloy is at high temperature easily deformable thereby make; And self-diffusion and the solute diffusivity of hydrogen in titanium or titanium alloy is higher, particularly higher in the diffusivity of β in mutually, thereby hydrogen can quicken the diffusion of alloying element, reduce atomic binding energy, reduce diffusion activation energy, improve diffusion compatible deformation ability, can realize under relatively low temperature that TiAl intermetallic compound joint spreads connection reliably.In addition, put hydrogen titanium or titanium alloy and connect in the heating process in vacuum diffusion dehydrogenation takes place, when temperature reached 600 ℃, hydrogen began to overflow, and reached when connecting temperature when temperature raises rapidly, and hydrogen is sharply outwards overflowed.The hydrogen and the material surface oxide-film of overflowing react, and this reduction reaction extremely helps the removal of oxide-film, help to shorten the diffusion connect hours, promote the diffusion connection process.The vacuum diffusion that is directed to the TiAl intermetallic compound connects, be connected with the direct diffusion of routine or adopt general T i paper tinsel to compare as the diffusion method of attachment in intermediate layer, the present invention propose to put hydrogen titanium or titanium alloy vacuum diffusion method of attachment and technology as the intermediate layer, diffusion connects temperature can reduce by 80～260 ℃, and the joint shear strength can improve 20～300%.
Description of drawings
Fig. 1 is TiAl/TC4 (putting hydrogen)/TiAl diffusion connecting process curve synoptic diagram.Fig. 2 is TiAl/TC4 (putting hydrogen)/TC4 diffusion connecting process curve synoptic diagram.Fig. 3 is TiAl/Ti600 (putting hydrogen)/SiC pottery diffusion connecting process curve synoptic diagram.Fig. 4 TiAl/TC4 (putting hydrogen)/Al
2O
3Pottery diffusion connecting process curve synoptic diagram.Fig. 5 TiAl/TC4 (putting hydrogen)/(C/SiC) composite diffusion connecting process curve synoptic diagram.T representative diffusion among Fig. 1-5 connects temperature, and P representative diffusion connects pressure, the t representative diffusion connect hours.
The specific embodiment
The specific embodiment one: the method for vacuum scattering intermetallic compound for coupling TiAL realizes by following step in the present embodiment: one, diffusion is cleared up the mother metal surface before connecting; Two, the diffusion intermediate layer is placed on the joint face of mother metal to be welded uniformly; Diffusion connects the intermediate layer for putting hydrogen titanium or titanium alloy paillon foil, and diffusion connects thickness 30～100 μ m in intermediate layer; Three, the weldment that will clamp places in the vacuum diffusion welding machine and heats, and is 1.33 * 10 in vacuum
-3～4.0 * 10
-3Spread connection under the Pa vacuum condition; Four, welding finishes to remove pressure when the back weldment is cooled to 100 ℃ under former vacuum condition, when cooling to room temperature, takes out weldment.
The diffusion connecting process parameter should connect pressure and diffusion connect hours with corresponding diffusion connection temperature, diffusion according to the different mining of mother metal in this implementation method.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: in step 1 the mother metal surface cleared up and adopt physics cleaning, soak cleaning or first physics cleaning back soak cleaning; Described physics cleaning is with 400
#, 50
#, 600
#, 80
#, 1000
#Abrasive paper for metallograph polishes step by step; Described soak cleaning is to prepare corresponding corrosive liquid to remove adsorption layer, impurity or the oxide-film on mother metal surface according to the difference of mother metal, is placed in the acetone soln with acetone wiping mother metal to be welded surface or mother metal then and cleans with ultrasonic wave.Other process conditions and technical process are identical with embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is: diffusion connects thickness 30～80 μ m in intermediate layer in step 2.Other process conditions and technical process are identical with embodiment one.
The specific embodiment four: what present embodiment and the specific embodiment one were different is: diffusion connects the thickness 40 μ m in intermediate layer in step 2.Other process conditions and technical process are identical with embodiment one.
The specific embodiment five: what present embodiment and the specific embodiment one were different is: diffusion connects the thickness 50 μ m in intermediate layer in step 2.Other process conditions and technical process are identical with embodiment one.
The specific embodiment six: what present embodiment and the specific embodiment one were different is: the hydrogen content at the mid-hydrogen titanium of step 2 is 0.2～0.5wt% (weight).Other process conditions and technical process are identical with embodiment one.
The specific embodiment seven: what present embodiment and the specific embodiment one were different is: the hydrogen content at the mid-hydrogen titanium of step 2 is 0.3～0.4wt% (weight).Other process conditions and technical process are identical with embodiment one.
The specific embodiment eight: what present embodiment and the specific embodiment one were different is: the hydrogen content at the mid-hydrogen titanium of step 2 is 0.35wt% (weight).Other process conditions and technical process are identical with embodiment one.
The specific embodiment nine: what present embodiment and the specific embodiment one were different is: mode of heating adopts eddy-current heating or resistance heated in step 3.Other process conditions and technical process are identical with embodiment one.
The specific embodiment ten: it is the TiAl intermetallic compound that the present embodiment diffusion connects mother metal, and the chemical composition of TiAl intermetallic compound sees Table 1.Diffusion connects intermediate layer material and adopts hydrogenated titanium alloy (TC4) paillon foil, and hydrogen content 0.3% (percentage by weight), thickness are 30～50 μ m.Adopt the eddy-current heating vacuum diffusion welding machine.Firing equipment all adopts oil pressure pressurization, vacuum 1.33 * 10
-3～4.0 * 10
-3Pa, but each technological parameter programme-control of welding process and manually control.The soldered surface of TiAl intermetallic compound mother metal is with 400
#, 500
#, 600
#, 800
#, 1000
#Abrasive paper for metallograph polishes step by step, is placed in the acetone soln then and cleans with ultrasonic wave.The hydrogenated titanium alloy intermediate layer is placed mother metal to be welded surface after the cleaning, clamp then, note preventing the misalignment of weldment.Close vacuum chamber after weldment installs, open vavuum pump, treat that vacuum reaches 1.33 * 10
-3～4.0 * 10
-3During Pa, connect power supply and weld weld procedure specification parameter curve such as Fig. 1.Welding is cut off the electricity supply after finishing, and removes pressure when weldment is cooled to 100 ℃ under former vacuum condition, when cooling to room temperature, takes out weldment from vacuum chamber, its objective is in order to prevent that weldment from oxidation at high temperature taking place.
The composition (at.% atomic percent) of table 1 TiAl intermetallic compound mother metal
| Al | Ni | Cr | Nb | Ti |
| 47.2 | 1.17 | 0.56 | 0.11 | 51.0 |
The diffusion of TiAl/TC4 (putting hydrogen)/TiAl connects and shows: TiAl/TC4 (putting hydrogen)/TiAl diffusion jointing room temperature shear strength can reach 450～480MPa, connects TiAl/TiAl under the pressure (10MPa) and directly spreads jointing intensity (the room temperature shear strength is 120～180MPa) high by 150～300% than connect temperature (940 ℃), diffusion connect hours (60min), diffusion in identical diffusion; Connect pressure (10MPa) TiAl/Ti paper tinsel/TiAl down and spread jointing intensity (the room temperature shear strength is 320～350MPa) high by 30～50% than connect temperature (940 ℃), diffusion connect hours (60min), diffusion in identical diffusion; Is connected under the temperature conditions TiAl/TiAl that (it is that 1200 ℃, diffusion connect hours 60min, diffusion connect pressure 10MPa that diffusion connects temperature) connect directly spreads jointing intensity (the room temperature shear strength is 460～480MPa) quite, and diffusion connection temperature has reduced by 260 ℃ with height diffusion.
The specific embodiment 11: the present embodiment diffusion connects TiAl and TC4 titanium alloy, and the chemical composition of TiAl sees Table 1.Diffusion connects intermediate layer material and adopts hydrogenated titanium alloy (TC4) paillon foil, and hydrogen content 0.4% (percentage by weight), thickness are 50 μ m.Weld procedure specification parameter curve such as Fig. 2.Other process conditions and technical process are identical with embodiment ten.
The diffusion of TiAl/TC4 (putting hydrogen)/TC4 connects and shows: TiAl/TC4 (putting hydrogen)/TC4 diffusion jointing room temperature shear strength can reach 440～450MPa, connects TiAl/TC4 under the pressure (10MPa) and directly spreads jointing intensity (the room temperature shear strength is 280～320MPa) high by 40～60% than connect temperature (860 ℃), diffusion connect hours (60min), diffusion in identical diffusion; Is connected under the temperature conditions TiAl/TC4 that (it is that 1000 ℃, diffusion connect hours 60min, diffusion connect pressure 10MPa that diffusion connects temperature) connect directly spreads jointing intensity (the room temperature shear strength is 430～450MPa) quite, and diffusion connection temperature has reduced by 140 ℃ with height diffusion.
The specific embodiment 12: the present embodiment diffusion connects TiAl and SiC pottery, and the SiC pottery is the Al that adds 2～3wt.% (percentage by weight) in the SiC powder
2O
3Normal pressure-sintered forming behind the agglutinant, the chemical composition of TiAl sees Table 1.Diffusion connects intermediate layer material and adopts hydrogenated titanium alloy (Ti600, Ti-6Al-2.8Sn-4Zr-0.5Mo-0.4Si-0.1Y (wt.% percentage by weight)) paillon foil, and hydrogen content 0.4% (percentage by weight), thickness are 30 μ m.Weld procedure specification parameter curve such as Fig. 3.Diffusion connects 1050 ℃ of temperature, and it is 10MPa that diffusion connects pressure, and the diffusion connect hours is 60min.Other process conditions and technical process are identical with embodiment ten.
TiAl/Ti600 (putting hydrogen)/SiC pottery diffusion jointing room temperature shear strength can reach 300～330MPa.
The specific embodiment 13: the present embodiment diffusion connects TiAl and Al
2O
3Pottery, the TiAl chemical composition sees Table 1, Al
2O
3The pottery chemical composition sees Table 2.Diffusion connects intermediate layer material and adopts hydrogenated titanium alloy (TC4) paillon foil, and hydrogen content 0.5% (mass percent), thickness are 100 μ m.Weld procedure specification parameter curve such as Fig. 4.Diffusion connects 950 ℃ of temperature, and it is 10MPa that diffusion connects pressure, and the diffusion connect hours is 60min.Other process conditions and technical process are identical with embodiment ten.
Table 2 Al
2O
3The composition of mother metal (wt.% percentage by weight)
| Al 2O 3 | SiO 2 | CaO | MgO | K 2O | Na 2O |
| 94.58 | 3.55 | 0.12 | 0.92 | 0.05 | 0.53 |
TiAl/TC4 (putting hydrogen)/Al
2O
3Pottery diffusion jointing room temperature shear strength can reach 200～220MPa.
The specific embodiment 14: the present embodiment diffusion connects TiAl and C/SiC composite, and the C/SiC composite is the 3 D weaving carbon fiber toughened silicon carbide composite material, and the TiAl composition sees Table 1.Diffusion connects intermediate layer material and adopts hydrogenated titanium alloy (TC4) paillon foil, and hydrogen content 0.3% (percentage by weight), thickness are 50 μ m.Weld procedure specification parameter curve such as Fig. 5.Other process conditions and technical process are identical with embodiment ten.
TiAl/TC4 (putting hydrogen)/C/SiC composite diffusion jointing room temperature shear strength can reach 170～200MPa.
Claims (10)
1. the method for a vacuum scattering intermetallic compound for coupling TiAL realizes by following step: one, before the diffusion connection mother metal surface is cleared up; Two, the diffusion intermediate layer is placed on the joint face of mother metal to be welded uniformly; Three, the weldment that will clamp places in the vacuum diffusion welding machine and heats, and is 1.33 * 10 in vacuum
-3～4.0 * 10
-3Spread connection under the Pa vacuum condition; Four, welding finishes to remove pressure when the back weldment is cooled to 100 ℃ under former vacuum condition, when cooling to room temperature, takes out weldment; It is characterized in that diffusion connects the intermediate layer for putting hydrogen titanium or titanium alloy paillon foil, diffusion connects thickness 30～100 μ m in intermediate layer.
2. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that in step 1 the cleaning of employing physics, soak cleaning or first physics cleaning back soak cleaning being cleared up in the mother metal surface.
3. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 2 is characterized in that in the cleaning of physics described in the step 1 be with 40
#, 50
#, 600
#, 80
#, 1000
#Abrasive paper for metallograph polishes step by step; Described soak cleaning is to prepare corresponding corrosive liquid to remove adsorption layer, impurity or the oxide-film on mother metal surface according to the difference of mother metal, is placed in the acetone soln with acetone wiping mother metal to be welded surface or mother metal then and cleans with ultrasonic wave.
4. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that spreading thickness 30～80 μ m that connect the intermediate layer in step 2.
5. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that spreading the thickness 40 μ m that connect the intermediate layer in step 2.
6. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that spreading the thickness 50 μ m that connect the intermediate layer in step 2.
7. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that the hydrogen content at the mid-hydrogen titanium of step 2 is 0.2～0.5wt%.
8. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that the hydrogen content at the mid-hydrogen titanium of step 2 is 0.3～0.4wt%.
9. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that the hydrogen content at the mid-hydrogen titanium of step 2 is 0.35wt%.
10. the method for a kind of vacuum scattering intermetallic compound for coupling TiAL according to claim 1 is characterized in that mode of heating adopts eddy-current heating or resistance heated in step 3.
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| CN108480838B (en) * | 2018-05-07 | 2020-08-11 | 中国航发北京航空材料研究院 | Diffusion welding connection method adopting Ti foil and titanium-based brazing filler metal foil as intermediate layer |
| CN111421218A (en) * | 2020-04-28 | 2020-07-17 | 上海交通大学 | Hydrogen-containing Ti2Low-temperature diffusion welding method for AlNb-based alloy and TC4 titanium alloy |
| CN112276330A (en) * | 2020-11-06 | 2021-01-29 | 西北工业大学 | Niobium-silicon intermetallic compound composite material, preparation method thereof and diffusion welding die |
| CN113319418A (en) * | 2021-06-29 | 2021-08-31 | 哈尔滨工业大学 | Molybdenum-rhenium alloy interlayer-free diffusion bonding method |
| CN114346397A (en) * | 2022-01-29 | 2022-04-15 | 哈尔滨工业大学 | Method for reducing titanium alloy diffusion bonding temperature through surface mechanical grinding treatment |
| CN114346397B (en) * | 2022-01-29 | 2023-08-08 | 哈尔滨工业大学 | Method for reducing diffusion connection temperature of titanium alloy by surface mechanical grinding treatment |
| CN115722785A (en) * | 2022-12-10 | 2023-03-03 | 昆明理工大学 | Method for preparing titanium-titanium composite double-layer blank by diffusion bonding process |
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