CN103949802A - Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal and preparing method thereof - Google Patents
Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal and preparing method thereof Download PDFInfo
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- CN103949802A CN103949802A CN201410165758.0A CN201410165758A CN103949802A CN 103949802 A CN103949802 A CN 103949802A CN 201410165758 A CN201410165758 A CN 201410165758A CN 103949802 A CN103949802 A CN 103949802A
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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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/32—Selection of soldering or welding materials proper with the principal constituent melting at more than 1550 degrees C
- B23K35/325—Ti as the principal constituent
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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
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
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Abstract
The invention belongs to the field of welding materials and discloses a Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal and a preparing method thereof. The brazing filler metal is formed by the following components in mass percent of 24-27% of Zr, 12-14% of Cu, 11-13% of Ni, 1.8-4.2% of Co, 1.2-2,8% of Mo and the balance of Ti. The preparing method comprises the steps of burdening according to the content of the components, then adopting a tungsten electric arc smelting method to prepare a brazing filler metal alloy ingot, crushing the alloy ingot into small particles, placing into a quartz tube for heating and melting, and preparing in a high-vacuum single-roll rotary quenching system to obtain the Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal by adopting a fast solidification technology. The brazing filler metal has the advantages of low melting point, short melting range, high connection strength in brazing of a TiAl joint and the like.
Description
Technical field
The invention belongs to field of welding material, be specifically related to a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal and preparation method thereof.
Background technology
TiAl base intermetallic compound alloy has that density is little (is about 3.8g/cm
3), the feature such as specific strength and elastic modelling quantity are high, mechanical behavior under high temperature and antioxygenic property excellence, is considered to a kind of high temperature structural material desirable, that have broad prospect of application.Yet the hard fragility of the essence of TiAl alloy makes it be difficult to carry out even machining of temperature-room type plasticity shaping, thereby limited the range of application of TiAl alloy.In order to expand and deepen the application of TiAI base alloy, solve connectivity problem and seem particularly important.At present, the method for attachment of TiAl alloy mainly contains melting, friction welding (FW), diffusion connection and soldering etc.When melting connects TiAl alloy, inevitably can crack and high residual thermal stress the extremely difficult high performance connector that obtains.Friction welding (FW) is connected because relevant device cost is higher with diffusion, and TiAl workpiece dimension and surface accuracy is required also higher, so that the application in the connection of TiAl alloy has been subject to significant limitation.Compare with other methods of attachment, soldering has the advantages such as the temperature of connection is low, residual stress is little, joint design is flexible, heat affecting is little, equipment cost is low, joint good connecting effect, thereby is considered to a kind of method that is comparatively applicable to connecting TiAl alloy.
The solder that soldering TiAl alloy is conventional mainly contains Ag base, Al base and Ti base alloy.While adopting Ag base solder brazing TiAl alloy, can obtain higher room temperature strength of joint.The people such as R.K.Shiue adopt Ag-Cu eutectic solder BAg-8 induction brazing Ti50Al50 in the article " Infrared brazing of TiAl intermetallic using BAg-8braze alloy " of delivering on the 51st phase < < Acta Materialia > > for 2003, the development of maximum shear strength of the joint obtaining through 950 ℃, insulation 60s soldering has reached 343MPa, once yet environment temperature surpasses 400 ℃, the shearing strength of joint sharply declines.And the antioxygenic property of Ag base solder brazing joint is also poor.Obviously, adopt Ag base solder brazing to be difficult to give full play to the hot properties of TiAl alloy.Although Al base solder brazing temperature is low, during soldering TiAl alloy, easily generate stable fragility Ti
3al interfacial reaction layer, and this conversion zone be difficult to adopt heat treated way to remove at postwelding, so that the non-constant of joint mechanical property.The people such as R.K.Shiue adopt pure Al and BAlSi-4 solder to carry out induction brazing to Ti50Al50 in the article " Infrared brazing of TiAl using Al-based braze alloys " of delivering on o. 11th < < Intermetallics > > for 2003, result shows, adopt the strength of joint of fine aluminium soldering TiAl extremely low, while adopting BAlSi-4 soldering, the development of maximum shear strength of joint is significantly improved, but also only has 86.2MPa.Ti base solder because of its main constituent element and mother metal TiAl alloy phase with, thereby there is good wetability during soldering, the joint of acquisition is in conjunction with firmly, room temperature and mechanical behavior under high temperature are excellent, and its soldered fitting corrosion resistance is good.The people such as S.J.Lee adopt the thick Ti-15Cu-15Ni foil of 50 μ m to carry out infrared induction soldering to Ti-48Al-2Nb-2Cr in the article " Infrared joining strength and interfacial microstructures of Ti-48Al-2Nb-2Cr intermetallics using Ti-15Cu-15Ni foil " of delivering on the 7th phase < < Intermetallics > > for 1999, and the joint shearing strength obtaining through 1200 ℃ of soldering 42s has reached 320MPa.The people such as the Song Xiaoguo of Harbin Institute of Technology adopt Ti40Ni40Nb20 solder alloy to Ti-45Al-5Nb-(W in the article " Brazing high Nb containing TiAl alloy using TiNi-Nb eutectic braze alloy " of delivering on the 22nd phase < < Intermetallics > > for 2012, B.Y) alloy carries out vacuum brazing, when brazing temperature is within the scope of 1160~1260 ℃, obtained better soldered fitting, shearing strength during gentle 600 ℃ of junction chamber has reached respectively 308MPa and 172MPa.Although adopt the Ti base solder brazing TiAl alloy of above-mentioned research and development can obtain the joint that higher force is learned performance, but brazing temperature is higher, be difficult to meet some and brazing temperature required to the soldering of comparatively harsh TiAl parts, and brazing temperature height easily generates thicker intermetallic compound and can increase the dissolution extent to mother metal.Therefore, be necessary to develop that a kind of low melting point (≤900 ℃), low cost, manufacturing process performance are good, the Ti base solder of joint excellent combination property during soldering TiAl.
Summary of the invention
In order to solve the shortcoming and defect part of prior art, primary and foremost purpose of the present invention is to provide a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal.
Another object of the present invention is to provide the preparation method of above-mentioned Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal.
The object of the invention is achieved through the following technical solutions:
A Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal, is comprised of Ti, Zr, Cu, Ni, Co and Mo, and the quality percentage composition of said components is: Zr24~27%, Cu12~14%, Ni11~13%, Co1.8~4.2%, Mo1.2~2.8%, surplus is Ti.
Described solder is that thickness is 25~45 μ m, the foil solder that width is 10~12mm, and the fusing point of described solder is minimum reaches 847 ℃, and fusion temperature scope is 832 ℃~870 ℃, and melting range is 15 ℃~30 ℃.
The preparation method of above-mentioned Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal, comprises the following steps:
(1) batching: take Ti, Zr, Cu, Ni, Co, Mo metallic particles is raw material, the purity of every kind of raw material all >=99.9%, press the quality percentage composition prepared furnace charge of following element: Zr24%~27%, Cu12%~14%, Ni11%~13%, Co1.8%~4.2%, Mo1.2%~2.8%, surplus is Ti;
(2) melting brazing filler metal alloy: the furnace charge that step (1) is prepared is put into vacuum arc furnace ignition adopts tungsten electrode arc melting to obtain brazing filler metal alloy ingot, alloy pig melt back 5~6 times under high-purity argon gas protection;
(3) foil preparation: put into quartz ampoule heat fused after adopting Mechanical Crushing mode that brazing filler metal alloy ingot in step (2) is broken into the granule of being convenient to load, adopt flash set technology to revolve and prepare Ti-Zr-Cu-Ni-Co-Mo amorphous foil solder in the system of quenching at high vacuum single roller.
Before the described batching of step (1), need feed metal particle surface to carry out deoxidation film and impurity processing, be specially: metallic particles is carried out to pickling, alkali bubble, then with absolute ethyl alcohol, rinse and dry up, finally Ultrasonic Cleaning dries up in acetone bath agent.
The described melting of step (2) is prepared brazing filler metal alloy step and is specially: adopt tungsten electrode arc melting brazing filler metal alloy ingot, before melting, first vacuum in the furnace chamber of vacuum arc furnace ignition is evacuated to 5 * 10
-3more than Pa, applying argon gas is to 0.05MPa~0.075MPa, and operation is at least 3 times so repeatedly, and then, under the atmosphere of argon shield, the tungsten electrode arc that is 125A~150A by size of current carries out melting to furnace charge.
The described foil preparation process of step (3) is specially: adopt Mechanical Crushing mode brazing filler metal alloy ingot in step (2) to be broken into the granule of being convenient to filling, alcohol cleans to dry up and is placed in quartz ampoule, then the quartz ampoule that is filled with brazing filler metal alloy particle is arranged on to high vacuum single roller and revolves in the system of quenching, then the vacuum that high vacuum single roller is revolved in the system furnace chamber of quenching is evacuated to 8 * 10
-4more than Pa; then applying argon gas is to 0.04MPa~0.06MPa; operation is at least 3 times so repeatedly; again under argon shield atmosphere; to quartz ampoule, heating is melted alloying pellet completely; then with argon gas, the melt jet in quartz ampoule is revolved behind the copper roller surface of the system high speed rotation of quenching coolingly rapidly to high vacuum single roller, prepare Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil.
The described foil preparation technology parameter of step (3) is specially: the linear velocity of rotation copper roller is 25m/s~40m/s, and the distance of the quartz ampoule mouth of pipe and copper roller upper surface is 1mm~2mm, for the argon pressure of melt jet, is 0.07MPa~0.08MPa.
The described Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal of step (3) foil refers to that thickness is 25~45 μ m, the foil that width is 10~12mm.
The preparation principle of solder of the present invention is: by increasing Zr content and controlling the total content (< 30%) of Cu+Ni element, reduced the fusing point of solder, reduced Ti in weld seam
xcu
yand Ti
xni
ythe growing amount of intermetallic compound, has improved glass-forming ability and the tapability of solder, has increased the wetting and spreading of solder at TiAl alloy surface, and has reduced the soldering assembling difficulty causing due to solder embrittlement; By adding appropriate Co and Mo element, can reduce the eutectoid reaction speed of solder to the corrosion of mother metal and inhibition brazing filler metal alloy, effectively prevent the enrichment of intermetallic compound in brazing process, improved the bonding strength of solder brazing TiAl alloy-junction.
By preparation method of the present invention and resulting product tool, have the following advantages and beneficial effect:
(1) fusing point of solder of the present invention is low, and its fusion temperature scope is 832 ℃~870 ℃, and corresponding brazing temperature is 900 ℃~1050 ℃;
(2) solder melting range of the present invention is short, and I reaches 15 ℃;
(3) bonding strength of solder brazing TiAl alloy-junction of the present invention is high;
(4) glass-forming ability of solder of the present invention and tapability are high, and solder is good at the wetting and spreading of TiAl alloy surface.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of amorphous brazing filler metal Ti43.7Zr25.65Cu13.3Ni12.35Co3Mo2 (wt.%) in example 2 of the present invention;
Fig. 2 is transmission electron microscope (TEM) and SEAD (SAED) figure of amorphous brazing filler metal Ti43.7Zr25.65Cu13.3Ni12.35Co3Mo2 (wt.%) in example 2 of the present invention;
Fig. 3 is the DSC curve of amorphous brazing filler metal Ti44.6Zr26.2Cu13.6Ni12.6Co1.8Mo1.2 (wt.%) in example 1 of the present invention;
Fig. 4 is the DSC curve of amorphous brazing filler metal Ti43.7Zr25.65Cu13.3Ni12.35Co3Mo2 (wt.%) in example 2 of the present invention;
Fig. 5 is the DSC curve of amorphous brazing filler metal Ti42.8Zr25.1Cu13Ni12.1Co4.2Mo2.8 (wt.%) in example 3 of the present invention.
The specific embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
(1) batching: take Ti, Zr, Cu, Ni, Co, Mo metallic particles is raw material, the purity of every kind of raw material all>=99.9%, by quality percentage composition, be Ti44.6%, Zr26.2%, Cu13.6%, Ni12.6%, Co1.8%, Mo1.2% prepared furnace charge, before batching, particle surface is removed to oxide-film and impurity processing, adopt 1.5%HF-2.5%HNO
3-5%HCl-91%H
2the first pickling of O (Vol%), then soak 5min in the NaOH of 2mol/L solution, then with absolute ethyl alcohol, rinse, dry up, finally in acetone, after Ultrasonic Cleaning 10min, dry up;
(2) melting brazing filler metal alloy: the furnace charge that step (1) is prepared is put into the water jacketed copper crucible of WS-4 type non-consumable arc furnace, first vacuum in furnace chamber is evacuated to 4.5 * 10
-3pa again applying argon gas, to 0.06MPa, operates 3 times so repeatedly, and then under the atmosphere of argon shield, adopting size of current is that the melting of 150A tungsten electrode arc obtains brazing filler metal alloy ingot 5 times;
(3) preparation of foil: adopt Mechanical Crushing mode that brazing filler metal alloy ingot in step (2) is broken into granule, alcohol is got after cleaning and drying up in the flat formula quartz ampoule that 8g packs exit width 0.3mm, length 10mm into, then the quartz ampoule that brazing filler metal alloy particle is housed being arranged on to WK-II Type B high vacuum single roller revolves in the system of quenching, guarantee that the quartz ampoule distance that the coaxial and quartz ampoule mouth of pipe and high vacuum single roller revolve the copper roller upper surface in the system of quenching with heat induced circle is 1.5mm, the vacuum of then high vacuum single roller being revolved in the system furnace chamber of quenching is evacuated to 7.8 * 10
-4pa again applying argon gas to 0.06MPa, so repeatedly operate 5 times, the force value of adjusting injection argon gas is 0.07MPa, and setting liquid quench device copper roller rotational line speed is 35m/s, after the speed that accelerates to setting until copper roller, open high frequency electric source switch, pin brazing filler metal alloy in the mode fused quartz pipe that high-frequency heating switch adopts high-frequency induction heating to yellow-white, and start to flow, press immediately insufflation switch, when melt no longer spills, unclamp high-frequency heating switch and insufflation switch.Under gas jet effect, liquid solder is ejected on the copper roller surface of High Rotation Speed, forms 30 μ m thick under chilling condition, and width is 12mm continuously, the Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil of toughness and excellent surface quality.
The Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil surface-brightening that adopts present embodiment to prepare, edge is neat, good toughness, its DSC curve is as shown in Figure 3.The amorphous foil solder molten temperature region that as seen from Figure 3 prepared by the present embodiment is 833~848 ℃, and melting range is 15 ℃; 1000 ℃ of heating-up temperatures, under the condition of temperature retention time 30min, 0.52 gram of amorphous brazing filler metal is 256mm at Ti-48Al-2Nb-2Cr alloy spreading area
2; 950 ℃ of brazing temperatures, vacuum brazing Ti-48Al-2Nb-2Cr alloy under the condition of holding time 5min, its soldered fitting room temperature shearing strength mean value is 273MPa, is about 68% of strength of parent; 800 ℃ of shearing strength mean values are 211MPa.
Embodiment 2
(1) batching: take Ti, Zr, Cu, Ni, Co, Mo metallic particles is raw material, the purity of every kind of raw material all>=99.9%, by quality percentage composition, be Ti43.7%, Zr25.65%, Cu13.3%, Ni12.35%, Co3%, Mo2% prepared furnace charge, before batching, particle surface is removed to oxide-film and impurity processing, adopt 1.5%HF-2.5%HNO
3-5%HCl-91%H
2the first pickling of O (Vol%), then soak 5min in the NaOH of 2mol/L solution, then with absolute ethyl alcohol, rinse, dry up, finally in acetone, after Ultrasonic Cleaning 10min, dry up;
(2) melting brazing filler metal alloy: the furnace charge that step (1) is prepared is put into the water jacketed copper crucible of WS-4 type non-consumable arc furnace, first vacuum in furnace chamber is evacuated to 4 * 10
-3pa again applying argon gas, to 0.055MPa, operates 4 times so repeatedly, and then under the atmosphere of argon shield, adopting size of current is that the melting of 140A tungsten electrode arc obtains brazing filler metal alloy ingot 6 times;
(3) preparation of foil: adopt Mechanical Crushing mode that brazing filler metal alloy ingot in step (2) is broken into granule, alcohol is got after cleaning and drying up in the flat formula quartz ampoule that 8g packs exit width 0.3mm, length 10mm into, then the quartz ampoule that brazing filler metal alloy particle is housed being arranged on to WK-II Type B high vacuum single roller revolves in the system of quenching, guarantee that the quartz ampoule distance that the coaxial and quartz ampoule mouth of pipe and high vacuum single roller revolve the copper roller upper surface in the system of quenching with heat induced circle is 2mm, the vacuum of then high vacuum single roller being revolved in the system furnace chamber of quenching is evacuated to 7.8 * 10
-4pa again applying argon gas to 0.05MPa, so repeatedly operate 3 times, the force value of adjusting injection argon gas is 0.07MPa, and setting liquid quench device copper roller rotational line speed is 40m/s, after the speed that accelerates to setting until copper roller, open high frequency electric source switch, pin brazing filler metal alloy in the mode fused quartz pipe that high-frequency heating switch adopts high-frequency induction heating to yellow-white, and start to flow, press immediately insufflation switch, when melt no longer spills, unclamp high-frequency heating switch and insufflation switch.Under gas jet effect, liquid solder is ejected on the copper roller surface of High Rotation Speed, forms 25 μ m thick under chilling condition, and width is 11.6mm continuously, the Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil of toughness and excellent surface quality.
The Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil surface-brightening that adopts present embodiment to prepare, edge is neat, good toughness, the X-ray diffraction of gained amorphous brazing filler metal (XRD) collection of illustrative plates as shown in Figure 1, as shown in Figure 2, DSC curve as shown in Figure 4 for transmission electron microscope (TEM) and SEAD (SAED) figure.Transmission electron microscope (TEM) shown in (XRD) collection of illustrative plates of X-ray diffraction as shown in Figure 1 and Fig. 2 and SEAD (SAED) figure can confirm that solder prepared by the present embodiment is non crystalline structure; As seen from Figure 4, amorphous brazing filler metal foil molten temperature region prepared by the present embodiment is 832~847 ℃, and melting range is 15 ℃; 950 ℃ of heating-up temperatures, under the condition of temperature retention time 30min, 0.46 gram of solder is 268mm at Ti-48Al-2Nb-2Cr alloy spreading area
2; 950 ℃ of brazing temperatures, vacuum brazing Ti-48Al-2Nb-2Cr alloy under the condition of holding time 5min, its soldered fitting room temperature shearing strength mean value is 316MPa, is about 80% of strength of parent; 800 ℃ of shearing strength mean values are 280MPa.
Embodiment 3
(1) batching: take Ti, Zr, Cu, Ni, Co, Mo metallic particles is raw material, the purity of every kind of raw material all>=99.9%, by quality percentage composition, be Ti42.8%, Zr25.1%, Cu13.0%, Ni12.1%, Co4.2%, Mo2.8% prepared furnace charge, before batching, particle surface is removed to oxide-film and impurity processing, adopt 1.5%HF-2.5%HNO
3-5%HCl-91%H
2the first pickling of O (Vol%), then soak 5min in the NaOH of 2mol/L solution, then with absolute ethyl alcohol, rinse, dry up, finally in acetone, after Ultrasonic Cleaning 10min, dry up;
(2) melting brazing filler metal alloy: the furnace charge that step (1) is prepared is put into the water jacketed copper crucible of WS-4 type non-consumable arc furnace, first vacuum in furnace chamber is evacuated to 4 * 10
-3pa again applying argon gas, to 0.065MPa, operates 5 times so repeatedly, and then under the atmosphere of argon shield, adopting size of current is that the melting of 130A tungsten electrode arc obtains brazing filler metal alloy ingot 6 times;
(3) preparation of foil: adopt Mechanical Crushing mode that brazing filler metal alloy ingot in step (2) is broken into granule, alcohol is got after cleaning and drying up in the flat formula quartz ampoule that 8g packs exit width 0.3mm, length 10mm into, then the quartz ampoule that brazing filler metal alloy particle is housed being arranged on to WK-II Type B high vacuum single roller revolves in the system of quenching, guarantee that the quartz ampoule distance that the coaxial and quartz ampoule mouth of pipe and high vacuum single roller revolve the copper roller upper surface in the system of quenching with heat induced circle is 1mm, the vacuum of first high vacuum single roller being revolved in the system furnace chamber of quenching is evacuated to 7.8 * 10
-4pa again applying argon gas to 0.05MPa, so repeatedly operate 4 times, the force value of adjusting injection argon gas is 0.08MPa, and setting liquid quench device copper roller rotational line speed is 25m/s, after the speed that accelerates to setting until copper roller, open high frequency electric source switch, pin brazing filler metal alloy in the mode fused quartz pipe that high-frequency heating switch adopts high-frequency induction heating to yellow-white, and start to flow, press immediately insufflation switch, when melt no longer spills, unclamp high-frequency heating switch and insufflation switch.Under gas jet effect, liquid solder is ejected on the copper roller surface of High Rotation Speed, forms 45 μ m thick under chilling condition, and width is 10.4mm continuously, the Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil of toughness and excellent surface quality.
The Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil surface-brightening that adopts present embodiment to prepare, edge is neat, good toughness, its DSC curve is as shown in Figure 5.The amorphous foil solder molten temperature region that as seen from Figure 5 prepared by the present embodiment is 833~855 ℃, and melting range is 22 ℃; 1000 ℃ of heating-up temperatures, under the condition of temperature retention time 30min, 0.52 gram of solder is 240mm at Ti-48Al-2Nb-2Cr alloy spreading area
2; 1000 ℃ of brazing temperatures, vacuum brazing Ti-48Al-2Nb-2Cr alloy under the condition of holding time 5min, its soldered fitting room temperature shearing strength mean value is 258MPa, is about 65% of strength of parent; 800 ℃ of shearing strength mean values are 207MPa.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (8)
1. a Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal, it is characterized in that: described amorphous brazing filler metal is comprised of Ti, Zr, Cu, Ni, Co and Mo, the quality percentage composition of said components is: Zr24~27%, Cu12~14%, Ni11~13%, Co1.8~4.2%, Mo1.2~2.8%, surplus is Ti.
2. a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal according to claim 1, is characterized in that: described amorphous brazing filler metal is that thickness is 25~45 μ m, the foil solder that width is 10~12mm.
3. a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal according to claim 1, is characterized in that: the fusing point of described amorphous brazing filler metal is 847 ℃~870 ℃, and melting range is 15 ℃~30 ℃.
4. the preparation method of a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal described in claim 1~3 any one, is characterized in that: concrete preparation process is as follows:
(1) batching: take Ti, Zr, Cu, Ni, Co, Mo metallic particles is raw material, the purity of every kind of raw material all >=99.9%, press the quality percentage composition prepared furnace charge of following element: Zr24%~27%, Cu12%~14%, Ni11%~13%, Co1.8%~4.2%, Mo1.2%~2.8%, surplus is Ti;
(2) melting brazing filler metal alloy: the furnace charge that step (1) is prepared is put into vacuum arc furnace ignition adopts tungsten electrode arc melting to obtain brazing filler metal alloy ingot, alloy pig melt back 5~6 times under high-purity argon gas protection;
(3) foil preparation: put into quartz ampoule heat fused after adopting Mechanical Crushing mode that brazing filler metal alloy ingot in step (2) is broken into the granule of being convenient to load, adopt flash set technology to revolve and prepare Ti-Zr-Cu-Ni-Co-Mo amorphous foil solder in the system of quenching at high vacuum single roller.
5. the preparation method of a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal according to claim 4, it is characterized in that: before the described batching of step (1), need feed metal particle surface to carry out deoxidation film and impurity processing, be specially: metallic particles is carried out to pickling, alkali bubble, then with absolute ethyl alcohol, rinse and dry up, finally in acetone bath agent, Ultrasonic Cleaning dries up.
6. the preparation method of a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal according to claim 4, is characterized in that: before the described melting of step (2), first vacuum in the furnace chamber of vacuum arc furnace ignition is evacuated to 5 * 10
-3pa above again applying argon gas to 0.05MPa~0.075MPa, so repeatedly operate 3~5 times, then, under the atmosphere of argon shield, the tungsten electrode arc that is 125A~150A by size of current carries out melting to furnace charge.
7. the preparation method of a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal according to claim 4, it is characterized in that: the described foil preparation process of step (3) is specially: adopt Mechanical Crushing mode brazing filler metal alloy ingot in step (2) to be broken into the granule of being convenient to filling, alcohol cleans to dry up and is placed in quartz ampoule, then the quartz ampoule that is filled with brazing filler metal alloy particle is arranged on to high vacuum single roller and revolves in the system of quenching, the vacuum that high vacuum single roller is revolved in the system furnace chamber of quenching is evacuated to 8 * 10
-4pa above again applying argon gas to 0.04MPa~0.06MPa; so repeatedly operate 3~5 times; again under argon shield atmosphere; to quartz ampoule, heating is melted alloying pellet completely; then with argon gas, the melt jet in quartz ampoule is revolved behind the copper roller surface of the system high speed rotation of quenching coolingly to high vacuum single roller, prepare Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal foil.
8. the preparation method of a kind of Ti-Zr-Cu-Ni-Co-Mo amorphous brazing filler metal according to claim 7, it is characterized in that: the linear velocity of the copper roller of described rotation is 25m/s~40m/s, the distance of the quartz ampoule mouth of pipe and copper roller upper surface is 1mm~2mm, for the argon pressure of melt jet, is 0.07MPa~0.08MPa.
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CN104722955A (en) * | 2015-03-20 | 2015-06-24 | 江苏科技大学 | High-temperature brazing filler metal for brazing Si3N4 ceramic and stainless steel, preparing method and brazing process |
CN105195917A (en) * | 2015-10-30 | 2015-12-30 | 江苏科技大学 | Al-Si-Mg series amorphous brazing material for brazing foamed aluminum plate as well as preparation method and brazing method |
CN106392363A (en) * | 2016-12-06 | 2017-02-15 | 北京航空航天大学 | Titanium and zirconium-based amorphous alloy brazing filler metal with low contents of Cu and Ni and without containing Si element and preparation method thereof |
CN106392363B (en) * | 2016-12-06 | 2020-02-21 | 北京航空航天大学 | Titanium-zirconium-based amorphous alloy brazing filler metal with low Cu and Ni contents and without Si element and preparation method thereof |
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CN109226951A (en) * | 2018-11-09 | 2019-01-18 | 湖北三江航天江北机械工程有限公司 | The connection method of titanium alloy precision complex structural member |
CN109590635A (en) * | 2019-01-23 | 2019-04-09 | 贵研铂业股份有限公司 | A kind of titanium based solder powder and preparation method thereof |
WO2020223162A1 (en) * | 2019-04-30 | 2020-11-05 | Oregon State University | Cu-based bulk metallic glasses in the cu-zr-hf-al and related systems |
US11821064B2 (en) | 2019-04-30 | 2023-11-21 | Oregon State University | Cu-based bulk metallic glasses in the Cu—Zr—Hf—Al and related systems |
CN111020412A (en) * | 2019-12-20 | 2020-04-17 | 常州世竟液态金属有限公司 | Environment-friendly titanium-based bulk amorphous alloy |
CN111438465A (en) * | 2020-05-11 | 2020-07-24 | 中国航发北京航空材料研究院 | Ti-Ni-Nb brazing material of Nb-Si based ultra-high temperature structure material and brazing connection process |
CN111496417A (en) * | 2020-05-11 | 2020-08-07 | 中国航发北京航空材料研究院 | Ti-Ni-Nb-Zr brazing material of Nb-Si-based ultrahigh-temperature structural material and brazing connection process |
CN111438464B (en) * | 2020-05-11 | 2021-12-24 | 中国航发北京航空材料研究院 | Ti-Ni-Nb-Zr-Hf brazing material of Nb-Si-based ultrahigh-temperature structure material and brazing connection process |
CN111438465B (en) * | 2020-05-11 | 2021-12-24 | 中国航发北京航空材料研究院 | Ti-Ni-Nb brazing material of Nb-Si based ultra-high temperature structure material and brazing connection process |
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CN111702278A (en) * | 2020-05-13 | 2020-09-25 | 中国科学院金属研究所 | Ti2Medium-temperature Ti-based brazing filler metal for brazing same or different AlNb-based alloys as well as preparation method and brazing process thereof |
CN111702278B (en) * | 2020-05-13 | 2021-10-22 | 中国科学院金属研究所 | Ti2Medium-temperature Ti-based brazing filler metal for brazing same or different AlNb-based alloys as well as preparation method and brazing process thereof |
CN113769824A (en) * | 2021-08-16 | 2021-12-10 | 昆明贵研新材料科技有限公司 | Grinding device and preparation method of spherical titanium-zirconium-based brazing filler metal |
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CN114346519A (en) * | 2022-03-04 | 2022-04-15 | 哈尔滨工业大学 | High-entropy brazing filler metal for TiAl alloy brazing and preparation method and application thereof |
CN114273819B (en) * | 2022-03-04 | 2022-05-17 | 湖南湘投金天科技集团有限责任公司 | Welding flux for welding titanium alloy and preparation method and application thereof |
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