CN105252169A - Active amorphous brazing filler metal for brazing ZrB2-SiC ceramic materials, preparation method for active amorphous brazing filler metal and brazing process - Google Patents

Active amorphous brazing filler metal for brazing ZrB2-SiC ceramic materials, preparation method for active amorphous brazing filler metal and brazing process Download PDF

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CN105252169A
CN105252169A CN201510582911.4A CN201510582911A CN105252169A CN 105252169 A CN105252169 A CN 105252169A CN 201510582911 A CN201510582911 A CN 201510582911A CN 105252169 A CN105252169 A CN 105252169A
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brazing
filler metal
solder
melting
amorphous
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王刚
肖平
黄仲佳
徐超群
丁鹏飞
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Anhui Polytechnic University
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Anhui Polytechnic University
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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
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu as the principal constituent
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/006—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of metals or metal salts
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/124—Metallic interlayers based on copper
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/126—Metallic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/12—Metallic interlayers
    • C04B2237/126—Metallic interlayers wherein the active component for bonding is not the largest fraction of the interlayer
    • C04B2237/127—The active component for bonding being a refractory metal

Abstract

The invention discloses active amorphous brazing filler metal for brazing ZrB2-SiC ceramic materials, a preparation method for the active amorphous brazing filler metal and a brazing process, particularly relates to Cu-Ti-Ni-Zr high-temperature active amorphous brazing filler metal for brazing ZrB2-SiC ultra-high-temperature ceramic materials, a preparation method for the Cu-Ti-Ni-Zr high-temperature active amorphous brazing filler metal and a brazing process, and belongs to brazing filler metal in the amorphous and metallurgy fields. The components of the brazing filler metal comprise, by atomic percentage, 36.0-42.0% of Cu, 30.0-35.0% of Ti, 16.0-23.0% of Zr and the balance Ni. The melting temperature of the active amorphous brazing filler metal is 1110-1150 K, and the brazing temperature is 1183-1273 K. The Cu-Ti-Ni-Zr high-temperature active amorphous brazing filler metal obtained through the rapid condensation technology has good wettability. The room temperature shearing strength of the ZrB2-SiC ultra-high-temperature ceramic materials brazed through the amorphous brazing filler metal in a vacuum brazing mode can be as high as 160 MPa and much higher than that of Cu-based and Ag-based brazing filler metal.

Description

A kind of soldering ZrB 2active amorphous solder of-SiC ceramic and preparation method thereof and soldering processes
Technical field
The present invention relates to a kind of soldering ZrB 2active amorphous solder of-SiC ceramic and preparation method thereof and soldering processes, be specifically related to a kind of soldering ZrB 2cu-Ti-Ni-Zr high temperature active amorphous filler metal of-SiC superhigh temperature ceramic material and preparation method thereof and soldering processes, belong to the brazing material of amorphous state and field of metallurgy.
Background technology
In recent years, along with fast development and the great-leap-forward progress of space flight and aviation technology, hypersonic aircraft, sky and space plane, reusable Step atmospheric layers vehicle etc. have become the focus competitively studied various countries, and hypersonic aircraft is reusable, long-time, the combination property of the military service feature of High Mach number flight to the material of the crucial thermal part of aircraft proposes more and more higher requirement.In numerous high-temperature materials, superhigh temperature ceramic material has excellent high temperature and superhigh temperature (> 2100K) combination property because of it, be be expected to one of material solving following hypersonic aircraft superhigh temperature anti-heat problem most potentiality, become the study hotspot of domestic and international investigation of materials personnel in recent years.
ZrB 2because having lower density (6.09g/cm 3), higher thermal conductivity (65-135W/mK), moderate thermal coefficient of expansion and higher anti-oxidant ablation property, be widely regarded as one very promising non-ablative type superhigh temperature heat insulation material.Meanwhile, adding of wild phase SiC particle, ZrB is further improved 2heat endurance and mechanical performance, and the anti-oxidant ablation property of material, makes ZrB 2-SiC superhigh temperature ceramic material is subject to international material circle and pays close attention to greatly.But, ZrB 2-SiC superhigh temperature ceramic material is because material hardness is high, fragility is large, processing forming is poor, the manufacture being difficult to be realized by the method for direct machine-shaping complex-shaped component or large-size components is produced, and traditional complicated shape superhigh temperature ceramics component is obtained by machining or electric processing method usually.But electric machining process is complicated, with high costs, and can cause unavoidable machining damage to superhigh temperature ceramics component, and these all greatly limit the practical application of this material.In recent years, lot of domestic and foreign scientific worker has carried out the trial of the method for attachment of large amount of complex shaped ceramic material members, and this is that the acquisition of Large Size Special Shaped superhigh temperature ceramic material structural member provides new thinking.In numerous method of attachment, diffusion connection is connected with active soldering and is considered to the most effective two kinds of methods.Soldering tech because its technique is simple, bonding strength is higher, the wide adaptability of joint dimension and shape, cost be lower, be applicable to the advantages such as suitability for industrialized production and become the one preferred technique that superhigh temperature ceramic material is connected.
At present, in comparatively common Cu base, Ni based active solder, due to the existence of a large amount of active element, the fragility of solder own is comparatively large, is difficult to be prepared into foil-like and uses; Meanwhile, the strength of joint of the soldering sample of acquisition is lower, and these unfavorable factors limit the practical application of active solder all greatly.In numerous active solder systems, the marvellous usefulness gone out shown by amorphous filler metal attracts people's attention most.Compare with thread crystalline state solder with conventional fragility powdered filler metal, strip brazing material, amorphous filler metal has the advantage of many uniquenesses, such as, seam organization and uniform composition, wetability, good fluidity, composition is adjustable, easy to use etc.Therefore, certain non-crystaline amorphous metal method for designing and non-crystaline amorphous metal technology of preparing is adopted to develop novel foil-like active solder for ZrB 2the connection of-SiC superhigh temperature ceramic material has extremely important theory and practical value.
Summary of the invention
The problem that 1, will solve
For the above-mentioned problems in the prior art, the invention provides out a kind of soldering ZrB 2active amorphous solder of-SiC ceramic and preparation method thereof and soldering processes, solve the common Cu base of employing, Ni base at present and be connected ZrB with Ag base solder 2the problem that room-temperature property is poor and the fragility of solder own is large of-SiC superhigh temperature ceramic material.The amorphous filler metal that the present invention adopts corresponding method for designing and flash set technology to prepare can increase substantially ZrB 2the room-temperature property of-SiC superhigh temperature ceramic material.
2, technical scheme
In order to solve the problem, soldering ZrB of the present invention 2the active amorphous solder of-SiC ceramic, is characterized in that: the component of described solder and content by atomic percentage are: Cu:36.0 ~ 42.0%; Ti:30.0 ~ 35.0%; Zr:16.0 ~ 23.0%; All the other are Ni.
Above-mentioned amorphous brazing filler metal follows these steps to be prepared from technique:
(1) after electrolysis copper billet (Cu), titanium sponge (Ti), iodate zirconium (Zr) and nickel sheet (Ni) being pulverized, according to above-mentioned formula weighing raw materials on electronic balance, the purity of Cu, Ti and Ni is more than 99.9%, and the purity of Zr reaches more than 99.99%;
(2) electric arc furnaces batching by above-mentioned formula being placed in DHL-500II type gets rid of the vacuum magnetic control tungsten electrode arc furnace of band machine combination plant, five stations (half ball-and-socket) are had in electric arc furnaces, three molten alloy stations (band magnetic stirs), inhale foundry work position for one, a melting degas station, wherein placing titanium sponge sample in melting degas station, three molten alloy stations can put the batching of three kinds of same formulas or different formulations simultaneously;
(3), before melting, first utilize mechanical pump that vacuum in stove is evacuated to 10 -1pa, keeps 3 minutes, opens molecular pump afterwards and vacuum in stove is evacuated to 6.0 × 10 -3more than Pa, then be filled with high-purity argon gas to-0.05MPa;
(4) before sample melting, first by the titanium sponge melt back in melting degas station in stove at least 4 times, to ensure the oxygen fully removed in atmosphere;
(5) during melting sample, in order to accelerate dissolving each other and obtaining uniform alloying component of different-alloy element, the induction coil starting water-cooled copper dish bottom carries out electromagnetic agitation, and under function composite by electromagnetic stirring, alloy overturns melting more than 4 times at least repeatedly;
(6) after electric arc melting, sample is weighed, finds that the weightlessness of sample is within 0.1%, can think alloy actual constituent and nominal composition basically identical, the sample after melting is the foundry alloy of follow-up preparation amorphous state paillon foil;
(7), after foundry alloy sample comminution melting obtained, loading nozzle is in rectangular quartz glass tube, and nozzle length is 8mm, and width is 1mm;
(8) what the electric arc furnaces quartz ampoule installing foundry alloy being contained in DHL-500II type got rid of band machine combination plant gets rid of in the induction coil of band machine, again the distance between nozzle and copper roller surface is adjusted between 2 ~ 3mm, to ensure that the liquid be injected on copper roller is dull and stereotyped stream, and form condition of steady flow;
(9) close fire door, and before eddy-current heating, adopt mechanical pump that vacuum in stove is evacuated to 10 -1pa, keeps 3 minutes, opens molecular pump afterwards and vacuum in stove is evacuated to 6.0 × 10 -3more than Pa, and then be filled with high-purity argon gas to 0.01MPa;
(10) induction heating power is opened, after foundry alloy is heated to complete molten state, insulation superheated melt 30 seconds; And motor is opened while unlatching induction heating power, make copper roller rotate (copper roller diameter 250mm, width 40mm), rotating speed is 35m/s;
(11) argon pressure is adjusted to 0.05MPa, utilize the pressure differential formed in stove the melt continuous spraying in glass tube to be mapped to the copper roller surface of High Rotation Speed, motlten metal forms foil-like due to chilling effect, thus obtains amorphous filler metal of the present invention.
The amorphous brazing filler metal soldering ZrB that said method and technique are prepared from 2the soldering processes of-SiC ceramic are as follows:
(1) before soldering, first by solder interface with 800 ﹟abrasive paper for metallograph polishes, then by solder and ZrB 2take out after-SiC ceramic carries out Ultrasonic Cleaning 20min respectively in acetone soln and dry up;
(2) by ZrB 2-SiC ceramic/solder/ZrB 2the assembled in sequence of-SiC ceramic in brazing jig, and puts it in vacuum brazing furnace, closes fire door, starts to be evacuated to 5.0 × 10 to furnace chamber -3more than Pa;
(3) after vacuum reaches requirement, start heating, with the ramp of 10K/min to 573K, insulation 20min, makes the binding agent of bonding sample fully volatilize, thus ensures that brazing face is not contaminated;
(4) rise to brazing temperature (1183K ~ 1273K) with the speed of 10K/min, insulation 10 ~ 50min, ensure that solder can fully melt, make it fully to be combined with mother metal;
(5) be down to 573K with the speed of 5k/min, open fire door after finally cooling to room temperature with the furnace and take out test specimen, adopt this amorphous filler metal vacuum brazing ZrB 2-SiC superhigh temperature ceramic material, its room temperature shear strength is up to 160MPa.
3, beneficial effect
Compared to prior art, beneficial effect of the present invention is:
(1) solder that the present invention obtains is complete amorphous state, compared with crystalline state solder, amorphous filler metal has more excellent wettability, it is almost melt simultaneously, equably and sprawl in heating process, the uniform weld seam of easy formation, thus be conducive to the soldered fitting obtaining dense structure; And crystalline state solder each phase fusing point is inconsistent, low melting point first melts mutually, and high-melting-point part is piled up because flow velocity is slow subsequently, easily causes lamination; In addition, due to the unstability of amorphous structure, there is the precipitation of crystal phase when close fusing, therefore a large amount of heat can be released instantaneously in fusing, under the impact of this exothermic reaction, the atom in solder moves aggravation, be conducive to Elements Diffusion in aggravation solder, thus improve the wettability of solder;
(2) solder that the present invention obtains has good toughness, traditional high-temp solder owing to containing the elements such as Ni, Fe, Si, B, P more, these elements very easily cause the fragility of solder, therefore, be difficult to the paillon foil forming large-size, often make sheet with Linear cut etc. or directly adopt lamination shape, it is very inconvenient to use, and adjustment solder composition is also very difficult; The amorphous filler metal that the present invention obtains only need configure foundry alloy remelting on amorphous state device for making of component ratio by design mix, direct spray forms, the solder paper tinsel made has excellent pliability, can bend 180 ° and do not rupture, and the paillon foil size obtained is comparatively large, therefore, in actual use can according to the actual needs treating weldment, be prefabricated into definite shape, be placed in the gap of soldered fitting exactly, raise the efficiency;
(3) solder that the present invention obtains contains the necessary active element of ceramic soldering material, i.e. Ti element and Zr element; Prepare angle from solder, these two kinds of elements have the precipitation being beneficial to amorphous phase, heavy alloyed glass forming ability can be carried greatly;
(4) the present invention can also improve soldered fitting performance, and amorphous filler metal chemical composition is even, and impurity content is few, both without crystal grain, separate out again without eutectic phase, fusing evenly, the diffusivity of alloying element is strong, easily forms uniform weld seam, in addition, amorphous filler metal can make brazing filler metal gap reduce further, fusion temperature scope is extremely narrow, and fusing time is short, thus has good moment mobility, capillary absorption function can be given full play to, thus be conducive to the high strength soldered fitting obtaining dense structure;
(5) the solder foil thickness that prepared by the present invention is 30 ± 2um, and any surface finish, both sides are smooth.
Accompanying drawing explanation
Fig. 1 is amorphous filler metal XRD collection of illustrative plates prepared by the present invention;
Fig. 2 is amorphous filler metal soldering ZrB prepared by the present invention 2angle of wetting variation diagram in-SiC superhigh temperature ceramic material process.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further.
In the method that numerous amorphous alloy component designs, " binary eutectic component ratio " method is regarded as very easy and effective method.Its central idea is: the formation of amorphous phase depends on the forming core of crystal phase in cooling procedure and growth is effectively suppressed, and can form intermetallic compound between its solvent element and solute element in non-crystaline amorphous metal.Therefore, how to reduce and even eliminate the possibility that these intermetallic compounds separate out and become the key that can amorphous phase be formed.As everyone knows, for Binary Alloy System, its subcooling films of the alloy of eutectic composition has higher heat endurance.Several bianry alloy with eutectic composition is supposed to mix by a certain percentage, the tendency forming eutectic phase between solvent constituent element and solute constituent element is balanced mutually, like this, the possibility that any one bianry alloy forms eutectic product all can reduce and makes melt continue be chilled to lower temperature and crystallization does not occur, and final melt " is freezed " and forms amorphous phase.
Choosing CuTiZrNi quaternary alloy system in the design, selecting Cu by consulting phasor handbook 43ti 57, Cu 61.8zr 38.2, Ti 39ni 61and Zr 64ni 36four groups of eutectic compositions with lower eutectic temperature, according to above-mentioned " binary eutectic component ratio " method, this alloying component C amcan be expressed as:
C am＝α(Cu 43Ti 57)+β(Cu 61.8Zr 38.2)+γ(Ti 39Ni 61)+θ(Zr 64Ni 36)(1)
, simultaneously for ensureing that the possibility that in process of setting, each intermetallic compound is separated out balances mutually, then should there is following relation between α, β, γ and θ in wherein alpha+beta+γ+θ=1:
α△H (CuTi)＝β△H (CuZr)＝γ△H (TiNi)＝θ△H (ZrNi)(2)
Wherein △ H (CuTi), △ H (CuZr), △ H (TiNi)with △ H (ZrNi)be respectively Cu 43ti 57, Cu 61.8zr 38.2, Ti 39ni 61, and Zr 64ni 36enthalpy of mixing between cluster, Takeuchi etc. [18]report that above-mentioned enthalpy of mixing is respectively-9 ,-23 ,-35 and-49kJ/mol.
Connection separates (1) and (2) two formulas, can obtain this alloying component and be about Cu 40ti 32zr 19ni 9(at.%), obtain by suitably adjusting, this alloy (Cu xti yzr zni u, wherein x, y, z and u are atomic percentage) at x=36.0% ~ 42.0%, y=30.0% ~ 35.0%, z=16.0% ~ 23.0%, all the other be Ni scope in be amorphous structure.
Embodiment 1
A kind of soldering ZrB 2the active amorphous solder of-SiC ceramic, its component and content by atomic percentage are: Cu:39.0%; Ti:35.0%; Zr:19.0%; All the other are Ni.
Preparation method follows these steps to carry out with technique:
(1) after electrolysis copper billet (Cu), titanium sponge (Ti), iodate zirconium (Zr) and nickel sheet (Ni) being pulverized, according to above-mentioned formula weighing raw materials on electronic balance, the purity of Cu, Ti and Ni is more than 99.9%, and the purity of Zr reaches more than 99.99%;
(2) electric arc furnaces batching by above-mentioned formula being placed in DHL-500II type gets rid of the vacuum magnetic control tungsten electrode arc furnace of band machine combination plant, five stations (half ball-and-socket) are had in electric arc furnaces, three molten alloy stations (band magnetic stirs), inhale foundry work position for one, a melting degas station, wherein placing titanium sponge sample in melting degas station, three molten alloy stations can put the batching of three kinds of same formulas or different formulations simultaneously;
(3), before melting, first utilize mechanical pump that vacuum in stove is evacuated to 10 -1pa, keeps 3 minutes, opens molecular pump afterwards and vacuum in stove is evacuated to 6.0 × 10 -3more than Pa, then be filled with high-purity argon gas to-0.05MPa;
(4) before sample melting, first by the titanium sponge melt back in melting degas station in stove at least 4 times, to ensure the oxygen fully removed in atmosphere;
(5) during melting sample, in order to accelerate dissolving each other and obtaining uniform alloying component of different-alloy element, the induction coil starting water-cooled copper dish bottom carries out electromagnetic agitation, and under function composite by electromagnetic stirring, alloy overturns melting more than 4 times at least repeatedly;
(6) after electric arc melting, sample is weighed, finds that the weightlessness of sample is within 0.1%, can think alloy actual constituent and nominal composition basically identical, the sample after melting is the foundry alloy of follow-up preparation amorphous state paillon foil;
(7), after foundry alloy sample comminution melting obtained, loading nozzle is in rectangular quartz glass tube, and nozzle length is 8mm, and width is 1mm;
(8) what the electric arc furnaces quartz ampoule installing foundry alloy being contained in DHL-500II type got rid of band machine combination plant gets rid of in the induction coil of band machine, again the distance between nozzle and copper roller surface is adjusted between 2 ~ 3mm, to ensure that the liquid be injected on copper roller is dull and stereotyped stream, and form condition of steady flow;
(9) close fire door, and before eddy-current heating, adopt mechanical pump that vacuum in stove is evacuated to 10 -1pa, keeps 3 minutes, opens molecular pump afterwards and vacuum in stove is evacuated to 6.0 × 10 -3more than Pa, and then be filled with high-purity argon gas to 0.01MPa;
(10) induction heating power is opened, after foundry alloy is heated to complete molten state, insulation superheated melt 30 seconds; And motor is opened while unlatching induction heating power, make copper roller rotate (copper roller diameter 250mm, width 40mm), rotating speed is 35m/s;
(11) argon pressure is adjusted to 0.05MPa, utilize the pressure differential formed in stove the melt continuous spraying in glass tube to be mapped to the copper roller surface of High Rotation Speed, motlten metal forms foil-like due to chilling effect, thus obtains amorphous filler metal of the present invention.
The fusion temperature scope of this solder is 1110 ~ 1150K, and the solder paper tinsel adopting this to make has excellent pliability, can bend 180 ° and do not rupture, and the paillon foil size obtained is larger, the solder foil thickness of preparation is 30 ± 2um, and any surface finish, both sides are smooth.
Soldering process step is as follows:
(1) before soldering, first by solder interface with 800 ﹟abrasive paper for metallograph polishes, then by solder and ZrB 2take out after-SiC ceramic carries out Ultrasonic Cleaning 20min respectively in acetone soln and dry up;
(2) by ZrB 2-SiC ceramic/solder/ZrB 2the assembled in sequence of-SiC ceramic in brazing jig, and puts it in vacuum brazing furnace, closes fire door, starts to be evacuated to 5.0 × 10 to furnace chamber -3more than Pa;
(3) after vacuum reaches requirement, start heating, with the ramp of 10K/min to 573K, insulation 20min, makes the binding agent of bonding sample fully volatilize, thus ensures that brazing face is not contaminated;
(4) rise to brazing temperature (1183K ~ 1273K) with the speed of 10K/min, insulation 10 ~ 50min, ensure that solder can fully melt, make it fully to be combined with mother metal;
(5) be down to 573K with the speed of 5k/min, open fire door after finally cooling to room temperature with the furnace and take out test specimen.
As shown in Figure 1, amorphous filler metal prepared by the present invention XRD collection of illustrative plates between 30 °-50 °, can find out that XRD collection of illustrative plates presents the distinctive diffuse scattering peak of amorphous phase, illustrate that this foil is complete amorphous structure.Figure 2 shows that this amorphous filler metal soldering ZrB 2angle of wetting change in-SiC superhigh temperature ceramic material process, can find out on the whole, embody good wetability between this amorphous filler metal and mother metal, this characteristic is that the acquisition of good soldered fitting quality is laid a good foundation.
Prepare Cu-Ti-Ni-Zr active amorphous state solder by the method for the present embodiment, and adopt this amorphous brazing filler metal vacuum brazing ZrB 2the room temperature shear strength of-SiC superhigh temperature ceramics can reach 160MPa, is far longer than common Cu base, Ag base solder.
Embodiment 2
A kind of soldering ZrB 2the active amorphous solder of-SiC ceramic, its component and content by atomic percentage are: Cu:36.0%; Ti:30.0%; Zr:23.0%; All the other are Ni.
Soldering processes are identical with soldering processes described in embodiment 1, adopt the ZrB of this amorphous filler metal vacuum brazing 2-SiC superhigh temperature ceramic material, its room temperature shear strength is up to 143MPa.
Embodiment 3
A kind of soldering ZrB 2the active amorphous solder of-SiC ceramic, its component and content by atomic percentage are: Cu:42.0%; Ti:35.0%; Zr:16.0%; All the other are Ni.
Soldering processes are identical with soldering processes described in embodiment 1, adopt the ZrB of this amorphous filler metal vacuum brazing 2-SiC superhigh temperature ceramic material, its room temperature shear strength is up to 124MPa.
Schematically above be described the present invention and embodiment thereof, this description is not restricted.So, if those of ordinary skill in the art enlightens by it, when not departing from the invention aim, designing the frame mode similar to this technical scheme and embodiment without creationary, all should protection scope of the present invention be belonged to.

Claims (3)

1. a soldering ZrB 2the active amorphous solder of-SiC ceramic, is characterized in that: the component of described solder and content by atomic percentage are: Cu:36.0 ~ 42.0%; Ti:30.0 ~ 35.0%; Zr:16.0 ~ 23.0%; All the other are Ni.
2. a soldering ZrB 2the preparation method of the active amorphous solder of-SiC ceramic, is characterized in that following these steps to carry out with technique:
(1) after electrolysis copper billet (Cu), titanium sponge (Ti), iodate zirconium (Zr) and nickel sheet (Ni) being pulverized, according to above-mentioned formula weighing raw materials on electronic balance, the purity of Cu, Ti and Ni is more than 99.9%, and the purity of Zr reaches more than 99.99%;
(2) electric arc furnaces batching by above-mentioned formula being placed in DHL-500II type gets rid of the vacuum magnetic control tungsten electrode arc furnace of band machine combination plant, five stations (half ball-and-socket) are had in electric arc furnaces, three molten alloy stations (band magnetic stirs), inhale foundry work position for one, a melting degas station, wherein placing titanium sponge sample in melting degas station, three molten alloy stations can put the batching of three kinds of same formulas or different formulations simultaneously;
(3), before melting, first utilize mechanical pump that vacuum in stove is evacuated to 10 -1pa, keeps 3 minutes, opens molecular pump afterwards and vacuum in stove is evacuated to 6.0 × 10 -3more than Pa, then be filled with high-purity argon gas to-0.05MPa;
(4) before sample melting, first by the titanium sponge melt back in melting degas station in stove at least 4 times, to ensure the oxygen fully removed in atmosphere;
(5) during melting sample, in order to accelerate dissolving each other and obtaining uniform alloying component of different-alloy element, the induction coil starting water-cooled copper dish bottom carries out electromagnetic agitation, and under function composite by electromagnetic stirring, alloy overturns melting more than 4 times at least repeatedly;
(6) after electric arc melting, sample is weighed, finds that the weightlessness of sample is within 0.1%, can think alloy actual constituent and nominal composition basically identical, the sample after melting is the foundry alloy of follow-up preparation amorphous state paillon foil;
(7), after foundry alloy sample comminution melting obtained, loading nozzle is in rectangular quartz glass tube, and nozzle length is 8mm, and width is 1mm;
(8) what the electric arc furnaces quartz ampoule installing foundry alloy being contained in DHL-500II type got rid of band machine combination plant gets rid of in the induction coil of band machine, again the distance between nozzle and copper roller surface is adjusted between 2 ~ 3mm, to ensure that the liquid be injected on copper roller is dull and stereotyped stream, and form condition of steady flow;
(9) close fire door, and before eddy-current heating, adopt mechanical pump that vacuum in stove is evacuated to 10 -1pa, keeps 3 minutes, opens molecular pump afterwards and vacuum in stove is evacuated to 6.0 × 10 -3more than Pa, and then be filled with high-purity argon gas to 0.01MPa;
(10) induction heating power is opened, after foundry alloy is heated to complete molten state, insulation superheated melt 30 seconds; And motor is opened while unlatching induction heating power, make copper roller rotate (copper roller diameter 250mm, width 40mm), rotating speed is 35m/s;
(11) argon pressure is adjusted to 0.05MPa, utilize the pressure differential formed in stove the melt continuous spraying in glass tube to be mapped to the copper roller surface of High Rotation Speed, motlten metal forms foil-like due to chilling effect, thus obtains amorphous filler metal of the present invention.
3. a soldering ZrB 2the soldering processes of the active amorphous solder of-SiC ceramic, is characterized in that:
(1) before soldering, first by solder interface with 800 ﹟abrasive paper for metallograph polishes, then by solder and ZrB 2take out after-SiC ceramic carries out Ultrasonic Cleaning 20min respectively in acetone soln and dry up;
(2) by ZrB 2-SiC ceramic/solder/ZrB 2the assembled in sequence of-SiC ceramic in brazing jig, and puts it in vacuum brazing furnace, closes fire door, starts to be evacuated to 5.0 × 10 to furnace chamber -3more than Pa;
(3) after vacuum reaches requirement, start heating, with the ramp of 10K/min to 573K, insulation 20min, makes the binding agent of bonding sample fully volatilize, thus ensures that brazing face is not contaminated;
(4) rise to brazing temperature (1183K ~ 1273K) with the speed of 10K/min, insulation 10 ~ 50min, ensure that solder can fully melt, make it fully to be combined with mother metal;
(5) be down to 573K with the speed of 5k/min, open fire door after finally cooling to room temperature with the furnace and take out test specimen, adopt this amorphous filler metal vacuum brazing ZrB 2-SiC superhigh temperature ceramic material, its room temperature shear strength is up to 160MPa.
CN201510582911.4A 2015-09-14 2015-09-14 Active amorphous brazing filler metal for brazing ZrB2-SiC ceramic materials, preparation method for active amorphous brazing filler metal and brazing process Pending CN105252169A (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106041238A (en) * 2016-06-13 2016-10-26 西安理工大学 Probe shell structure for measuring specific retention of petroleum well and seal welding material of probe shell structure
CN106112310A (en) * 2016-07-27 2016-11-16 江苏科技大学 A kind of solder for ZrB2 SiC superhigh temperature ceramics soldering and the technique using this solder to carry out soldering
CN106112309A (en) * 2016-07-27 2016-11-16 江苏科技大学 A kind of brazing material for SiC ceramic soldering and use the technique that this material carries out soldering
CN106242606A (en) * 2016-07-20 2016-12-21 哈尔滨工业大学 One utilizes Zr Ni base solder brazing ZrB2the method of SiC composite ceramics
CN106363265A (en) * 2016-10-08 2017-02-01 哈尔滨工业大学 Method for brazing SiC and Zr-4 alloy with Ti-Zr-Ni-Cu brazing filler metal
CN107160059A (en) * 2017-05-17 2017-09-15 北京科技大学 A kind of preparation of Ni base solders for soldering Nb Ti high temperature alloys and method for welding
CN108381057A (en) * 2018-01-22 2018-08-10 北京科技大学 A kind of preparation and method for welding for being brazed the CoTiNb solders of Nb-Ti high temperature alloys
CN108453332A (en) * 2018-02-08 2018-08-28 中国科学院金属研究所 The soldering processes of amorphous state Ti-Zr-Cu-Ni solder vacuum brazing TiAl-base alloys
CN108637197A (en) * 2018-05-24 2018-10-12 钢铁研究总院 A kind of big heat size, high-efficiency and continuous prepare the vacuum quick quenching device and method of amorphous band
CN108941306A (en) * 2018-06-13 2018-12-07 华中科技大学 A kind of amorphous alloy steam explosion impact thermo shaping method
CN110153591A (en) * 2019-05-29 2019-08-23 安徽工程大学 A kind of amorphous composite soldering for ceramic soldering and alloy
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CN112658528A (en) * 2020-12-04 2021-04-16 四川大学 Brazing filler metal for SiC ceramic brazing and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0350735A1 (en) * 1988-07-11 1990-01-17 Lonza Ag Cu-Zr brazing foil
CN1146391A (en) * 1996-06-25 1997-04-02 吉林工业大学 Solder for ceramic soldering
CN101157567A (en) * 2007-09-11 2008-04-09 江苏科技大学 Boron-containing titanium-based amorphous solder for braze welding Si3N4 ceramic and preparation method thereof
CN101172880A (en) * 2007-09-21 2008-05-07 江苏科技大学 Titanium group high temperature amorphous solder of hard solder Si*N* ceramic and method for producing the same
CN102633518A (en) * 2012-04-20 2012-08-15 江苏科技大学 Connection method of Si3N4 ceramics and titanium alloy

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0350735A1 (en) * 1988-07-11 1990-01-17 Lonza Ag Cu-Zr brazing foil
CN1146391A (en) * 1996-06-25 1997-04-02 吉林工业大学 Solder for ceramic soldering
CN101157567A (en) * 2007-09-11 2008-04-09 江苏科技大学 Boron-containing titanium-based amorphous solder for braze welding Si3N4 ceramic and preparation method thereof
CN101172880A (en) * 2007-09-21 2008-05-07 江苏科技大学 Titanium group high temperature amorphous solder of hard solder Si*N* ceramic and method for producing the same
CN102633518A (en) * 2012-04-20 2012-08-15 江苏科技大学 Connection method of Si3N4 ceramics and titanium alloy

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
李卓然 等: "ZrB2-SiC钎焊接头界面产物及反应层生长规律", 《材料工程》 *
李培友: "Ti-Cu-Ni-Zr 非晶合金的热力学特征及力学", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (21)

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CN106041238A (en) * 2016-06-13 2016-10-26 西安理工大学 Probe shell structure for measuring specific retention of petroleum well and seal welding material of probe shell structure
CN106242606B (en) * 2016-07-20 2019-09-13 哈尔滨工业大学 A method of utilizing Zr-Ni base solder brazing ZrB2-SiC composite ceramics
CN106242606A (en) * 2016-07-20 2016-12-21 哈尔滨工业大学 One utilizes Zr Ni base solder brazing ZrB2the method of SiC composite ceramics
CN106112310A (en) * 2016-07-27 2016-11-16 江苏科技大学 A kind of solder for ZrB2 SiC superhigh temperature ceramics soldering and the technique using this solder to carry out soldering
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CN108637197A (en) * 2018-05-24 2018-10-12 钢铁研究总院 A kind of big heat size, high-efficiency and continuous prepare the vacuum quick quenching device and method of amorphous band
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