CN105479030A - Active anti-corrosion SnZn base brazing filler metal, manufacturing method thereof and low-temperature ultrasonic brazing method of ceramic and/or composite material and aluminum and magnesium alloy - Google Patents

Active anti-corrosion SnZn base brazing filler metal, manufacturing method thereof and low-temperature ultrasonic brazing method of ceramic and/or composite material and aluminum and magnesium alloy Download PDF

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CN105479030A
CN105479030A CN201610008561.5A CN201610008561A CN105479030A CN 105479030 A CN105479030 A CN 105479030A CN 201610008561 A CN201610008561 A CN 201610008561A CN 105479030 A CN105479030 A CN 105479030A
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corrosion
solder
resistant
snzn
ceramic
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陈晓光
徐
郭卫兵
闫久春
于汉臣
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Harbin Institute of Technology
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Harbin Institute of Technology
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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
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/06—Soldering, e.g. brazing, or unsoldering making use of vibrations, e.g. supersonic vibrations
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
    • 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
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/026—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used 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

Abstract

The invention provides active anti-corrosion SnZn base brazing filler metal and an active anti-corrosion SnZn base brazing filler metal low-temperature ultrasonic brazing method of ceramic and/or a composite material and aluminum and magnesium alloy and belongs to the technical field of brazing of ceramics and ceramic base composite materials. The active anti-corrosion SnZn base brazing filler metal and the method aim at solving the problem that brazing can be conducted only under the high temperature and weld cracks are generated due to residual heat stress formed in the cooling process by means of the existing ceramic and/or ceramic-based composite material connection technology. The active anti-corrosion SnZn base brazing filler metal is composed of Sn, Zn, Al, Ag and misch metal (RE). The manufacturing method includes the steps that a muffle furnace is heated, Ar gas is injected into the muffle furnace, Ag in a crucible is heated to be molten, Zn, Al, Sn and the misch metal are added in sequence, and the temperature is kept for 30 minutes. The brazing method includes the steps that pressure is applied, an ultrasonic tool head is directly pressed to a workpiece to be welded in a clamping tool to be heated to 270 DEG C to 300 DEG C under the atmosphere environment, and ultrasonic brazing is conducted. The active anti-corrosion SnZn base brazing filler metal and the method are used for connection of ceramic, sapphires, silicon wafers, glass, aluminum alloy, magnesium alloy, composite materials containing ceramic particles and the like through ultrasonic brazing, wherein the composite materials comprises aluminum alloy containing the ceramic particles, magnesium alloy containing the ceramic particles, titanium alloy containing the ceramic particles and the like.

Description

Active corrosion-resistant SnZn base solder and preparation method thereof and low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method
Technical field
The invention belongs to the soldering tech field of pottery and ceramic matric composite, be specifically related to a kind of active corrosion-resistant SnZn base solder and preparation method thereof, and low temperature ultrasonic ceramic soldering and/or composite and aluminium alloy, magnesium alloy method.
Background technology
Along with RoHS instruction is forbidden using environmentally harmful lead element in electronic product, SnZn base solder, due to its lower fusing point, as a kind of lead-free brazing, receives publicity in electronic industry, has potential application prospect.
The eutectic temperature of SnZn is 198.5 DEG C, lower than the eutectic temperature 217 DEG C of SnAgCu nearly 20 DEG C.Therefore, SnZn base leadless solder should as the first-selection of lead-free brazing in electronic industry.But have stronger activity due to Zn and be a kind of loose structure at the ZnO of solder Surface Creation, therefore, SnZn base solder very easily corrodes and the ZnO of porous can not protect solder matrix well.So the corrosion resistance of SnZn base solder and antioxygenic property need further to be improved.
Pottery has the advantages such as high-melting-point, high rigidity, high-wearing feature, oxidative resistance.Structural material, cutter material can be used as.Meanwhile, pottery is also because its special character is used as functional material.Sapphire is one the most frequently used in pottery.
Sapphire has good mechanical property and optical property.Be applied in the middle of a lot of civilian high-tech field, such as, in medicine equipment, laser equipment and high-vacuum apparatus.Sapphire welding derives from two demands: be tightly connected reliably between sapphire and metal on the one hand; That undersized sapphire is welded into large scale window on the other hand.Now widely used sapphire welding method has bonded process, reaction sintering and active reaction method for brazing.Connect sapphire by bonded process, the macromolecule ageing resistace in joint is poor.There is a large amount of porosity defects in the weld seam that reaction sintering obtains, become the source, crack in welding seam breaking process.Soldering realizes ceramic material to connect the most frequently used method, the sapphire active solder of the soldering mainly Ag-Cu-Ti solder of current extensive use.Form interface by active element Ti with sapphire interface place priming reaction to be connected.Whole welding process needs 850 DEG C of high temperature and vacuum environment could realize connecting.Because in weld seam, the thermal coefficient of expansion of solder is far longer than sapphire thermal coefficient of expansion, from the process of high temperature (850 DEG C) cool to room temperature, welding point leaves very large residual stress, becomes the main cause of joint cracking.
This patent adopts active corrosion-resistant SnZn base solder low temperature ultrasonic soldering sapphire, by adding active element Al in SnZn base solder, to improve the activity of solder, and applying ultrasonic further activation, successfully achieving low temperature ultrasonic soldering sapphire.Meanwhile, in SnZn base solder, add the Ag element of corrosion resistance, the corrosion resistance of solder is improved greatly.
Summary of the invention
The present invention solves the existing active solder soldering sapphire of application can only soldering under high temperature (850 DEG C), and is difficult to form the problem causing weld cracking in effective connection, cooling procedure due to residual thermal stress; And provide ultrasonic cryogenic SnZn base solder and ultrasonic brazing sapphire method thereof.
For solving the problems of the technologies described above, activity of the present invention corrosion-resistant SnZn base solder chemical composition is by percentage to the quality: 1.0 ~ 10.0%Zn, 0.25 ~ 2.5%Ag, 0.01 ~ 1.0%Al, 0.01 ~ 0.05% mishmetal, and surplus is Sn; Described mishmetal is that Pr forms by 40% ~ 60%Ce, 10% ~ 30%La, 10 ~ 15%Nd and surplus by weight percentage.Its preparation method carries out in the steps below: put into by Ag in crucible, Muffle furnace is heated to 1000 DEG C, and fills Ar gas wherein, crucible is put in Muffle furnace, insulation, until Ag melts completely, in succession adds Al, Zn, Sn and mixed rare earth, is then incubated 20 ~ 60 minutes; Active corrosion-resistant SnZn base solder is obtained after cooling.
Active corrosion-resistant SnZn base solder low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method are carried out in the steps below:
Step one, get two pieces of potteries or one piece of pottery and one block of ceramic matric composite or two blocks of ceramic matric composites or Al alloys andMg alloys as to-be-welded pieces, be placed in acetone ultrasonic cleaning;
Step 2, by corrosion-resistant for activity according to claim 1 SnZn base solder compressing tablet, the thickness of sheet is 0.3 ~ 0.5mm, is cut into the size corresponding with to-be-welded pieces, obtains solder sheet;
Step 3, solder sheet in step 2 is clipped between surface to be welded that step one processes rear to-be-welded pieces and obtains treating weldment, then will treat that weldment is put into jig and clamped;
Step 4, apply the pressure of 0.2 ~ 1Mpa, be directly pressed in by Ultrasonic probe and treat on weldment in step 3 jig, under atmospheric environment, be heated to 270 ~ 300 DEG C, applying amplitude is that the ultrasonic wave of 5 μm carries out ultrasonic wave added soldering 50 ~ 1000s.
The SnZn base solder that the present invention adopts using Al element as active element, Ag is corrosion resistance element, achieve (270 ~ 300 DEG C) ultrasonic brazing at a lower temperature connect pottery, sapphire and contain ceramic matric composite as the aluminium alloy containing ceramic particle, magnesium alloy, titanium alloy etc., and glass, silicon chip, aluminium alloy, magnesium alloy etc.Present invention, avoiding the cracking of joint, achieve effective connection of pottery and/or ceramic matric composite, particularly sapphire welding.
The invention has the advantages that compared to existing technology:
1, SnZn base solder is not only in the middle of the tradition application of the Cu interconnected in electronic industry, and is developed, in the middle of the ultrasonic brazing being applied to pottery and/or ceramic matric composite as low temperature ultrasonic solder.
2, the activity of Zn element is comparatively strong, and have good affinity with pottery, adding of Zn element makes weld strength be greatly improved.
3, the present invention take Al as the active element of ceramic soldering and/or ceramic matric composite, generates Al by Al to solder and pottery and/or ceramic matric composite interface diffusion and reaction 2o 3nano particle transition zone, and this Al 2o 3nano particle transition zone achieves solder and is connected with pottery and/or the effective of ceramic matric composite substrate.
4, element al has higher activity, and adding of Al can at the Surface Segregation of melt in the process of solder melting, the Al of formation 2o 3oxide-film has very high compactness, prevents the further oxidation of alloy substrate.Meanwhile, in solder, the content of Al is only trace, with the Al preventing the more generation of Al content thicker 2o 3oxide-film, reduces the wetability of solder and ceramic matrix.
5, Ag element add improve brazing filler metal alloy plasticity, add corrosion resistance.When the content of Ag reaches 1.5%, the percentage elongation of solder rises to 60% from 30%.The resistance to corrosion of solder under comparatively wet and corrosive environment is made the adding of Ag element to increase.
6, the size due to solder sheet is thinner, and ultrasonication is when narrow gap, and ultrasonic losses is less, and ultrasonication is enhanced.At the Al of Interface debond of SnZn base solder and pottery or ceramic matric composite 2o 3the thickness of nano-particle layer is enhanced, thus the intensity of weld seam is significantly improved.
7, in the present invention, by SnZn base solder sheet and ultrasonic wave added soldering, (270 DEG C) sapphire connection under achieving low temperature.And existing active solder pricker (Ag-Cu-Ti solder) welds sapphire temperature (850 DEG C), because the thermal coefficient of expansion of sapphire and solder does not mate, cause under larger cooling range, residual stress accumulation in weld seam, thus make weld cracking.
8, existing active solder (Ag-Cu-Ti solder) soldering sapphire needs to carry out in a vacuum furnace, harsher to the requirement of welding surroundings.And activity of the present invention corrosion-resistant SnZn base solder just can at soldering sapphire under ultrasonic wave added, and realize effectively connecting in atmospheric environment.
9, Ti's is expensive, and the less expensive of Al, production cost can be made to decrease using Al as the solder of active element.
10, active element Al ceramic surface wetting in pottery and ceramic matric composite can be significantly improved adding of mixed rare earth, promote reaction forming; Simultaneously adding of mixed rare earth can the tissue of refinement SnZn base solder, increases the intensity of weld seam.
11, high strength alumin ium alloy at high temperature welding can have a negative impact to mother metal, reduces strength of parent.And adopt activity of the present invention corrosion-resistant SnZn base solder can welding aluminum alloy at low temperatures, thus avoid the reduction of aluminium alloy strength of parent.
Accompanying drawing explanation
Fig. 1 is ultrasonic wave added soldering sapphire schematic diagram; Fig. 2 is active corrosion-resistant Sn9Zn1Ag0.5Al brazing filler metal alloy DSC curve; Fig. 3 is the SEM image of the corrosion-resistant SnZn base solder alloy of activity of preparation; Fig. 4 is the SEM image of Sn9Zn brazing filler metal alloy prepared by same procedure; Fig. 5 is joints morphology SEM image after ultrasonic brazing; Fig. 6 is the polarization curve of active corrosion-resistant Sn9Zn1Al0.5Ag brazing filler metal alloy; Fig. 7 is the polarization curve of Sn9Zn brazing filler metal alloy; Fig. 8 is the change of welding point shear strength with Zn element; Fig. 9 welding point shear strength is with the change of ultrasonic amplitude; Figure 10 is the change that welding point shear strength adds with rare earth element; Figure 11 is the nanometer Al of sapphire/solder Interface debond 2o 3particle SEM image; Figure 12 is active element Al and Al 2o 3interracial contact atomic arrangement schematic diagram; Figure 13 is active element Al and Al 2o 3reaction epitaxial growth Al 2o 3thin layer schematic diagram; Wherein 1 in Fig. 1-upper sapphire to be welded, 2-lower sapphire to be welded, 3-solder, 4-Ultrasonic probe, 5-heater coil, 6-fixed mould, 7-variable-sized fixture.
Detailed description of the invention
Detailed description of the invention one: the chemical group prejudice table 1 of active corrosion-resistant SnZn base solder in present embodiment:
Table 1 is the chemical composition (by weight percentage) of low temperature ultrasonic SnBi base solder
Wherein, the chemical group prejudice table 2 of minipool rare earth (RE):
Table 2 is the chemical composition (by weight percentage) of mishmetal (RE)
In present embodiment, the preparation method of active corrosion-resistant SnZn base solder is as follows:
Put into by Ag in crucible, Muffle furnace is heated to 1000 DEG C, and fill Ar gas wherein, put into by crucible in Muffle furnace, insulation, until Ag melts completely, adds Al, Sn, Bi and the mixed rare earth of certain ingredients in succession, is then incubated 30 minutes; Active corrosion-resistant SnZn base solder is obtained after cooling.
In present embodiment, active corrosion-resistant SnZn base solder ultrasonic brazing sapphire method carries out in the steps below:
Step one, sapphire to be welded is placed in acetone ultrasonic cleaning 10min;
Step 2, active corrosion-resistant SnZn base solder by mill milling, or rotate to get rid of in band carry out compressing tablet by getting rid of band machine, measure pricker material thickness, until pricker material thickness is 0.5mm, and be cut into the size of 10cm × 10cm with spiral micrometer;
Step 3, solder sheet folder and step one in step 2 are processed after two pieces of sapphire surfaces to be welded between form and treat weldment, then will treat that weldment is put into jig and clamped;
Step 4, applying 0.2Mpa pressure, be directly pressed on the sapphire weldment in step 3 jig, under atmospheric environment by Ultrasonic probe, be heated to 270 DEG C, setting ultrasonic amplitude is 5 μm, and ultrasonic wave application time is 50s, carry out ultrasonic wave added soldering, as shown in Figure 1.
Carry out Measurement accuracy to the ultrasonic cryogenic SnZn base solder liquidus temperature of present embodiment, carry out heating differential analysis, result as shown in Figure 2.Learnt by DSC curve, liquidus curve initial temperature 218.6 DEG C, end temp is 245.3 DEG C.Usually, brazing temperature is more than liquidus temperature tens degree.So design temperature is 270 ~ 300 DEG C, realize soldering sapphire under low temperature.
The SEM figure of the microstructure of active corrosion-resistant Sn9Zn1Ag0.5Al brazing filler metal alloy as shown in Figure 3.In SEM figure, circular black particle is γ-AgZn (Ag5Zn8) intermetallic compound (IMC phase), and bar-shaped black is rich Zn phase, and matrix is β-Sn+ ε-AgZn binary eutectic tissue.
The microstructure SEM figure of Sn9Zn solder as shown in Figure 4.In SEM figure, black is bar-shaped is rich Zn phase, and matrix is β-Sn and SnZn eutectic structure.
Adopt the tissue topography of joint after active corrosion-resistant Sn9Zn1Ag0.5Al solder ultrasonic brazing as shown in Figure 5.Can see from SEM picture, solder is combined closely with sapphire substrates, does not have obvious weld defect.Visible, adopting with Al is the SnZn base solder of active element, and under ultrasonic wave added, lower temperature just effectively can realize the connection between sapphire.
What the electrochemical corrosion test corrosive liquid of solder was chosen is mass fraction be 3.5% the NaCl aqueous solution, test temperature 20 DEG C, initial voltage-2V, final voltage 1V, quiescent time 10s.Respectively electrochemical corrosion test is carried out to Sn9Zn1Ag0.5Al solder and Sn9Zn solder.Obtain the polarization curve of two kinds of solders as shown in Figure 6 and Figure 7.
For Sn9Zn1Ag0.5Al solder, its electrochemical corrosion can be divided into 4 stages by polarization curve analysis:
(1) oxygen course of dissolution, its reaction equation is:
O 2+2H 2O+4e -＝4OH -
(2) corrosion of AgZn, reaction equation is:
2OH -+AgZn＝ZnO+Ag+H 2O+2e -
(3) Sn oxidizing process, its reaction equation is:
Sn+2OH -＝Sn(OH) 2+2e -
Sn(OH) 2＝SnO+H 2O
(4) when the voltage section of being increased to, surface oxidation film rupture, makes corrosion current sharply rise, and the reaction of this section is:
3Sn+4OH -+2Cl --6e -＝Sn 3O(OH) 2Cl 2+H 2O
For Sn-4Zn solder, corrosion can be divided into 3 stages:
(1) the O course of dissolution of generation similar to Sn9Zn1Ag0.5Al;
(2) corrosion reaction of the Zn in Sn9Zn solder, reaction equation is:
Zn+2OH -＝ZnO+H 2O+2e -
Zn in corrosion process because the generation of ZnO should have a passivating process.But because ZnO is a kind of loose structure, along with the rising of voltage, ZnO ratio is easier to break, electric current just raises along with voltage and constantly rises, and polarization curve does not appear as obvious passivation platform.
(3) oxidation of Sn and the oxide-film fragmentation of Sn are until corrosion test terminates.The passivation platform occurred due to Sn oxidation in Sn9Zn1Ag0.5Al solder is there is not in this stage.
For the polarization curve of Sn9Zn1Ag0.5Al solder, its corrosion potential is-1.295V, rises to some extent, show that corrosion resistance increases relative to the corrosion potential-1.358V of Sn-9Zn.In addition, there is the passivation of two places in the polarization curve of Sn9Zn1Ag0.5Al solder, and in Sn9Zn solder, do not find the obvious passivation stage, illustrate that the passivation effect of Sn9Zn1Ag0.5Al solder is better than Sn9Zn.On the whole, the corrosion resistance of Sn9Zn1Ag0.5Al solder is better than Sn9Zn solder.
For the reason of two kinds of solder Sn9Zn1Ag0.5Al and Sn9Zn polarization curve notable difference, we can find reason by the difference of two kinds of solder tissues.Form primarily of rich Zn phase, γ-AgZn and β-Sn+ ε-AgZn eutectic phase in Sn9Zn1Ag0.5Al solder microstructure.And Sn9Zn solder microstructure is primarily of rich Zn phase, ZnSn eutectic phase and β-Sn phase composition.In Sn9Zn1Ag0.5Al solder, due to the existence of γ-AgZn intermetallic compound, in corrosion process, the simple substance Ag separated out is wrapped in the outside of ZnO, prevent the ZnO of porous in the rising along with voltage, and break instantaneously, on polarization curve, therefore occur a passivation platform.In addition, the corrosion of Sn9Zn1Ag0.5Al solder about-1V is the β-Sn+ ε-AgZn eutectic structure in solder matrix, and Sn9Zn solder corrodes about-1V is ZnSn eutectic phase in solder matrix and β-Sn phase.From SEM image, in Sn9Zn1Ag0.5Al matrix, crystal grain is comparatively coarse, and therefore crystal boundary is less, and resistance to corrosion is stronger.And crystal grain is comparatively tiny in Sn9Zn matrix, the crystal grain of refinement has more crystal boundary, and because crystal boundary energy is higher, resistance to corrosion is poor, and polarization curve has shown as a platform, but the comparatively not obvious passivation stage.
In SnZn base solder, there are two effects adding of element Zn.First, the solid solubility of Al element in Sn element is less, and solid solubility in Zn element is larger.Therefore, adding of Zn element active element Al can be added in the middle of solder.Secondly, the activity of Zn element is comparatively strong, the Al generated with sapphire surface 2o 3the adhesion of nano particle is stronger.Thus the intensity of weld seam is significantly improved.Welding point shear strength with Zn content change as shown in Figure 8, along with increasing of Zn constituent content, the shear strength of weld seam becomes large gradually.
Mechanics Performance Testing is carried out to the joint obtained with Sn4.0Zn1.0Ag0.5Al solder ultrasonic brazing sapphire.Fig. 9 is for when pricker material thickness is 150 μm, and under different ultrasonic amplitude, ultrasonic brazing sapphire obtains the compression shear strength value of joint.As can be seen from the figure, along with the raising of ultrasonic amplitude, shear strength improves thereupon.When ultrasonic power is 3 μm, the average shear strength obtained is 44MPa; When ultrasonic power is 5 μm, the average shear strength obtained is 58MPa; When ultrasonic power is 9 μm, the average shear strength obtained is 41MPa.
Wetting on surface of active element Al in solder can be improved the adding of mixed rare earth, thus promote that Al is better combined with sapphire.Meanwhile, mixed rare earth can the tissue of refinement Sn base solder, improve solder corrosion resistance.Employing does not add mishmetal and carries out ultrasonic brazing with the solder adding mishmetal, obtains the shear strength of weld seam as shown in Figure 10.Add the weld seam shear strength after mishmetal and can bring up to 68MPa.
In solder, there are two main effects adding of Al.First, the Zn element in solder easily generates the ZnO of porous in atmosphere, in the air of humidity and containing in halide environments, easily generates the corrosion product being easy to dissolve further.The free energy of formation of ZnO is lower, is easy to be formed and stablizes, but ZnO is different and other dense oxide (Al 2o 3), comparatively loose, well can not protect matrix below, therefore one of Sn-Zn base solder large drawback is exactly corrosion resistance difference.For this reason, in SnZn base solder, add Al element can utilize Al element to molten solder surface segregation in solder fusion process, and generate fine and close Al 2o 3film, prevents inner solder oxidized.Secondly, Al element, as active element, generates Al in sapphire surface reaction extension 2o 3nano particle transition zone.And this layer of Al just 2o 3nano-particle layer achieves the interconnection between sapphire and solder.By fracture volume fraction be 20% nitric acid alcohol corrode, after solder is corroded, spill sapphire and solder interface.Observe interface by SEM to find to generate fine and close nano-particle layer, and nano particle is evenly distributed in the middle of interface, as shown in figure 11.Carry out energy spectrum analysis to it, result shows, only containing Al, O two kinds of elements in surface resultant, for the particle generated at sapphire surface after ultrasonic is the Al that epitaxial growth goes out 2o 3.The nano particle generated is combined well with sapphire substrates and solder.This layer of Al 2o 3nano particle plays function served as bridge, is connected to sapphire substrates and solder.
In solder brazing, major issue is that the oxidation film layer on solder surface is difficult to be removed.The existence of this layer of oxide-film hinders the contact, wetting of liquid solder and sapphire substrates, thus is difficult to form effective connection.Ultrasonic have cavitation effect, and more easily occur in interface, the instantaneous pressure produced during cavitation bubble collapse, makes the oxide-film on solder surface broken, facilitate the contact of fresh liquid solder and sapphire substrates, soak.After the oxide-film fragmentation of solder, active element Al and sapphire contact also start reaction.When just having started to contact, Al/ sapphire interface atomic arrangement schematic diagram as shown in figure 12.Subsequently, active element Al and O reacts at sapphire substrates Epitaxial growth Al 2o 3the process schematic of thin layer as shown in figure 13.

Claims (8)

1. active corrosion-resistant SnZn base solder, it is characterized in that the chemical composition of active corrosion-resistant SnZn base solder is by weight percentage: 1.0 ~ 10.0%Zn, 0.25 ~ 2.5%Ag, 0.01 ~ 1.0%Al, 0.01 ~ 0.05% mishmetal, surplus is Sn; Described mishmetal is that Pr forms by 40% ~ 60%Ce, 10% ~ 30%La, 10 ~ 15%Nd and surplus by weight percentage.
2. activity according to claim 1 corrosion-resistant SnZn base solder, is characterized in that the chemical composition of active corrosion-resistant SnZn base solder is by weight percentage: 9.0%Zn, 1.0%Ag, 0.5%Al, 0.05%RE, surplus is Sn.
3. activity according to claim 1 corrosion-resistant SnZn base solder, it is characterized in that described mishmetal by weight percentage by 55%Ce, 20%La, 11%Nd and surplus be Pr form.
4. the preparation method of active corrosion-resistant SnZn base solder as claimed in claim 1, it is characterized in that the preparation method of active corrosion-resistant SnZn base solder carries out in the steps below: put into by Ag in crucible, Muffle furnace is heated to 1000 DEG C, and fill Ar gas wherein, crucible is put in Muffle furnace, insulation, until Ag melts completely, in succession adds Al, Zn, Sn and mishmetal, is then incubated 20 ~ 60 minutes; Active corrosion-resistant SnZn base solder is obtained after cooling.
5. active corrosion-resistant SnZn base solder low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method as claimed in claim 1, is characterized in that active corrosion-resistant SnZn base solder low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method carry out in the steps below:
Step one, get two pieces of potteries or one piece of pottery and one block of ceramic matric composite or two blocks of ceramic matric composites or Al alloys andMg alloys as to-be-welded pieces, be placed in acetone ultrasonic cleaning;
Step 2, by corrosion-resistant for activity according to claim 1 SnZn base solder compressing tablet, the thickness of sheet is 0.3 ~ 0.5mm, is cut into the size corresponding with to-be-welded pieces, obtains solder sheet;
Step 3, solder sheet folder and step one in step 2 are processed rear to-be-welded pieces surface to be welded between obtain treating weldment, then will treat that weldment is put into jig and clamped;
Step 4, apply the pressure of 0.2 ~ 1Mpa, be directly pressed in by Ultrasonic probe and treat on weldment in step 3 jig, under atmospheric environment, be heated to 270 ~ 300 DEG C, applying amplitude is that the ultrasonic wave of 5 μm carries out ultrasonic wave added soldering 50 ~ 1000s.
6. active corrosion-resistant SnZn base solder low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method according to claim 5, to is characterized in that in step 2 by mill milling or gets rid of band machine and rotate and get rid of band compressing tablet.
7. active corrosion-resistant SnZn base solder low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method according to claim 5, is characterized in that the step one ultrasonic cleaning time is 10min.
8. active corrosion-resistant SnZn base solder low temperature ultrasonic ceramic soldering and/or composite and Al alloys andMg alloys method according to claim 5, is characterized in that the thickness of sheet in step 2 is 0.5mm.
CN201610008561.5A 2016-01-07 2016-01-07 Active anti-corrosion SnZn base brazing filler metal, manufacturing method thereof and low-temperature ultrasonic brazing method of ceramic and/or composite material and aluminum and magnesium alloy Pending CN105479030A (en)

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CN106944698A (en) * 2017-05-12 2017-07-14 哈尔滨工业大学 The SiC ceramic and the direct method for welding of SiC ceramic reinforced aluminum matrix composites ultrasonic cryogenic being modified based on thermal oxide surface
CN107030412A (en) * 2017-05-17 2017-08-11 常州鑫力航金属新材料有限公司 A kind of aluminium alloy brazing it is environmentally friendly corrosion-free from braze-welding rings and preparation method thereof
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