CN102581507B - Tin, zinc and bismuth multi-element eutectic lead-free solder and preparation method - Google Patents
Tin, zinc and bismuth multi-element eutectic lead-free solder and preparation method Download PDFInfo
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- CN102581507B CN102581507B CN201210018765.9A CN201210018765A CN102581507B CN 102581507 B CN102581507 B CN 102581507B CN 201210018765 A CN201210018765 A CN 201210018765A CN 102581507 B CN102581507 B CN 102581507B
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 80
- 230000005496 eutectics Effects 0.000 title claims abstract description 37
- 229910052718 tin Inorganic materials 0.000 title claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000011701 zinc Substances 0.000 title claims description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title 1
- JVCDUTIVKYCTFB-UHFFFAOYSA-N [Bi].[Zn].[Sn] Chemical compound [Bi].[Zn].[Sn] JVCDUTIVKYCTFB-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000008018 melting Effects 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 30
- 229910020785 La—Ce Inorganic materials 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000010935 stainless steel Substances 0.000 claims abstract description 19
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 5
- 238000005219 brazing Methods 0.000 claims description 49
- 239000011833 salt mixture Substances 0.000 claims description 20
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- 230000000630 rising effect Effects 0.000 claims description 9
- 238000003723 Smelting Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000002910 rare earth metals Chemical class 0.000 abstract 3
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910020994 Sn-Zn Inorganic materials 0.000 description 10
- 229910009069 Sn—Zn Inorganic materials 0.000 description 10
- 239000010949 copper Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000003026 anti-oxygenic effect Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910020836 Sn-Ag Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 229910009071 Sn—Zn—Bi Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- -1 rare earth modified tin zinc bismuth Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 238000005275 alloying Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Abstract
本发明涉及一种锡锌铋多元共晶无铅钎料及制备方法，其特征在于它由4.0～6.0%Zn、1.0～5.0%Bi、0.1～0.5%Sb、0.01～0.5%Te、0.01～0.5%La-Ce混合稀土和余量Sn组成；将KCl和LiCl的混合盐加热熔化后覆盖在熔炼炉内熔融的90.2～93.78％Sn液面上，保温，将熔炼的Sn温度升高到500～600℃，加入Zn、Bi、Sb、Te，搅拌，保温再继续升高炉温到600～650℃，将0.01～0.5%La-Ce混合稀土用壁上带孔的不锈钢钟罩压入到熔融的锡液中，转动钟罩，待La-Ce混合稀土完全熔融后，均匀搅拌，保温，最后将炉温降到500～600℃，待合金混合后，静置出炉，浇注，凝固后去除混合盐，即制得多元共晶无铅钎料，该产品具有熔点低、润湿性好，抗氧化性能好，力学性能高，耐腐蚀性也得到进一步提高的优点及效果。The invention relates to a tin-zinc-bismuth multi-component eutectic lead-free solder and its preparation method, which is characterized in that it consists of 4.0-6.0% Zn, 1.0-5.0% Bi, 0.1-0.5% Sb, 0.01-0.5% Te, 0.01-0.5 It is composed of %La-Ce mixed rare earth and the balance of Sn; the mixed salt of KCl and LiCl is heated and melted, and then it is covered on the molten 90.2-93.78% Sn liquid surface in the melting furnace, and the temperature of the smelted Sn is raised to 500-500 600°C, add Zn, Bi, Sb, Te, stir, keep warm and then continue to raise the furnace temperature to 600-650°C, press 0.01-0.5% La-Ce mixed rare earth into the molten stainless steel bell jar with holes on the wall In the tin liquid, turn the bell jar. After the La-Ce mixed rare earth is completely melted, stir evenly and keep it warm. Finally, lower the furnace temperature to 500-600°C. , that is, the multi-component eutectic lead-free solder is obtained. This product has the advantages and effects of low melting point, good wettability, good oxidation resistance, high mechanical properties, and further improved corrosion resistance.
Description
Technical field
The present invention relates to the polynary eutectic lead-free brazing of a kind of tin zinc bismuth, the polynary eutectic lead-free brazing of a kind of rare earth modified tin zinc bismuth particularly, belongs to the solder technical field of electronic and electrical equipment.
The present invention relates to the preparation method of the polynary eutectic lead-free brazing of this tin zinc bismuth.
Technical background
In recent years, the enhancing day by day of and common people environmental consciousness day by day serious due to plumbous problem of environmental pollution, countries in the world are promulgated the plumbous decree of various taboos in succession, wherein European Union takes the lead in having implemented in July, 2006 WEEE/RoHs instruction, the electronic product of forbidding the harmful substance such as leaded enters EU market, and China also starts to limit the use of solder containing lead in March, 2007 and Korea S in July, 2008.At present, Electronic Packaging solder is unleaded to launch in the whole world, all the time, development substitute traditional Sn-Pb solder high-performance, lead-free brazing is extensively subject to the attention of researcher and manufacturer cheaply.
At present, the scientific research institutions of countries in the world, electronics manufacturing enterprise and material manufacturing company are devoted to the research of lead-free brazing one after another, and accomplished tangible results, developed multiple lead-free alloy system, wherein Sn-Ag, Sn-Cu and Sn-Ag-Cu brazing filler metal are that industry is known as good lead-free brazing, be accepted and be applied to the production of electronic product, but their fusing points are than 183 ℃ of traditional Sn-Pb eutectic solder high nearly 40 ℃, still undesirable with existing equipment and processing compatibility, exist many shortcomings that self are difficult to overcome; In addition, Sn-Ag and Sn-Ag-Cu lead-free brazing are expensive, and this has also limited their practical applications in electronic enterprise.In contrast to this, Sn-Zn series leadless solder rely on suitable fusing point, cheap cost, rich in natural resources, good mechanical property and with the advantage such as existing equipment processing compatibility is good, more and more receive the concern of industry.Yet also there are three technical problems in Sn-Zn series leadless solder at present:
(1) in this brazing filler metal, Zn is a kind of very active element, very easily at the oxide of the oxidized formation short texture in solder surface, makes Sn-Zn brazing filler metal non-oxidizability variation;
(2) in this brazing filler metal, Zn is that a kind of to increase capillary element and its oxidizable Sn-Zn of making brazing filler metal sprawling with wettability on Cu substrate poor;
(3) this brazing filler metal Zn element current potential is very low, easily with printed circuit board (PCB) in the element formation galvanic cell such as pad metal Cu, Ni, corrosion rate is very fast, makes Sn-Zn brazing filler metal corrosion resistance poor.
Existing a large amount of about improving the research of Sn-Zn brazing filler metal non-oxidizability and corrosion resistance at present, but find after the patent of multianalysis and the outer Sn-Zn brazing filler metal occurring of research Now Domestic, can improve the solder patent of Sn-Zn brazing filler metal combination property still seldom, in disclosed solder patent, the capable energy of mechanics, physical property and processing performance are often attended to one thing and lose sight of another.For example, US Patent No. 6241942, applying date 1998-03-30, (76～78) Sn-(7～10) Zn-(0.2～6) Bi-(0.1～3.5) Ag-(0.1～3) Cu-(0.5～3) In-(0.001～1) P or (0.01～1) Ni solder that open day 2001-06-05 proposes, by adding In in the Sn-Zn alloy traditional, P and Ag, the oxidation of Zn and the problem that corrosion forms have been solved, but In has formed irregular acicular crystal in microstructure, thereby reduced mechanical property, In content in the earth's crust is few simultaneously, price is high, it adds the significantly rising that must bring solder cost, US Patent No. 4248905, applying date 1980-01-21, Sn-(3～5) Zn-(10～23) that open day 1981-02-03 provides is although Bi solder has solved the poor problem of wetability, but when Bi content is higher than 5% time, the mechanical property of solder obviously reduces, solder becomes fragile, and is difficult to be drawn into solder stick, Chinese patent literature CN1337293A, applying date 2001-09-05, Sn-(4～10) Zn-(0.05～1) the RE solder that open day 2002-02-27 provides, by add RE in Sn-Zn, solder is organized finer and close, the stretch-resistance of solder, shear resistant and croop property are improved, but too high RE can be oxidized and wetability is declined at solder surface enrichment, Chinese patent literature CN101439444A applying date 2008-12-24, Sn-(82～98) Zn-(0.08～1.2) Sb-(0.1～4) Al-(0.01～0.5) Si-(0.1～1) Cu-(0.08～1.2) Sb-(0.01～0.5) Pd-(0.001～0.01) the Nd solder that open day 2009-05-27 provides, although the Zn content adding is 82～98%, the cost of solder is obviously reduced, but too high Zn will cause the non-oxidizability of solder and wetability obviously to reduce, when the Al simultaneously adding surpasses 1%, Al can form excess oxide on solder surface, increase solder surface tension and wetability is declined, in addition, it is too much that this patent is added alloying element, cause complex proceduresization and cost to increase, also likely bring too much impurity element into.
Summary of the invention
Object of the present invention provides a kind of polynary eutectic lead-free brazing of tin zinc bismuth with the mechanical property that fusing point is low, good in order to overcome the shortcoming of prior art existence just with deficiency, thereby also improved wetability, non-oxidizability and ductility, corrosion resistance is also further enhanced.
Object of the present invention is by realizing with following technical proposal:
The polynary eutectic lead-free brazing of tin zinc bismuth, it is comprised of the raw material of following weight percentage:
Described La-Ce mishmetal, its percentage by weight of La, Ce is that La:Ce is 1:1～1:3.
The preparation method of the polynary eutectic lead-free brazing of described tin zinc bismuth, it carries out in the steps below:
(a) salt-mixture that is 1.3:1 by KCl:LiCl by weight covers on 90.2～93.78%Sn liquid level of melting in smelting furnace after 400～450 ℃ of heat fused, is incubated 15～20 minutes;
(b) the Sn temperature of (a) melting is elevated to 500～600 ℃, adds 4.0～6.0%Zn, 1.0～5.0%Bi, 0.1～0.5%Sb, 0.01～0.5%Te, and uniform stirring, be incubated 20～30 minutes;
(c) continue again rising furnace temperature to 600～650 ℃, 0.01～0.5%La-Ce the mishmetal that is 1:1～1:3 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, is incubated 20～30 minutes;
(d) finally furnace temperature is dropped to 500～600 ℃ of insulations 60～120 minutes, after alloy mixes, standing coming out of the stove, is cast in stainless steel mould, solidifies the surperficial salt-mixture of rear removal, makes the polynary eutectic lead-free brazing of tin zinc bismuth.
Described solder also can be processed into solder post or solder bar, and solder wire, solder ball, solder powder.
In the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention, added 4.0～6.0% Zn.Due to the easily oxidizable of Zn, the Zn content in solder can not be too high, and Zn too high levels can cause the non-oxidizability of solder to reduce on the one hand, can cause on the other hand the wetability variation being caused by oxidizable.Experimental result shows, in the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention, when the content of Bi, Sb, Te and La-Ce mishmetal is fixed and is changed Zn content, the wetability of the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention on copper base first rises and declines afterwards, and the wetability of the solder wherein configuring when Zn content is 5% is best.Therefore, the addition of Zn, 4.0～6.0% better, is preferably 4.5%～5.0%.
In the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention, added 1.0～5.0% Bi, according to existing thermodynamic data, calculate rear discovery of DHv value of Sn, Zn, Bi, the DHv of Bi is lower than Sn, Zn, therefore Bi is easily at surface aggregation, surface tension when this can reduce the polynary eutectic lead-free brazing of tin zinc bismuth molten condition, the wetability of the polynary eutectic lead-free brazing of raising tin zinc bismuth.In addition, add Bi element can effectively suppress the formation of acicular constituent, reduce the fusion temperature of solder, under same heating-up temperature, the polynary eutectic lead-free brazing of tin zinc bismuth is in relative superheat state, reduced viscosity, mobility increases, and solder is more easily sprawled on Cu substrate.Yet Bi is a kind of fragility element phase, if addition surpasses 5%, can reduce the mechanical properties such as percentage elongation of solder, solder is become fragile, reliability decrease, is not easy to, in subsequent technique, solder is drawn into silk.
In the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention, added 0.1～0.5% Sb, adding for tensile property and the anti-shear performance of solder joint of Sb is very favourable, but during Sb too high levels, can make brazing filler metal alloy fragility increase and electrical and thermal conductivity performance decline, its optimal addn is 0.1～0.5%.
In the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention, added 0.01～0.5% Te, Te is very favourable to the antioxygenic property of solder and wettability, this is main because micro-Te adds the surface that can be enriched in solder in solder, reduce the surface tension of solder, improve antioxygenic property and the wettability of solder; In addition, the Te of trace also can improve corrosion resistance and the ductility of solder, makes solder be easy to be drawn into solder wire, but can make solder softening during its too high levels, so its optimal addn is 0.01～0.5%.
In the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention, added 0.01～0.5% La-Ce mishmetal, La-Ce mishmetal is the product of market sale, conventionally in alloy, add rare earth element, can improve uniformity, tensile strength and the creep-resistant property of solder tissue.Zn in Sn-Zn-Bi system is very active; and ZnO has lower Gibbs free energy of formation; so the oxide-film on Sn-Zn-Bi brazing filler metal surface mostly is ZnO; its short texture porous; can not play the effect of protection solder joint; along with the growth of fusion temperature, the ZnO that covers molten solder surface is more and more, and the existence of this layer of ZnO film will certainly produce extremely adverse influence to the wettability of solder.In the polynary eutectic lead-free brazing of tin zinc bismuth, add after suitable La-Ce mishmetal, because La-Ce mishmetal has surface-active action, the surface that its surface that is easy to be enriched in liquid solder reduces solder can be improved wetting; In addition, La-Ce mishmetal can also refinement solder inside microscopic structure, improve the compactness of solder oxidation product and improve solder intensity, greatly reducing the oxidation rate of the polynary eutectic lead-free brazing of tin zinc bismuth, and then improve the wettability of the polynary eutectic lead-free brazing of tin zinc bismuth.
Owing to reaching on taking, state technical scheme and make skill wood of the present invention and oneself have technology to compare to have that fusing point is low, wetability good, antioxygenic property is good, and mechanical property is high, the advantage that corrosion resistance is also further enhanced and effect.
The specific embodiment
Below in conjunction with specific embodiment, the present invention will be further described,
Embodiment 1
Raw material components and consumption: Zn4.0g, Bi2.0g, Sb0.2g, Te0.01g, La-Ce mishmetal 0.01g and Sn93.78g.
The salt-mixture of 19.5gKCl and 15gLiCl is covered after 450 ℃ of heat fused on the 93.78g Sn liquid level of melting in smelting furnace, be incubated 15 minutes, Sn temperature is elevated to 600 ℃, add 4.0gZn, 2.0gBi, 0.2gSb and 0.01gTe, and uniform stirring, be incubated 20 minutes, continue again rising furnace temperature to 650 ℃, the 0.01gLa-Ce mishmetal that is 1:1 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, be incubated 20 minutes, finally furnace temperature is dropped to 600 ℃ of insulations 60 minutes, after alloy mixes, standing coming out of the stove, be cast in stainless steel mould, solidify the surperficial salt-mixture of rear removal, make the polynary eutectic lead-free brazing of tin zinc bismuth and be processed into solder post.
Embodiment 2
Raw material components and consumption: Zn5.0g, Bi4.0g, Sb0.4g, Te0.3g, La-Ce mishmetal 0.05g and Sn90.25g.
The salt-mixture of 19.5gKCl and 15gLiCl is covered after 400 ℃ of heat fused on the 90.25g Sn liquid level of melting in smelting furnace, be incubated 20 minutes, Sn temperature is elevated to 550 ℃, add 5.0gZn, 4.0gBi, 0.4gSb and 0.3gTe, and uniform stirring, be incubated 25 minutes, continue again rising furnace temperature to 650 ℃, the 0.05gLa-Ce mishmetal that is 1:3 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, be incubated 20 minutes, finally furnace temperature is dropped to 500 ℃ of insulations 120 minutes, after alloy mixes, standing coming out of the stove, be cast in stainless steel mould, solidify the surperficial salt-mixture of rear removal, make the polynary eutectic lead-free brazing of tin zinc bismuth, be processed into solder bar.
Embodiment 3
Raw material components and consumption: Zn4.5g, Bi5.0g, Sb0.1g, Te0.1g, La-Ce mishmetal 0.05g and Sn90.25g.
The salt-mixture of 19.5gKCl and 15gLiCl is covered after 450 ℃ of heat fused on the 90.25g Sn liquid level of melting in smelting furnace, be incubated 15 minutes, Sn temperature is elevated to 500 ℃, add 4.5gZn, 5.0gBi, 0.1gSb and 0.1gTe, and uniform stirring, be incubated 30 minutes, continue again rising furnace temperature to 600 ℃, the 0.05gLa-Ce mishmetal that is 1:2 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, be incubated 30 minutes, finally furnace temperature is dropped to 530 ℃ of insulations 100 minutes, after alloy mixes, standing coming out of the stove, be cast in stainless steel mould, solidify the surperficial salt-mixture of rear removal, make the polynary eutectic lead-free brazing of tin zinc bismuth, be processed into solder wire.
Embodiment 4
Raw material components and consumption: Zn5.0g, Bi1.0g, Sb0.5g, Te0.02g, La-Ce mishmetal 0.1g and Sn93.38g.
The salt-mixture of 19.5gKCl and 15gLiCl is covered after 430 ℃ of heat fused on the 93.38g Sn liquid level of melting in smelting furnace, be incubated 18 minutes, Sn temperature is elevated to 600 ℃, add 5.0gZn, 1.0gBi, 0.5gSb and 0.02gTe, and uniform stirring, be incubated 20 minutes, continue again rising furnace temperature to 650 ℃, the 0.1gLa-Ce mishmetal that is 1:2.5 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, be incubated 20 minutes, finally furnace temperature is dropped to 550 ℃ of insulations 90 minutes, after alloy mixes, standing coming out of the stove, be cast in stainless steel mould, solidify the surperficial salt-mixture of rear removal, make the polynary eutectic lead-free brazing of tin zinc bismuth and be processed into solder ball.
Embodiment 5
Raw material components and consumption: Zn6.0g, Bi3.0g, Sb0.1g, Te0.5g, La-Ce mishmetal 0.2g and Sn90.2g.
The salt-mixture of 19.5gKCl and 15gLiCl is covered after 450 ℃ of heat fused on the 90.2g Sn liquid level of melting in smelting furnace, be incubated 15 minutes, Sn temperature is elevated to 550 ℃, add 6.0g Zn, 3.0gBi, 0.1gSb and 0.5gTe, and uniform stirring, be incubated 25 minutes, continue again rising furnace temperature to 650 ℃, the 0.2gLa-Ce mishmetal that is 1:1.5 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, be incubated 20 minutes, finally furnace temperature is dropped to 550 ℃ of insulations 90 minutes, after alloy mixes, standing coming out of the stove, be cast in stainless steel mould, solidify the surperficial salt-mixture of rear removal, make the polynary eutectic lead-free brazing of tin zinc bismuth and be processed into solder powder.
Embodiment 6
Raw material components and consumption: Zn5.0g, Bi1.0g, Sb0.3g, Te0.3g, La-Ce mishmetal 0.5g and Sn92.9g.
The salt-mixture of 19.5gKCl and 15gLiC is covered after 430 ℃ of heat fused on the 92.9g Sn liquid level of melting in smelting furnace, be incubated 18 minutes, Sn temperature is elevated to 500 ℃, add 5.0gZn, 1.0gBi, 0.3gSb and 0.3gTe uniform stirring, be incubated 30 minutes, continue again rising furnace temperature to 600 ℃, the 0.5gLa-Ce mishmetal that is 1:1 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, be incubated 30 minutes, finally furnace temperature is dropped to 500 ℃ of insulations 120 minutes, after alloy mixes, standing coming out of the stove, be cast in stainless steel mould, solidify the surperficial salt-mixture of rear removal, make the polynary eutectic lead-free brazing of tin zinc bismuth and be processed into solder powder.
Comparative example 1
Raw material components and consumption: Zn9.0g, Sn91.0g.
The salt-mixture of 19.5gKCl and 15gLiC is covered after 450 ℃ of heat fused on the 91.0g Sn liquid level of melting, at 450 ℃, be incubated 20 minutes; Temperature is elevated to 500 ℃, adds 9.0gZn, and uniform stirring, be incubated 120 minutes, after alloy mixes, standing coming out of the stove, is cast in stainless steel mould, solidifies the surperficial salt-mixture of rear removal, makes described solder.
Comparative example 2
Raw material components and consumption: Zn8.0g, Bi1.0g, Sn91.0g.
The salt-mixture of 19.5gKCl and 15gLiC is covered after 400 ℃ of heat fused on the 91.0g Sn liquid level of melting, at 400 ℃, be incubated 30 minutes; Temperature is elevated to 500 ℃, adds 8.0gZn and 1.0gBi, and uniform stirring, be incubated 120 minutes, after alloy mixes, standing coming out of the stove, is cast in stainless steel mould, solidifies the surperficial salt-mixture of rear removal, makes described solder.
The present invention has carried out the assessment of the polynary eutectic lead-free brazing of rare earth modified tin zinc bismuth.Embodiment 1 to embodiment 6 and comparative example's 1 to 2 testing result is in Table 1.
Table 1 embodiment 1-6 and comparative example's 1 to 2 testing result
As can be seen from Table 1, the fusing point of the polynary eutectic lead-free brazing of tin zinc bismuth of the present invention is 184～192 ℃, when Bi content is 5%, the fusing point of solder of the present invention is 184 ℃, be starkly lower than Sn-8Zn-1Bi and Sn-9Zn solder, very approaching with 183 ℃ of the fusing points of traditional Sn-37Pb solder, good with existing equipment and soldering processes compatibility; In addition, solder of the present invention spreading ratio are also significantly greater than Sn-8Zn-1Bi and Sn-9Zn solder, and on copper base or gold-plated, nickel plating substrate, wetability is good.
Claims (3)
1. the polynary eutectic lead-free brazing of tin zinc bismuth, is characterized in that, it is comprised of the raw material of following weight percentage:
Described La-Ce mishmetal, its percentage by weight of La, Ce is that La:Ce is 1:1～1:3.
2. according to the preparation method of the polynary eutectic lead-free brazing of described tin zinc bismuth of claim 1, it is characterized in that it carries out in the steps below:
(a) salt-mixture that is 1.3:1 by KCl:LiCl by weight covers on 90.2～93.78%Sn liquid level of melting in smelting furnace after 400～450 ℃ of heat fused, is incubated 15～20 minutes;
(b) the Sn temperature of (a) melting is elevated to 500～600 ℃, adds 4.0～6.0%Zn, 1.0～5.0%Bi, 0.1～0.5%Sb, 0.01～0.5%Te, and uniform stirring, be incubated 20～30 minutes;
(c) continue again rising furnace temperature to 600～650 ℃, 0.01～0.5%La-Ce the mishmetal that is 1:1～1:3 by the La:Ce of weight ratio is pressed in the tin liquor of melting with stainless steel bell jar with holes on wall, rotate bell jar, after the complete melting of La-Ce mishmetal, uniform stirring, is incubated 20～30 minutes;
(d) finally furnace temperature is dropped to 500～600 ℃ of insulations 60～120 minutes, after alloy mixes, standing coming out of the stove, is cast in stainless steel mould, solidifies the surperficial salt-mixture of rear removal, makes the polynary eutectic lead-free brazing of tin zinc bismuth.
3. the preparation method of the polynary eutectic lead-free brazing of tin zinc bismuth according to claim 2, is characterized in that described solder also can be processed into solder post, solder bar, solder wire, solder ball or solder powder.
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| CN102825396B (en) * | 2012-09-18 | 2015-06-03 | 金华市双环钎焊材料有限公司 | Sn-Zn leadless brazing filler metal containing Pr, Ga and Te |
| CN102862000B (en) * | 2012-09-18 | 2014-12-03 | 常熟市华银焊料有限公司 | Sn-Zn lead-free brazing filler metal containing Nd, Ga and Te |
| CN103240541B (en) * | 2013-05-13 | 2014-08-13 | 金封焊宝有限责任公司 | Tin zinc multi-element alloy solder for soldering copper and aluminum and preparation method thereof |
| CN106041353B (en) * | 2016-06-17 | 2018-05-25 | 天津大学 | A kind of Sn-Zn-Bi series lead-free solders alloy and preparation method thereof |
| JP6998557B2 (en) | 2017-09-29 | 2022-01-18 | パナソニックＩｐマネジメント株式会社 | Solder alloy and joint structure using it |
| CN107699736B (en) * | 2017-10-24 | 2019-09-06 | 河南科技大学 | A kind of tin alloy for copper alloy hot-plating and preparation method thereof |
| CN107699735B (en) * | 2017-10-24 | 2019-09-06 | 河南科技大学 | Tin alloy for copper alloy hot-plating and preparation method thereof |
| CN109513747B (en) * | 2018-09-25 | 2020-06-30 | 深圳市兴鸿泰锡业有限公司 | A kind of preparation method of difficult-to-deform tin-bismuth alloy preform solder |
| CN109465562A (en) * | 2018-11-28 | 2019-03-15 | 东莞理工学院 | Lead-free solder and soldering flux matched with same |
| CN112548251B (en) * | 2020-12-07 | 2021-06-18 | 镇江百永电气设备有限公司 | High-heat-resistance high-conductivity flexible connection and preparation process thereof |
| CN119035867B (en) * | 2024-10-31 | 2025-07-18 | 维特瑞交通科技有限公司 | A kind of oxidation-resistant low-temperature-resistant solder material and preparation method thereof |
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