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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Abstract
The invention relates to a tin, zinc and bismuth multi-element eutectic lead-free solder and a preparation method. The tin, zinc and bismuth multi-element eutectic lead-free solder is characterized by comprising from 4.0 to 6.0% of Zn, from 1.0 to 5.0% of Bi, from 0.1 to 0.5% of Sb, from 0.01 to 0.5% of Te, from 0.01 to 0.5% of La-Ce mischmetal and the balance Sn. The preparation method includes covering mixed salt containing KCl and LiCl on the liquid surface of the 90.2-93.7% of Sn which is melted in a smelting furnace after the mixed salt is heated and melted; keeping the temperature of the liquid level of the balance Sn covered with the mixed salt unchanged; heating the melted Sn to reach the temperature ranging from 500 DEG C to 600 DEG C; adding the Zn, the Bi, the Sb and the Te into the Sn; stirring mixture of the Zn, the Bi, the Sb, the Te and the Sn; keeping the temperature of the mixture unchanged; continuing to heat up the furnace to reach the temperature ranging from 600 DEG C to 650 DEG C; pressing the from 0.01 to 0.5% of La-Ce mischmetal into melted tin liquid by the aid of a stainless steel immersion bell with a hole on the wall; driving the immersion bell to rotate; uniformly stirring mixture of the tin liquid and the La-Ce mischmetal; keeping the temperature of the mixture unchanged; finally cooling the furnace to reach the temperature ranging from 500 DEG C to 600 DEG C; allowing alloy to stand still after the alloy is mixed; discharging the alloy from the furnace; pouring the alloy; removing the mixed salt after the alloy is solidified; and obtaining the multi-element eutectic lead-free solder. The tin, zinc and bismuth multi-element eutectic lead-free solder has the advantages that the solder has low melting point, and is fine in wettability and antioxidant performance and high in mechanical property, and corrosion resistance is further improved.
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 | One Albatra metal hot dip tin alloy and preparation method thereof |
| CN107699735B (en) * | 2017-10-24 | 2019-09-06 | 河南科技大学 | Copper alloy hot dip tin alloy and preparation method thereof |
| CN109513747B (en) * | 2018-09-25 | 2020-06-30 | 深圳市兴鸿泰锡业有限公司 | Method for preparing tin-bismuth alloy preformed soldering lug difficult to deform |
| CN109465562A (en) * | 2018-11-28 | 2019-03-15 | 东莞理工学院 | A kind of lead-free brazing and its with applying scaling powder |
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| US5851482A (en) * | 1996-03-22 | 1998-12-22 | Korea Institute Of Machinery & Metals | Tin-bismuth based lead-free solder for copper and copper alloys |
| JP2000210788A (en) * | 1999-01-27 | 2000-08-02 | Matsushita Electronics Industry Corp | Lead-free solder alloy and its manufacture |
| WO2003021664A1 (en) * | 2001-08-31 | 2003-03-13 | Hitachi, Ltd. | Semiconductor device, structural body and electronic device |
| CN1498713A (en) * | 2002-10-31 | 2004-05-26 | 株式会社东芝 | Lead-less joining material and joining method using such material |
| JP2004188453A (en) * | 2002-12-11 | 2004-07-08 | Harima Chem Inc | Sn-BASED SOLDER ALLOY |
| CN1764515A (en) * | 2003-04-01 | 2006-04-26 | 千住金属工业株式会社 | Solder paste and printed board |
| CN101549441A (en) * | 2008-04-01 | 2009-10-07 | 东莞市中实焊锡有限公司 | Lead-free solder |
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| CN102581507A (en) | 2012-07-18 |
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