CN103934590A - ZnAlMgIn high temperature lead-free solder - Google Patents

ZnAlMgIn high temperature lead-free solder Download PDF

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Publication number
CN103934590A
CN103934590A CN201410146904.5A CN201410146904A CN103934590A CN 103934590 A CN103934590 A CN 103934590A CN 201410146904 A CN201410146904 A CN 201410146904A CN 103934590 A CN103934590 A CN 103934590A
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CN
China
Prior art keywords
solder
alloy
znalmgin
high temperature
free solder
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CN201410146904.5A
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Chinese (zh)
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CN103934590B (en
Inventor
杨晓军
闫鑫
胡伟
雷永平
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Beijing University of Technology
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Beijing University of Technology
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Priority to CN201410146904.5A priority Critical patent/CN103934590B/en
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Publication of CN103934590B publication Critical patent/CN103934590B/en
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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
    • B23K35/28—Selection of soldering or welding materials proper with the principal constituent melting at less than 950 degrees C
    • B23K35/282—Zn as the principal constituent

Abstract

The invention relates to ZnAlMgIn high temperature lead-free solder, and belongs to the technical field of manufacturing lead-free solder for electronic first-grade encapsulation in the micro-electronic industry. The ZnAlMgIn high temperature lead-free solder comprises (by mass) 3.9 to 4.1 percent of Al, 2.4 to 3.1 percent of Mg, 0.5 to 3.0 percent of In, or 0.05 to 1.0 percent of P, and the balancing Zn. The ZnAlMgIn high temperature lead-free solder is smelted with a fused salt protection method, alloy burning losses are small, and texture is even. According to the ZnAlMgIn high temperature lead-free solder, on the basis of Zn4Al3Mg near-eutectic alloy, the elements of In and P are proposed to be added in a micro amount to lower the melting point of the alloy and improve the oxidation resistance and wettability of the alloy. The ZnAlMgIn high temperature lead-free solder is low in cost, free from toxic elements such as Pb, good in wettability, good in mechanical property and capable of meeting the requirement for replacing traditional high-lead solder.

Description

A kind of ZnAlMgIn high-temp leadless solder
Technical field:
The present invention relates to the high temperature lead-free solder in solder field, is a kind of novel ZnAlMg-xIn lead-free brazing, belongs to the encapsulation of microelectronic industry electronics one-level with lead-free brazing manufacturing technology field, is also applied in the soldering of automobile circuit plate and household electrical appliance welding field.
Background technology:
Along with social development, people are more and more higher to environmental protection and healthy requirement, and RoHS Directive and China " electronics and IT products pollution control management way " have all provided against use solder containing lead.Leaded high-temp solder Pb5Sn and Pb10Sn(fusing point are respectively 305 DEG C and 310 DEG C) but never find suitable unleaded alternative solder.At present, the research of high-temp leadless solder mainly concentrates on following system: Au base, Bi base, Zn-Sn and Zn-Al base leadless solder.Au20Sn and Au-Ge solder have better wetability and electrical and thermal conductivity, but cause solder cost to be mentioned because it has used Au in a large number, have limited it and have applied widely.And AuSn solder can form more crisp intermetallic compound, reduce the tensile strength of solder joint.Bi-Ag solder has suitable fusing point (270 DEG C), but because the fragility of matrix Bi causes the processing characteristics of solder very poor, and poor electric conductivity.ZnSn solder is because its serious corrosivity and very low solidus temperature (198 DEG C) limit its development.And the advantage such as Zn-Al base alloy has that cost is low, good processability, electrical and thermal conductivity performance are good and thermal coefficient of expansion is low becomes the optimal selection of high-temp leadless solder.
Due to 381 DEG C of Zn6Al(fusing points) matrix of solder alloy is mainly activity Metal Zn, as easy as rolling off a log oxidized under high temperature, thus affect the wetability of solder.Thereby, the non-oxidizability of raising solder, it is necessary reducing alloy melting point.In recent years, main on the basis of Zn6Al eutectic composition, improve the performance of alloy by adding alloy element Mg, In, Cu, Ga etc.Wherein bibliographical information lead-free brazing Zn4Al3Mg3Ga is successfully applied in reality, but due to the poor ductility of this solder, is difficult to be processed into banded or thread; Bibliographical information ZnAlCu solder alloy, Cu adds alloy melting point depression not obvious; Zn12Al-xIn(x=0.5～1.5at.%) solder alloy, the interpolation of In has improved the wetability of alloy, but the melting point depression of alloy is not obvious.The present invention proposes on the basis of ZnAl solder, adds alloy element Mg and falls low-alloyed fusing point, and further add alloying element In on the basis of ZnAlMg ternary alloy three-partalloy, puies forward heavy alloyed non-oxidizability and further reduces alloy melting point.
Summary of the invention:
The present invention is on the basis of ZnAl solder, and the Mg that adds 3wt% forms 343 DEG C of near-eutectic alloy Zn4Al3Mg(fusing points), and on Zn4Al3Mg basis, further add alloying element In, improve the non-oxidizability of brazing filler metal alloy and further reduce temperature.The quaternary ZnAlMg-xIn new type high temperature solder forming, this alloy has reduced fusing point to a great extent, has improved the wetability of solder.
The invention provides a kind of ZnAlMgIn high-temp leadless solder, it is characterized in that: this solder mass percent consists of Al3.9～4.1%, Mg2.4～3.1%, In0.5～3.0%, Zn90～93%.
Further, this solder also includes P0.05～1.0%.
The preparation method of a kind of ZnAlMgIn high-temp leadless solder of the present invention carries out according to the following steps: one, weigh fused salt: example takes fused salt KCl:LiCl=(1.2～1.4 in mass ratio): (0.9～1.1); Two, weigh metal: taking 3.9～4.1 parts of Al pieces, 2.4～3.1 parts of Mg pieces, 0.5～3.0 part of In piece, surplus by mass percent is Zn piece; Three, melting; Step 1 is obtained to fused salt evenly mixes and is placed in ceramic crucible, crucible is placed in resistance furnace and is heated to 400 DEG C, the Zn piece after fused salt melts completely, step 2 being obtained is placed under fused salt, being heated to 450 DEG C is placed in Al and Mg piece under Zn liquid successively, be heated to 600 DEG C of insulations 10～30 minutes, be cooled to 500 DEG C fully to stir with quartz glass bar, obtain ZnAlMg alloy.Four, remelting: the alloy that step 3 is obtained melting again, 400 DEG C add after In piece and fully stir, and obtain high-temp solder.
Effect of the present invention and advantage are: solder of the present invention is suitable higher than fusing point for the one-level Electronic Packaging of 260 DEG C for temperature, and wetability is good, and microhardness and the tensile strength of alloy are higher, can meet 300 DEG C of instructions for uses of soldered fitting.With respect to Au base solder and BiAg solder, solder main component Zn metal price of the present invention is cheap, and does not contain the noble metals such as Ag, Au in composition, with low cost.The interpolation of Mg element has improved the corrosion resistance of solder alloy, and Zn alloy itself has very strong corrosivity, and research shows that the interpolation of micro Mg can improve the intercrystalline corrosion of Zn alloy.After interpolation microalloying element In, the melting point depression of alloy is obvious, the fusing point of near-eutectic alloy Zn4Al3Mg is 343 DEG C, in the time that the mass percent of In in alloy is 2～3%, the fusing point of alloy is 320～330 DEG C, has met alternative traditional solder Pb5Sn and the requirement of Pb10Sn fusing point.The interpolation of In, improve the non-oxidizability of alloy, increase the wetability of solder, this is main because the oxidation resistent susceptibility of In element itself, and atomic radius is little compared with large surface tension, In is enriched in the surface of liquid solder, reduces the surface tension of liquid solder, therefore, the interpolation of In element has improved the wettability of solder.In addition, In resistance to chemical attack, and can strengthen the resistance to chemical corrosion of alloy.The interpolation of P element can improve the non-oxidizability of brazing filler metal alloy, main because P element can promote liquid solder to form the surface film oxide of one deck densification, the further oxidation of prevention solder, thereby the non-oxidizability of raising solder.
The preparation method of a kind of high-temp solder of the present invention; be under molten protection, to carry out melting, protected alloy not oxidized, deposite metal at 600 DEG C; at 500 DEG C, carry out abundant stirring and not only can ensure the homogenising of alloy, and reduced the high temperature scaling loss of alloy.
Brief description of the drawings:
The electron scanning picture of Fig. 1 ZnAlMg
The electron scanning picture of Fig. 2 ZnAlMg-2In
Detailed description of the invention
High-temp leadless solder alloy of the present invention adopts molten protection method melting preparation, below in conjunction with specific embodiment, the present invention is described in further detail, but content of the present invention is not limited to embodiment.Embodiments of the invention are in table 1.Specific embodiment is as follows:
Embodiment 1: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, surplus is Zn.
Embodiment 2: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, In1.0, surplus is Zn.
Embodiment 3: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, In1.5, surplus is Zn.
Embodiment 4: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, In2.0, surplus is Zn.
Embodiment 5: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, In2.5, surplus is Zn.
Embodiment 6: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, In3.0, surplus is Zn.
Embodiment 7: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, P0.1, surplus is Zn.
Embodiment 8: the high-temp solder of a kind of electronic product one-level encapsulation of the present embodiment is grouped into by the one-tenth of following mass percent: Al4.0, Mg3.0, In1.0, P0.1, surplus is Zn.
The composition (wt%) of table 1 embodiment solder and fusion temperature (DEG C)
Table 1, except listing the chemical composition of 6 kinds of embodiment, gives liquidus temperature and the solidus temperature of each solder.The liquidus temperature of solder and solidus temperature are recorded by differential scanning calorimetry (DSC).As can be seen from Table 1, the specific embodiment of the invention 1～6, solid liquid phase temperature all reduces along with the increase of In content, and micro-In adds the fusing point that has reduced alloy, is suitable for electronics one-level packaging technology condition.
Table 2 is spreading area (carrying out the experiment of sprawling of solder according to standard GB/T/T11364-1989), electrical conductivity and microhardnesses of embodiment solder.The wetability of embodiment solder well and along with the increase wettability of In content improves constantly, electrical and thermal conductivity performance is outstanding, and microhardness is far above the high lead solder of traditional tradition.
Embodiment solder 1,2,7 and 8 keeps after 10h at 100 DEG C of temperature, and the sequence of solder surface-brightening degree size is: embodiment 7 ﹥ embodiment 1 ﹥ embodiment 8 ﹥ embodiment 2.The solder surface of only adding P element is light relatively, and it is the darkest on the contrary only to add In element solder surface, illustrate that the micro-p of interpolation can improve the non-oxidizability of solder alloy, but In element has increased the oxidation of brazing filler metal alloy on the contrary.This is main because P element can promote alloy surface to form compact oxidation layer, prevent that alloy from continuing oxidation, but In element radius is large, is easily segregated in alloy crystal boundary and has promoted the corrosion of solder.
At present, under fierce market competition, people are not only paying close attention to the performance of lead-free brazing, and the cost of solder is also taken much count of.Replace in the selection of traditional solder, Au20Sn and Au25Ge eutectic solder (fusing point is respectively 280 DEG C and 363 DEG C) although excellent performance, the cost of Au is too high has limited its development.And solder of the present invention is using cheap Zn as matrix, cost is reduced greatly, and solder electrical and thermal conductivity performance in example is good, along with the increase of In content, antioxygenic property and the wetability of solder are improved.
Spreading area (the mm of table 2 embodiment solder 2), electrical conductivity (MS/m) and microhardness (HV)
Classification Spreading area (mm 2) Electrical conductivity (MS/m) Microhardness (HV)
Embodiment 1 248.59 16.622 162.50
Embodiment 2 264.49 9.818 155.48
Embodiment 3 282.72 9.450 133.86
Embodiment 4 295.68 9.426 131.80
Embodiment 5 302.15 9.478 121.50
Embodiment 6 306.59 9.490 103.08

Claims (3)

1. a ZnAlMgIn high-temp leadless solder, is characterized in that: this solder comprises the component of following mass percent: Al3.9～4.1%, Mg2.4～3.1%, In0.5～3.0%, Zn90～93%.
2. a kind of ZnAlMgIn high-temp leadless solder according to claim 1, is characterized in that the In content in this solder is 0.5～2.0%.
3. a kind of ZnAlMgIn high-temp leadless solder according to claim 1, is characterized in that this solder also includes P0.05～1.0%.
CN201410146904.5A 2014-04-13 2014-04-13 A kind of ZnAlMgIn high-temp leadless solder Expired - Fee Related CN103934590B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106536108A (en) * 2014-04-17 2017-03-22 贺利氏材料新加坡私人有限公司 Lead-free eutectic solder alloy comprising zinc as the main component and aluminum as an alloying metal
CN106736006A (en) * 2016-11-30 2017-05-31 安徽华众焊业有限公司 Zn Al Cu base solders and preparation method thereof
WO2017187378A1 (en) * 2016-04-28 2017-11-02 Slovenská Technická Univerzita V Bratislave Active soft solder and method of soldering
CN111331278A (en) * 2020-03-26 2020-06-26 中机智能装备创新研究院(宁波)有限公司 High-corrosion-resistance Zn-Al solder powder, solder paste and preparation method

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106536108A (en) * 2014-04-17 2017-03-22 贺利氏材料新加坡私人有限公司 Lead-free eutectic solder alloy comprising zinc as the main component and aluminum as an alloying metal
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WO2017187378A1 (en) * 2016-04-28 2017-11-02 Slovenská Technická Univerzita V Bratislave Active soft solder and method of soldering
CN106736006A (en) * 2016-11-30 2017-05-31 安徽华众焊业有限公司 Zn Al Cu base solders and preparation method thereof
CN111331278A (en) * 2020-03-26 2020-06-26 中机智能装备创新研究院(宁波)有限公司 High-corrosion-resistance Zn-Al solder powder, solder paste and preparation method

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