CN102936669A - Low-melting-point lead-free solder alloy - Google Patents
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Abstract
The invention relates to a low-melting-point lead-free solder alloy which belongs to the technical field of welding materials and is used for solving the problem that the conventional solder alloys are high in melting point and low in shearing strength. The low-melting-point lead-free solder alloy comprises the following components in percentage by weight: 10-30% of Bi, 2.2-3.0% of Ag, 0.5-1.0% of In, 0.004-0.008% of P and the balance being tin. The low-melting-point lead-free solder alloy also can comprise 0.002-0.005% of RE and 0.002-0.005% of Co. According to the low-melting-point lead-free solder alloy, the melting point is low, the alloy eutectic temperature is about 170-200 DEG C, the shearing strength is good and between 21-28N/mm<2>, the RE is capable of improving the glossliness of the solder alloy and refining the grains, the Co is capable of improving the soldering performance and the shock resistance, and Zr has the function of homogenizing and refining the alloy tissues.
Description
Technical field
The present invention relates to a kind of scolder, relate in particular to a kind of low melting point lead-free solder alloy, belong to technical field of welding materials.
Background technology
All the time, the Sn-Pb alloy is occupied an leading position at the electronic unit fit on as the main packaged material of electronic industry, yet because lead and lead compound thereof belong to highly toxic substance, human body is had great toxicity.Especially in recent years along with the enhancing of people's environmental consciousness with for the concern of self health, Lead contamination more and more is subject to people's attention; And the taboo leads example of in recent years various countries' proposition makes the Electronic Packaging industry have higher requirement to pb-free solder, and ripe wiping solder must be substituted by lead-free solder.
The lead-free solder that current industry is comparatively approved is mainly take Sn-Ag-Cu as representative, because it obtains easily, technical problem is relatively also less, and better with the conventional solder consistency, reliability is higher, although it has avoided adopting plumbous raw material as scolder,, the Sn-Ag-Cu lead-free solder is except the cost of alloy factor, its the most fatal weakness is that alloy melting point is higher than Sn-Pb scolder, and Sn-Ag-Cu is that eutectic temperature is 217 ℃ to compare Sn-Pb eutectic solder fusing point be 183 ℃ high 34 ℃.Make for the easy cause thermal side of the relatively poor components and parts of thermotolerance, cause planar substrates flexural deformation, strengthen the possibility of its damage.This just means that employing Sn-Ag-Cu lead-free solder has proposed stern challenge to a series of engineerings such as heat resistance of welding set, weldprocedure, electronic component and baseplate material.
Such as Chinese patent application (publication number: CN101257995A, open day: on 09 03rd, 2008) a kind of solder composition is disclosed, said composition comprises tin, indium, silver and bismuth, and comprises about tin of 30% to 85% and about indium of 15% to 65%, also can further comprise copper.And further the content of restriction silver is 1% to 10%, and the content of bismuth is 0.25% to 6%, and the content of copper is 0.25% to 0.75%.The content of bismuth content less and indium is relatively high in this welding flux alloy, although the adding of bismuth can improve the intensity of scolder, but can't reach desirable temperature requirement.Simultaneously, too much as the amount that the In of precious metal adds, increased greatly production cost.Therefore, for the quality that improves welding flux alloy with consider the requirement of Electronic Assemblies processing condition, required lead-free solder should meet the following conditions: fusing point is low, and the alloy eutectic temperature is similar to 183 ℃ of the eutectic temperatures of Sn-Pb, roughly between 180 ℃～200 ℃; Has good wettability; Satisfactory mechanical property, solder joint will have the requirements such as enough physical strengths and thermal ageing resistant performance.
Summary of the invention
The present invention is directed to the defective that exists in the above prior art, a kind of low melting point lead-free solder alloy is provided, have the low and good effect of shearing resistance of welding flux alloy fusing point.
The objective of the invention is to be achieved by the following technical programs, a kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:10%～30%; Ag:2.2%～3.0%; In:0.5%～1.0%; P:0.004%～0.008%; All the other are tin.
Low melting point lead-free solder alloy of the present invention reduces the temperature of welding flux alloy by adding Bi, Sn-Bi is that scolder can form in 139 ℃～232 ℃ wide melting range, its fusing point in the time of 180 ℃ near the eutectic temperature of Sn-Pb welding flux alloy.Although, Sn-Bi is that the fusing point of scolder eutectic only is 139 ℃, low temperature about 160 ℃ just can be assembled, but because Bi is hard fragility, soldering coarse microstructure and inhomogeneous phenomenon are arranged, if the amount that adds conference cause alloy can't be made into wire, during welding because high-temperature impacts easy to crack, if and the amount that adds very little, then be not enough to reduce the temperature of welding flux alloy.There is content with Bi to be controlled at 40%～60% or be controlled at below 5% in the existing scolder, although the former can reach the effect that reduces solder temperature, the fragility that presents of Bi itself just, the too high levels of Bi, can make scolder present hard fragility, make the shearing resistance of scolder too poor; And the content of latter Bi very little, although can guarantee the intensity of scolder, temperature can't reach desirable requirement.Therefore, the present invention is controlled at 10%～30% with the content of Bi, thereby can either reach the effect that reduces solder temperature, can guarantee again the shearing resistance performance of scolder, simultaneously, improves the alloy property of scolder by adding Ag and In; And simultaneously by adding a small amount of P element, can improve the antioxidant property of scolder and reduce the oxidized degree of scolder, reduce the generation of scruff.Welding flux alloy eutectic temperature of the present invention is about 170 ℃～200 ℃.
In above-mentioned low melting point lead-free solder alloy, described Ag can form Sn-Ag eutectic (Ag3Sn) with the Sn matrix, improves the mechanical property of scolder, if but that the amount of Ag is added is too many, then can increase the cost of scolder; If add very little, the effect that then improves mechanical property is not remarkable.
In above-mentioned low melting point lead-free solder alloy, has synergy between described In and the Bi, can play equally the effect of the fusing point that reduces welding flux alloy, can also improve the physicals of welding flux alloy simultaneously, increase the luminance brightness of scolder and improve the effect of prolonging the rate of liter.
As preferably, in above-mentioned low melting point lead-free solder alloy, described leadless welding alloy contains the weight percent of following composition:
Bi:15%～25%; Ag:2.3%～2.8%; In:0.6%～0.8%; P:0.005%～0.006%; All the other are tin.
As further preferred, in above-mentioned low melting point lead-free solder alloy, described leadless welding alloy contains the weight percent of following composition:
Bi:25%; Ag:2.5%; In:0.8%; P:0.0058%; All the other are tin.
In above-mentioned low melting point lead-free solder alloy, low melting point lead-free solder alloy in the described preferable range, the fusing point that can further guarantee welding flux alloy of the present invention is more near the fusing point (183 ℃) of Sn-Pb welding flux alloy, between 180 ℃～200 ℃, thereby better realize both unleadedly, can reach again requirement and the better advantage of shearing resistance of leaded fusing point.
In above-mentioned low melting point lead-free solder alloy, it is 0.002%～0.005% RE that described leadless welding alloy also contains weight percent, and described RE is mishmetal.Can improve the glossiness of welding flux alloy, the effect of crystal grain thinning, simultaneously can also and scolder in Bi and the In element between form synergy, further play the performance that reduces temperature and guarantee shearing resistance.As preferably, described RE is selected from two or more among La, Pr, Er, Dy, the Nd.As further preferred, described RE is La, Pr, Er and Dy; Wherein, the weight ratio of La:Pr:Er:Dy is 1:0.5～0.8:0.2～0.4:0.3～0.6.
In above-mentioned low melting point lead-free solder alloy, in the described low melting point lead-free solder alloy, also contain weight percent and be 0.0002%～0.0005% Co.Add Co and can play brazing property and the impact resistance that improves welding flux alloy.
In above-mentioned low melting point lead-free solder alloy, in the described low melting point lead-free solder alloy, also contain weight percent and be 0.0001%～0.0005% Zr.Add Zr and play the homogenizing alloy structure, the effect of refinement alloy structure simultaneously with the Bi synergy, can also improve the shearing resistance performance of welding flux alloy, improves the existing hard fragility defective of Bi element.
Low melting point lead-free solder alloy of the present invention gets final product according to the method preparation of this area routine.
In sum, the present invention has the following advantages:
1. low melting point lead-free solder alloy of the present invention has lower fusing point, and the alloy eutectic temperature and has the good effect of shearing resistance simultaneously about 170 ℃～200 ℃, and shearing resistance is at 21N/mm2～28N/mm
2Between, alloy structure is even, and the advantage that physicals is good is applicable to the relatively poor electronic apparatus assembling industry of thermotolerance.
2. low melting point lead-free solder alloy of the present invention, only need to add a small amount of elements such as In, Ag, need not to add the elements such as a large amount of precious metals such as In, thereby also can play the effect that reduces cost, and the present invention is by adding the RE mishmetal, can improve the glossiness of welding flux alloy, the performance that reduces temperature and guarantee shearing resistance is further played in the effect of crystal grain thinning.
3. low melting point lead-free solder alloy of the present invention can play brazing property and the impact resistance that improves welding flux alloy by adding Co; Add Zr and play the homogenizing alloy structure, the effect of refinement alloy structure can also further improve the shearing resistance performance of welding flux alloy, improves scolder because of the defective of the existing hard fragility of Bi element that adds.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail, but the present invention is not limited to these embodiment.
Embodiment 1
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:10%; Ag:2.8%; I n:0.5%; P:0.005%; Surplus is Sn, also can comprise inevitable impurity.
Low melting point lead-free solder alloy in the present embodiment adopts following methods to prepare:
Weight percent according to the Bi in the present embodiment, Ag, In, P and Sn takes by weighing required raw material, joins in the stove, then is warmed up to 300 ℃ of meltings, then, put into stirrer and fully stirred 40 minutes, again cast molding namely gets low melting point lead-free solder alloy of the present invention.
Embodiment 2
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:15%; Ag:2.8%; In:0.5%; P:0.0052%; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 3
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:20%; Ag:2.5%; In:0.8%; P:0.0055%; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 4
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:25%; Ag:2.5%; In:0.8%; P:0.0058%; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 5
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:30%; Ag:2.2%; In:1.0%; P:0.006%; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 6
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:27%; Ag:3.0%; In:0.6%; P:0.004%; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 7
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:20%; Ag:2.3%; In:0.7%; P:0.0055%; RE:0.002%, described RE are mishmetal; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 8
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:22%; Ag:2.4%; In:0.6%; P:0.0057%; RE:0.005%, described RE are mishmetal; Co:0.0005%; Surplus is Sn, also comprises inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 9
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:18%; Ag:2.5%; In:0.7%; P:0.0055%; RE:0.003%, described RE are mishmetal; Co:0.0002%; Zr:0.0001%; Surplus is Sn, also comprises inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 10
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:28%; Ag:2.6%; In:0.8%; P:0.008%; Co:0.0004%; Surplus is Sn, also can comprise inevitable impurity.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 11
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:20%; Ag:2.3%; In:0.7%; P:0.0055%; RE:0.002%, described RE are mishmetal, and surplus is Sn, also can comprise inevitable impurity, and described RE mishmetal is the mishmetal of La and Dy, and the weight ratio of La:Dy is 1:0.5.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 12
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:23%; Ag:2.5%; In:1.0%; P:0.0055%; RE:0.005%, described RE are mishmetal, and surplus is Sn, also can comprise inevitable impurity, and described RE mishmetal is the mishmetal of La and Nd, and the weight ratio of La:Dy is 1:0.6.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 13
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:20%; Ag:2.3%; In:0.7%; P:0.0055%; RE:0.002%, described RE are mishmetal, and surplus is Sn, also can comprise inevitable impurity, and described RE mishmetal is the mishmetal of La, Pr, Er and Dy; Wherein, the weight ratio of La:Pr:Er:Dy is 1:0.8:0.4:0.3.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 14
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:25%; Ag:2.5%; In:0.5%; P:0.005%; RE:0.003%, described RE are mishmetal; Co:0.0004%; Surplus is Sn, also can comprise inevitable impurity, and described RE mishmetal is the mishmetal of La, Pr, Er and Dy; Wherein, the weight ratio of La:Pr:Er:Dy is 1:0.5:0.2:0.6.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 15
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:25%; Ag:2.3%; In:0.5%; P:0.0055%; RE:0.003%, described RE are mishmetal; Co:0.0005%; Surplus is Sn, also can comprise inevitable impurity, and described RE mishmetal is the mishmetal of La, Pr, Er and Dy; Wherein, the weight ratio of La:Pr:Er:Dy is 1:0.6:0.3:0.4.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Embodiment 16
A kind of low melting point lead-free solder alloy, this leadless welding alloy contains the weight percent of following composition:
Bi:20%; Ag:2.8%; In:0.8%; P:0.0065%; RE:0.004%, described RE are mishmetal; Co:0.0004%; Zr:0.0005%; Surplus is Sn, also can comprise inevitable impurity, and described RE mishmetal is the mishmetal of La, Pr, Er and Dy; Wherein, the weight ratio of La:Pr:Er:Dy is 1:0.5:0.35:0.5.
The preparation method of the low-melting point leadless scolder in the present embodiment is consistent with the method described in the embodiment 1, and difference only is that the weight percent of each composition of leadless welding alloy takes by weighing according to ratio in the present embodiment.
Choose at random the low melting point lead-free solder alloy that obtains in above-described embodiment, the performance of its liquidus temperature, solidus temperature, shearing resistance and unit elongation is tested, concrete test result is seen following table 1.
Table 1:
Specific embodiment described in the invention only is to the explanation for example of the present invention's spirit.Those skilled in the art can make various modifications or replenish or adopt similar mode to substitute described specific embodiment, but can't depart from spirit of the present invention or surmount the defined scope of appended claims.
Although the present invention has been made a detailed description and has quoted as proof some specific embodiments, to those skilled in the art, only otherwise it is obvious leaving that the spirit and scope of the present invention can make various changes or revise.
Claims (8)
1. a low melting point lead-free solder alloy is characterized in that, this leadless welding alloy contains the weight percent of following composition:
Bi:10%～30%; Ag:2.2%～3.0%; In:0.5%～1.0%; P:0.004%～0.008%; All the other are tin.
2. low melting point lead-free solder alloy according to claim 1 is characterized in that, this leadless welding alloy contains the weight percent of following composition:
Bi:15%～25%; Ag:2.3%～2.8%; In:0.6%～0.8%; P:0.005%～0.006%; All the other are tin.
3. low melting point lead-free solder alloy according to claim 2 is characterized in that, this leadless welding alloy contains the weight percent of following composition:
Bi:25%; Ag:2.5%; In:0.8%; P:0.0058%; All the other are tin.
4. the described low melting point lead-free solder alloy of any one is characterized in that according to claim 1-4, also contains weight percent and be 0.002%～0.005% RE, and described RE is mishmetal.
5. low melting point lead-free solder alloy according to claim 4 is characterized in that, described RE is selected from two or more among La, Pr, Er, Dy, the Nd.
6. low melting point lead-free solder alloy according to claim 5 is characterized in that, described RE is La, Pr, Er and Dy; Wherein, the weight ratio of La:Pr:Er:Dy is 1:0.5～0.8:0.2～0.4:0.3～0.6.
7. low melting point lead-free solder alloy according to claim 1 is characterized in that, also contains weight percent and be 0.0002%～0.0005% Co.
8. low melting point lead-free solder alloy according to claim 4 is characterized in that, also contains weight percent and be 0.0002%～0.0005% Co.
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| CN105583547A (en) * | 2016-03-11 | 2016-05-18 | 深圳市同方电子新材料有限公司 | SnBi lead-free solder and preparation method thereof |
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| CN106624432A (en) * | 2016-11-30 | 2017-05-10 | 安徽华众焊业有限公司 | Low-melting-point tin bismuth solder alloy |
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| CN114055007A (en) * | 2021-11-16 | 2022-02-18 | 陕西众森电能科技有限公司 | Superfine low-temperature soldering tin powder, soldering paste, preparation method and application thereof |
| CN114055007B (en) * | 2021-11-16 | 2023-03-14 | 陕西众森电能科技有限公司 | Superfine low-temperature soldering tin powder, soldering paste, preparation method and application thereof |
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