CN100439027C - Lead-free solder alloys for copper-aluminum dissimilar metal soldering - Google Patents
Lead-free solder alloys for copper-aluminum dissimilar metal soldering Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 60
- 239000000956 alloy Substances 0.000 title claims abstract description 60
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 24
- 239000002184 metal Substances 0.000 title claims abstract description 24
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000005476 soldering Methods 0.000 title claims description 18
- 238000003466 welding Methods 0.000 abstract description 23
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- 239000010949 copper Substances 0.000 description 36
- 229910052802 copper Inorganic materials 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052782 aluminium Inorganic materials 0.000 description 16
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- 238000007254 oxidation reaction Methods 0.000 description 8
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- 229910052718 tin Inorganic materials 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910020994 Sn-Zn Inorganic materials 0.000 description 4
- 229910009069 Sn—Zn Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical class [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
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- 229910000765 intermetallic Inorganic materials 0.000 description 4
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- 229910017518 Cu Zn Inorganic materials 0.000 description 3
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- 229910017943 Cu—Zn Inorganic materials 0.000 description 3
- 229910020888 Sn-Cu Inorganic materials 0.000 description 3
- 229910019204 Sn—Cu Inorganic materials 0.000 description 3
- 229910009038 Sn—P Inorganic materials 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
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Abstract
Description
技术领域 technical field
本发明涉及一种异种金属钎焊的无铅焊料合金，特别涉及一种适用于铜铝异种金属软钎焊的无铅焊料合金。The invention relates to a lead-free solder alloy for brazing dissimilar metals, in particular to a lead-free solder alloy suitable for soldering copper and aluminum dissimilar metals.
背景技术 Background technique
随着电子信息产业的不断发展，电子产品的数量急剧增多。铜由于具有良好的导电、导热及耐蚀性，广泛应用于印制电路板、各种导线，并且需求量越来越大，但其受自然界的蕴藏量影响，满足不了社会发展的需求。金属铜等不可再生资源大量消耗，使得人们强烈地意识到，必须合理、有效地利用资源。出于对资源利用和材料成本的考虑，人们提出了在某些产品(如铜导线)的开发上需以性能相近且蕴藏量相对丰富的铝取代的方案。在实施过程中，发现要实现铝代替铜，首先要解决的问题就是铜铝的连接问题。因为铝与铜焊接属异种金属的焊接，两者之间存在较大的物理及化学性能上的差异，所以给焊接带来很大困难。铜铝的连接主要有熔化焊、固相焊、钎焊等几种方法。熔化焊时由于铜铝熔点相差较大，电弧难以同时加热熔化铜和铝，焊缝存在金属间化合物，导致焊接接头脆性大，因此机械强度相当的低，只适合一些有特殊要求的场合；固相焊包括摩擦焊(低温摩擦焊和高温摩擦焊)、电阻焊、冷压焊等，上述这些方法在生产上都得以应用，但固相焊由于受零件结构形式的限制，在许多场合不能应用，特别是在电子行业中的一些精密元器件；大多数的方法是在铝侧加过渡层，变成同种金属的连接问题，这样的方法一是工艺复杂；二是在许多场合不适用。铜铝的连接问题在电子焊接领域一直都没有得到很好的解决，尤其是在软钎焊方面。但是由于钎焊方法的柔性，适应性强，可以选择不同的钎料，得到不同强度及不同工作温度的钎焊接头，适合不同的场合，因此开发满足新形势下符合环保要求的铜铝连接用的软钎焊材料，是实现以铝代铜的关键所在。With the continuous development of the electronic information industry, the number of electronic products has increased dramatically. Due to its good electrical conductivity, thermal conductivity and corrosion resistance, copper is widely used in printed circuit boards and various wires, and its demand is increasing. However, it is affected by the reserves in nature and cannot meet the needs of social development. The massive consumption of non-renewable resources such as metal copper makes people strongly aware that resources must be used rationally and effectively. In consideration of resource utilization and material cost, it has been proposed that the development of certain products (such as copper wires) should be replaced by aluminum with similar performance and relatively abundant reserves. During the implementation process, it was found that to realize the replacement of copper with aluminum, the first problem to be solved was the connection of copper and aluminum. Because the welding of aluminum and copper belongs to the welding of dissimilar metals, there is a large difference in physical and chemical properties between the two, which brings great difficulties to welding. The connection of copper and aluminum mainly includes several methods such as fusion welding, solid phase welding, and brazing. Due to the large difference in the melting points of copper and aluminum during fusion welding, it is difficult for the arc to heat and melt copper and aluminum at the same time, and there are intermetallic compounds in the weld, resulting in high brittleness of the welded joint, so the mechanical strength is quite low, and it is only suitable for some occasions with special requirements; Phase welding includes friction welding (low temperature friction welding and high temperature friction welding), resistance welding, cold pressure welding, etc. These methods can be applied in production, but solid phase welding cannot be applied in many occasions due to the limitation of the structural form of parts. , especially some precision components in the electronics industry; most of the methods are to add a transition layer on the aluminum side, which becomes the connection problem of the same metal. This method is complicated in the process; it is not applicable in many occasions. The connection problem of copper and aluminum has not been well solved in the field of electronic welding, especially in soldering. However, due to the flexibility and adaptability of the brazing method, different solders can be selected to obtain brazed joints with different strengths and different working temperatures, which are suitable for different occasions. Advanced soldering materials are the key to realizing the replacement of copper with aluminum.
Sn63Pb37共晶焊料合金作为电子工业的主要连接材料，提供电气、热传导和机械的连接，以其优良的性能满足了这一要求，在现代电子装配工业中得到了广泛应用。由于铅对环境的危害及对人体的毒害越来越受到人们的重视，电子、电力产品无铅化已是全球化的趋势。Sn63Pb37 eutectic solder alloy, as the main connecting material in the electronics industry, provides electrical, heat conduction and mechanical connections, meets this requirement with its excellent performance, and has been widely used in the modern electronic assembly industry. Due to the harm of lead to the environment and the poison to the human body, more and more people pay more and more attention to it. Lead-free electronic and electrical products have become a global trend.
目前，被广泛推荐使用的无铅软钎料如Sn-3.0Ag-0.5Cu、Sn-0.7Cu合金能与铜形成良好的润湿结合，但是与金属铝之间的互溶度小，都不能很好地兼容Cu-Al异种金属的钎焊。由于金属间化合物的脆性，大大降低了焊接接头的强度及韧性，且易导致热裂纹，使得焊接接头的可靠性明显下降。同时银还带来了焊料合金成本的上升，也限制了Sn-Ag-Cu系合金的使用。At present, widely recommended lead-free solders such as Sn-3.0Ag-0.5Cu and Sn-0.7Cu alloys can form a good wetting bond with copper, but the mutual solubility with metal aluminum is small and cannot be very good. Good compatibility with brazing of Cu-Al dissimilar metals. Due to the brittleness of intermetallic compounds, the strength and toughness of welded joints are greatly reduced, and thermal cracks are easily caused, which significantly reduces the reliability of welded joints. At the same time, silver also increases the cost of solder alloys, and also limits the use of Sn-Ag-Cu alloys.
发明内容 Contents of the invention
本发明的目的是提供了一种适用于铜铝异种金属软钎焊的无铅焊料合金。The object of the present invention is to provide a lead-free solder alloy suitable for copper-aluminum dissimilar metal soldering.
本发明所述的焊料合金，按重量百分比计由以下组分组成：Zn 0.1～3.0，Cu 0.2～3.5，Ce 0.001～0.6，P 0.001～0.14，Ge或/和Ga 0.001～0.13，余量为Sn。The solder alloy of the present invention is composed of the following components by weight percentage: Zn 0.1～3.0, Cu 0.2～3.5, Ce 0.001～0.6, P 0.001～0.14, Ge or/and Ga 0.001～0.13, and the balance is Sn.
从Zn-Al相图上可以看到，由于Zn、Al互溶度较大，在很大范围内生成固溶体，因此可提高钎料在Al母材上的结合强度及其润湿性。接头界面的研究结果表明，钎料与Al母材的结合同时存在两种结构。在钎剂的作用下，钎料在Al晶界及晶粒表面均有较强的润湿作用，钎料中的Zn沿表面能较高的晶界及晶粒的棱角处向Al晶粒内部渗透，在晶粒的边缘处产生Zn-Al固溶体，形成钎料与母材间的固溶结合。与此同时，自Al母材某些点上Al向钎料中突刺生长过程中，Zn与Sn渗入，形成Al-Sn-Zn针状固溶体的嵌入结合，这就是钎焊接头具有特殊强度的原因。钎料强度会随着Zn含量的增加而增加，熔化温度也呈下降趋势。但大量的Zn易在焊料表面形成氧化而造成合金具有较大的表面张力，严重影响了润湿性，所以试验证明Zn含量为0.1～3.0％，优选为0.2～2.8％，更进一步为0.5～2.4％。It can be seen from the Zn-Al phase diagram that due to the large mutual solubility of Zn and Al, a solid solution is formed in a wide range, so the bonding strength and wettability of the solder on the Al base material can be improved. The research results of the joint interface show that there are two structures in the combination of the solder and the Al base metal. Under the action of the flux, the solder has a strong wetting effect on the Al grain boundary and the surface of the grain, and the Zn in the solder moves toward the interior of the Al grain along the grain boundary with high surface energy and the corners of the grain. Infiltration, Zn-Al solid solution is generated at the edge of the grain, forming a solid solution bond between the solder and the base metal. At the same time, during the growth of Al from certain points on the Al base material into the solder, Zn and Sn infiltrate to form an embedded combination of Al-Sn-Zn needle-like solid solution, which is why the brazing joint has special strength. . The strength of solder increases with the increase of Zn content, and the melting temperature also shows a downward trend. However, a large amount of Zn is easy to form oxidation on the surface of the solder, causing the alloy to have a large surface tension, which seriously affects the wettability, so the test proves that the Zn content is 0.1-3.0%, preferably 0.2-2.8%, and further 0.5- 2.4%.
在含Zn的钎料中加入Cu，会使得合金富Zn相中游离态的Zn原子与Cu生成了Cu-Zn化合物，即使在熔化时，由于熔化温度较低，合金中会大量存在Cu-Zn的短程有序结构，甚至中程有序结构，这必然会降低Zn原子的活性，减少Zn原子在钎料表面的氧化，从而有效降低液态钎料的表面张力，使得液态钎料能较好地在Cu母材上铺展开来而获得更小的润湿角。Cu、Zn的同时加入可抑制铜界面处Cu-Zn金属间化合物的生长速度，减少Zn对铝的溶蚀，提高接头机械强度。Adding Cu to the Zn-containing solder will cause the free Zn atoms in the Zn-rich phase of the alloy to form Cu-Zn compounds with Cu. Even during melting, due to the low melting temperature, there will be a large amount of Cu-Zn in the alloy. Short-range ordered structure, even medium-range ordered structure, which will inevitably reduce the activity of Zn atoms, reduce the oxidation of Zn atoms on the surface of the solder, thereby effectively reducing the surface tension of the liquid solder, so that the liquid solder can be better in the Cu base material spread out to obtain a smaller wetting angle. The simultaneous addition of Cu and Zn can inhibit the growth rate of Cu-Zn intermetallic compounds at the copper interface, reduce the corrosion of aluminum by Zn, and improve the mechanical strength of the joint.
Cu的加入还可以改善钎料在铜上的润湿性，提高机械性能，可以抑制Cu基底向钎料合金中的溶蚀。钎料的抗拉强度也会因为Cu的添加而得到明显增强，Cu的加入会使钎料的延伸率和断面收缩率降低。如果Cu含量太小，性能改善不明显；过高的Cu含量则导致熔化温度升高，润湿性变差，还会生成脆性Cu-Sn金属间化合物，甚至Cu-Zn相的出现，降低了合金的结合强度。所以试验证明Cu含量为0.2～3.5％，优选为0.2～3.3％，更进一步为0.3～2.9％。The addition of Cu can also improve the wettability of the solder on copper, improve the mechanical properties, and inhibit the dissolution of the Cu substrate into the solder alloy. The tensile strength of the solder will also be significantly enhanced by the addition of Cu, and the addition of Cu will reduce the elongation and reduction of area of the solder. If the Cu content is too small, the performance improvement is not obvious; if the Cu content is too high, the melting temperature will increase, the wettability will deteriorate, and brittle Cu-Sn intermetallic compounds will be formed, and even the appearance of Cu-Zn phase will reduce the Alloy bond strength. Therefore, experiments have proved that the Cu content is 0.2-3.5%, preferably 0.2-3.3%, and further 0.3-2.9%.
由于稀土元素的净化作用、变质作用和微合金化作用，添加稀土能改善钎料的综合机械性能、工艺性能和使用性能。通常的办法都是加入以Ce、La为主的混合稀土。经过反复试验研究，结果表明La对提高合金性能没太大作用，而Ce做为一种表面活性元素，加入后可细化晶粒，提高钎料耐腐蚀性，改善接头强度，有效解决了发生蠕变、热疲劳等问题导致钎焊接头的失效隐患。稀土Ce的加入有除气和调制合金细化的作用。在焊料中通常溶解有氧、氮等气体，由于氧的存在，焊料合金很容易被氧化，而稀土元素Ce对氧有一定的吸附作用，使得氧的氧化能力下降，还能使氧化层表面由疏松变得致密，焊料不易进一步被氧化，从而提高焊料的抗氧化能力。但随着Ce含量的增加，会在焊接表面生成过多的氧化物，妨碍了焊料在母材上的铺展，所以Ce含量为0.001～0.6％，优选为0.005～0.3％，更进一步为0.009～0.2％。Due to the purification, modification and microalloying of rare earth elements, the addition of rare earth can improve the comprehensive mechanical properties, process performance and serviceability of the solder. The usual method is to add mixed rare earths mainly composed of Ce and La. After repeated experiments and research, the results show that La does not have much effect on improving the properties of the alloy, and Ce, as a surface active element, can refine the grains after adding, improve the corrosion resistance of the solder, improve the joint strength, and effectively solve the problem of Problems such as creep and thermal fatigue lead to potential failure of brazed joints. The addition of rare earth Ce has the effect of degassing and modulating alloy refinement. Oxygen, nitrogen and other gases are usually dissolved in solder. Due to the existence of oxygen, the solder alloy is easily oxidized, and the rare earth element Ce has a certain adsorption effect on oxygen, which reduces the oxidation ability of oxygen and makes the surface of the oxide layer from The loose becomes dense, and the solder is not easy to be further oxidized, thereby improving the oxidation resistance of the solder. However, as the Ce content increases, too many oxides will be generated on the welding surface, which hinders the spreading of the solder on the base metal, so the Ce content is 0.001-0.6%, preferably 0.005-0.3%, and further 0.009- 0.2%.
在焊料中加P可以改善合金的抗氧化性和润湿性。其抗氧化性和润湿性可以通过添加Ge、Ga得到进一步增强。焊料中存在的P、Ge或Ga熔化状态下会向焊料表面扩散，并在表面形成一层结构细腻、致密的集肤层。由于集肤层的作用，避免了熔融焊料直接与空气接触，防止了熔化的焊料被氧化，润湿性能得到了改善。Adding P to the solder can improve the oxidation resistance and wettability of the alloy. Its oxidation resistance and wettability can be further enhanced by adding Ge and Ga. The P, Ge or Ga existing in the solder will diffuse to the surface of the solder in the molten state, and form a fine and dense skin layer on the surface. Due to the effect of the skin layer, the molten solder is prevented from being in direct contact with the air, the molten solder is prevented from being oxidized, and the wettability is improved.
如果P添加量少，对性能基本上没什么改善，含量过多，会在其表面形成具有粘性的熔化焊料合金，引起焊接缺陷。所以P含量为0.001～0.14％，优选为0.0015～0.11％，最优选为0.002～0.1％。If the amount of P added is small, there is basically no improvement in performance, and if the content is too high, a viscous molten solder alloy will be formed on the surface, causing soldering defects. Therefore, the P content is 0.001-0.14%, preferably 0.0015-0.11%, most preferably 0.002-0.1%.
同样地，如果Ge、Ga含量过高会导致熔化焊料表面粘性的增加，妨碍焊接操作。所以Ge或/和Ga的含量为0.001～0.13％，优选为0.001～0.10％，最优选为0.0015～0.09％。Similarly, if the content of Ge and Ga is too high, the surface viscosity of the molten solder will increase, hindering the soldering operation. Therefore, the content of Ge and/or Ga is 0.001-0.13%, preferably 0.001-0.10%, most preferably 0.0015-0.09%.
抗氧化元素P、Ge、Ga的加入有效防止了由于Zn的易氧化性而带来钎料的易氧化，增强了钎料的实用性。The addition of anti-oxidation elements P, Ge, and Ga effectively prevents the easy oxidation of the solder due to the easy oxidation of Zn, and enhances the practicability of the solder.
具体实施方式Detailed ways
在本发明合金的制备过程中，由于Sn、Zn、Cu、Ce、P的熔点差异加大，且Ce、Zn和P容易烧损，为了精确地控制合金成分，保证产品质量，采用了中间合金的形式加入各种合金元素，制备方法如下：In the preparation process of the alloy of the present invention, since the differences in the melting points of Sn, Zn, Cu, Ce, and P increase, and Ce, Zn, and P are easily burned, in order to accurately control the alloy composition and ensure product quality, an intermediate alloy is used. Various alloying elements are added in the form of , the preparation method is as follows:
Sn-Cu中间合金：将99.95％的精Sn加入到石墨坩埚中，熔化后升温，至Cu的熔化温度，加入99.95％的纯Cu。精Sn与纯Cu的质量百分比按90∶10来配制，搅拌均匀，静置，浇铸成含Cu量为10％的Sn-Cu中间合金锭。Sn-Cu master alloy: Add 99.95% refined Sn into the graphite crucible, heat up after melting, and add 99.95% pure Cu to the melting temperature of Cu. The mass percentage of refined Sn and pure Cu is prepared according to 90:10, stirred evenly, left standing, and casted into a Sn-Cu master alloy ingot with a Cu content of 10%.
Sn-Zn中间合金：将99.95％的精Sn加入到石墨坩埚中，熔化后升温，至Zn的熔化温度，加入99.95％的Zn。精Sn与Zn的质量百分比按91∶9来配制，搅拌均匀，静置，浇铸成含Zn量为9％的Sn-Zn中间合金锭。Sn-Zn master alloy: Add 99.95% refined Sn into the graphite crucible, heat up after melting, and add 99.95% Zn to the melting temperature of Zn. The mass percentage of refined Sn and Zn is prepared according to 91:9, stirred evenly, left standing, and casted into a Sn-Zn master alloy ingot with a Zn content of 9%.
Sn-Ce中间合金：将99.95％的精Sn加入到石墨坩埚中，熔化后升温，至Ce的熔化温度，加入99.95％的Ce。精Sn与Ce的质量百分比按91∶3来配制，搅拌均匀，静置，浇铸成含Ce量为3％的Sn-Ce中间合金锭。Sn-Ce master alloy: Add 99.95% refined Sn into the graphite crucible, heat up after melting, and add 99.95% Ce to the melting temperature of Ce. The mass percentage of refined Sn and Ce is prepared according to 91:3, stirred evenly, left standing, and casted into a Sn-Ce master alloy ingot with a Ce content of 3%.
Sn-P中间合金：将99.95％的精Sn加入到石墨坩埚中，熔化后升温至500℃，加入AR级的P。精Sn与P的质量百分比按98∶2来配制，搅拌均匀，静置，浇铸成含P量为2.0％的Sn-P中间合金锭。Sn-P master alloy: Add 99.95% refined Sn into the graphite crucible, heat up to 500°C after melting, and add AR grade P. The mass percentage of refined Sn and P is prepared according to 98:2, stirred evenly, left standing, and casted into a Sn-P master alloy ingot with a P content of 2.0%.
按合金成分计算称量好Sn-Cu中间合金锭、Sn-Zn中间合金锭、Sn-Ce中间合金锭、Sn-P中间合金锭及Ge或/和Ga，将配好的合金成分采用坩锅感应熔炼。充分搅拌至完全熔化，静置一段时间，浇铸，得到的焊料合金锭，通过进一步加工制成本发明合金成分的产品如焊Sn条、焊Sn棒、焊Sn丝、焊Sn球及焊Sn膏等形式。具体实施方式如下：Calculate and weigh the Sn-Cu master alloy ingot, Sn-Zn master alloy ingot, Sn-Ce master alloy ingot, Sn-P master alloy ingot and Ge or/and Ga according to the alloy composition, and use the crucible to prepare the alloy composition induction melting. Fully stir to melt completely, leave standstill for a period of time, cast, the obtained solder alloy ingot, through further processing, make the product of alloy composition of the present invention such as welding Sn bar, welding Sn bar, welding Sn wire, welding Sn ball and welding Sn paste and other forms. The specific implementation is as follows:
实施例1：各组份按重量百分比计分别为：Zn 0.7％，Cu 0.6％，Ce 0.01％，P 0.002％，Ga 0.0015％，余量为Sn。Embodiment 1: each component is respectively by weight percent: Zn 0.7%, Cu 0.6%, Ce 0.01%, P 0.002%, Ga 0.0015%, and the balance is Sn.
实施例2：各组份按重量百分比计分别为：Zn 0.9％，Cu 0.8％，Ce 0.05％，P 0.0265％，Ga 0.0118％，Ge 0.0117％，余量为Sn。Embodiment 2: each component is respectively by weight percentage: Zn 0.9%, Cu 0.8%, Ce 0.05%, P 0.0265%, Ga 0.0118%, Ge 0.0117%, and the balance is Sn.
实施例3：各组份按重量百分比计分别为：Zn 1.1％，Cu 1.2％，Ce 0.08％，P 0.051％，Ga 0.0458％，余量为Sn。Embodiment 3: each component is respectively by weight percentage: Zn 1.1%, Cu 1.2%, Ce 0.08%, P 0.051%, Ga 0.0458%, and the balance is Sn.
实施例4：各组份按重量百分比计分别为：Zn 1.5％，Cu 1.6％，Ce 0.1％，P 0.0755％，Ga 0.0679％，余量为Sn。Embodiment 4: each component is respectively by weight percentage: Zn 1.5%, Cu 1.6%, Ce 0.1%, P 0.0755%, Ga 0.0679%, and the balance is Sn.
实施例5：各组份按重量百分比计分别为：Zn 1.85％，Cu 2.1％，Ce 0.12％，P 0.1％，Ga 0.09％，余量为Sn。Embodiment 5: each component is respectively by weight percentage: Zn 1.85%, Cu 2.1%, Ce 0.12%, P 0.1%, Ga 0.09%, and the balance is Sn.
对上述实施例中的焊料合金进行了拉伸性能和铺展性的测量，在260℃下实现铝线在铜板上的焊接，并在拉伸试验机上进行拉伸试验，记录断裂载荷。铺展性试验是采用焊料合金在铝片上进行铺展的。The tensile properties and spreadability of the solder alloys in the above examples were measured, and the welding of aluminum wires on copper plates was realized at 260° C., and a tensile test was performed on a tensile testing machine, and the breaking load was recorded. The spreadability test is performed by spreading the solder alloy on an aluminum sheet.
试验结果如下表所示：The test results are shown in the table below:
从上表可以看出，本发明的焊料合金在铜铝异种金属的连接上具有较好铺展性，且合金的拉伸性能优于Sn63Pb37和Sn-0.7Cu焊料合金。It can be seen from the above table that the solder alloy of the present invention has good spreadability in the connection of copper-aluminum dissimilar metals, and the tensile property of the alloy is better than that of Sn63Pb37 and Sn-0.7Cu solder alloys.
本发明并不局限于上述实施案例，在实际应用过程中，可根据的不同领域不同的性能要求的使用场合，选择上述各实施案例中的合金成分，或者除上述实施案例以外的不同成分配比，但均不超过本发明申请的权利要求书的范围。The present invention is not limited to the above-mentioned examples of implementation. In the actual application process, the alloy components in the above-mentioned examples of implementation can be selected according to the use occasions of different performance requirements in different fields, or different composition ratios other than the above-mentioned examples of implementation. , but none of them exceed the scope of the claims of the present application.
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| CN102814595B (en) * | 2012-05-05 | 2015-04-08 | 大连理工大学 | Sn-Zn based near-eutectic lead-free solder alloy for aluminum-copper soldering |
| CN102642099A (en) * | 2012-05-05 | 2012-08-22 | 大连理工大学 | A kind of Sn-Zn based lead-free solder alloy for aluminum-copper soldering and preparation method thereof |
| CN103317253B (en) * | 2013-06-03 | 2015-07-22 | 北京科技大学 | Zn-Al-Cu based brazing filler metal for aluminum/copper brazing and preparation method thereof |
| CN105618954A (en) * | 2016-03-15 | 2016-06-01 | 力创(台山)电子科技有限公司 | Welding flux for welding in electro-hydraulic servo valve assembly technology |
| 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 |
| CN107999996B (en) * | 2017-12-13 | 2019-12-10 | 华南理工大学 | tin-base lead-free solder alloy for soft soldering of aluminum and aluminum alloy |
| CN108213764A (en) * | 2017-12-13 | 2018-06-29 | 华南理工大学 | A kind of tin base leadless soldering-flux alloy for effectively reducing base material meltage |
| CN110303269A (en) * | 2019-07-02 | 2019-10-08 | 华侨大学 | Sn-Cu-Ti Alloy Solder for Low Temperature Brazing of Diamond and Its Application |
| CN113579547B (en) * | 2021-08-12 | 2023-03-10 | 郑州机械研究所有限公司 | A kind of solder paste for copper-aluminum dissimilar metal flux-free brazing and brazing method |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030021718A1 (en) * | 2001-06-28 | 2003-01-30 | Osamu Munekata | Lead-free solder alloy |
| JP2005254298A (en) * | 2004-03-12 | 2005-09-22 | Nippon Steel Corp | Solder alloy for semiconductor mounting, manufacturing method thereof, solder ball, electronic member |
| EP1647352A1 (en) * | 2004-10-16 | 2006-04-19 | Stannol GmbH | Solder material |
| WO2006059115A1 (en) * | 2004-12-01 | 2006-06-08 | Alpha Fry Limited | Solder alloy |
-
2007
- 2007-01-18 CN CNB2007100263789A patent/CN100439027C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030021718A1 (en) * | 2001-06-28 | 2003-01-30 | Osamu Munekata | Lead-free solder alloy |
| CN1400081A (en) * | 2001-06-28 | 2003-03-05 | 千住金属工业株式会社 | Lead-Free Solder Alloys |
| JP2003094195A (en) * | 2001-06-28 | 2003-04-02 | Senju Metal Ind Co Ltd | Lead-free solder alloy |
| JP2005254298A (en) * | 2004-03-12 | 2005-09-22 | Nippon Steel Corp | Solder alloy for semiconductor mounting, manufacturing method thereof, solder ball, electronic member |
| EP1647352A1 (en) * | 2004-10-16 | 2006-04-19 | Stannol GmbH | Solder material |
| WO2006059115A1 (en) * | 2004-12-01 | 2006-06-08 | Alpha Fry Limited | Solder alloy |
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