WO2007014529A1 - Alliage de brasage sans plomb a point de fusion bas - Google Patents

Alliage de brasage sans plomb a point de fusion bas Download PDF

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Publication number
WO2007014529A1
WO2007014529A1 PCT/CN2006/001942 CN2006001942W WO2007014529A1 WO 2007014529 A1 WO2007014529 A1 WO 2007014529A1 CN 2006001942 W CN2006001942 W CN 2006001942W WO 2007014529 A1 WO2007014529 A1 WO 2007014529A1
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Prior art keywords
alloy
solder alloy
melting point
lead
solder
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PCT/CN2006/001942
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English (en)
French (fr)
Inventor
Jusheng Ma
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Jusheng Ma
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Priority to JP2008524346A priority Critical patent/JP2009502512A/ja
Publication of WO2007014529A1 publication Critical patent/WO2007014529A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin

Definitions

  • the invention relates to a low melting point lead-free solder alloy, which is suitable for electronic assembly and packaging in the fields of telecommunications, aerospace, automobile and the like, and preparation of electronic, electrical equipment and communication equipment, and belongs to the technical field of electronic materials and electronic preparation. Background technique
  • Sn-Pb alloy plays a dominant role in the assembly of electronic components.
  • Sn-Pb alloy has excellent wettability and weldability, electrical conductivity, mechanical properties, low cost, etc., due to the toxicity of Pb and Pb compounds, improper use can pollute the environment and damage the health of workers. Protection regulations are becoming more sophisticated and strict, and the ban on the use of lead is growing.
  • Sn-Ag-Cu alloys have good application prospects and have been recommended by NEMI, DTI, Soldertec, etc. in the United States.
  • Sn-Ag-Cu solder alloy its comprehensive performance is superior, but it also has the disadvantages of poor wettability, coarse and uneven distribution of the alloy structure, and its biggest disadvantage is that it has too high melting temperature. ⁇ 220 °C. Therefore, if a Sn-Ag-Cu alloy is used, it is necessary to modify the existing production equipment, and it also involves quality problems such as poor heat resistance of the electronic components and the substrate, resulting in a decrease in reliability, thereby increasing the cost. Summary of the invention
  • the object of the present invention is to prepare a low melting point lead-free solder alloy, which has a lower melting temperature and a melting point of 183 ⁇ close to that of the Sn-Pb eutectic alloy, thereby having better soldering performance than the Sn-Zn eutectic. Replace the Sn-Pb alloy.
  • the balance is Sn.
  • the lead-free solder having the above composition can be produced by a general method of casting, that is, weighing a metal raw material, and heating and stirring in air in a crucible or a crucible.
  • the raw material metal is melted in the air, and impurities or non-metals in the raw material metal and alloy react with the air, and as a result, a soluble gas such as soluble nitrogen or oxygen remains in the solder alloy to lower the splicing performance. Therefore, the lead-free content alloy of the present invention is preferably smelted in a vacuum or in an inert gas.
  • the lead-free solder alloy of the present invention can be obtained by various general methods known in the art, such as pastes, powders, blocks, rods, balls and wires, etc., and then subjected to various welding processes, such as reflow soldering. , wave soldering and hand soldering to meet a variety of needs.
  • the low melting point lead-free solder alloy prepared by the method of the invention has the advantages of lowering the melting point of the solder alloy, generally less than 200 ° C, about 190 ° C or lower; second, the solid-liquid phase difference of the alloy can be Up to the following, it can avoid the defects of solder joint separation; Thirdly, the alloy structure is uniform, the microstructure of the microstructure is fine, and the strength of the alloy is improved.
  • the strength of the solder joint is more than 1/3; Fourth, the spreading of the solder alloy The rate can be similar to that of the original Pb-Sn eutectic alloy; the fifth is that the solder alloy can be easily processed into materials such as rods, wires, powders (up to about 1 micron), pastes, etc., which can be used for soldering of various soldering methods (sticks, Welding wire, solder balls, printing paste, etc.). detailed description
  • the low-melting-point-free solder alloy of the present invention wherein the composition of each chemical component is: Z 4 ⁇ 12, Ag: 0 ⁇ 2. 5, Bi: 0. 5 ⁇ 2. 5, In: 0 ⁇ 5. 0, P: 0. 005 ⁇ 0. 02, the margin is Sn.
  • Zn and Ag can form Sn-Zn, Sn-Ag eutectic with the Sn matrix to lower the melting point of the solder and improve the mechanical properties of the solder, especially the Sn-Ag solder and the conventional Sn-Pb eutectic phase. It has excellent creep fatigue resistance. If the amount of Ag added is less than 0.5%, these effects will not be obvious. Adding more than 0.5% of Ag causes the liquidus temperature of the solder alloy to rise sharply, resulting in an increase in the soldering temperature, which may cause thermal damage to the electronic components. 5% ⁇ The content of Ag is preferably 0-2. 5%.
  • the content of Zn in the present invention is limited to 4 to 12%.
  • Adding a large amount of Bi or In can lower the melting point of the alloy, but it also causes a lot of problems.
  • the addition of Bi will make the alloy very hard and brittle, so the alloy will not be able to be made into a linear electrode, and when the alloy is used for splicing, the solder joint will crack due to the inability to withstand minor impacts.
  • the content of Bi is limited to 0. 5-2. 5%. Since In is expensive, it is not appropriate to add a large amount of In. 0% ⁇ In the present invention, the content of In is limited to 0-5. 0%.
  • P If P is added to the alloy, P will form a film on the surface of the molten alloy during welding, thereby preventing the solder from directly contacting the surrounding air to prevent oxidation.
  • the content of P is less than 0.001%, this performance is not obvious.
  • the content of P exceeds 1%, the weldability of the alloy deteriorates. 005- 0. 02% ⁇ The content of P is 0. 005- 0. 02%.
  • the preparation method of each embodiment is as follows: The metal raw material is weighed according to the proportion (% by weight), and is added to the furnace for multiple smelting, and after casting, Sn-Zn-Ag-Bi-In-P is obtained. Lead solder alloy. It can replace the existing Sn-Pb alloy, has a melting point close to the Sn-Pb alloy and better welding performance.
  • Example 1 The metal raw material is weighed according to the proportion (% by weight), and is added to the furnace for multiple smelting, and after casting, Sn-Zn-Ag-Bi-In-P is obtained.
  • Lead solder alloy It can replace the existing Sn-Pb alloy, has a melting point close to the Sn-Pb alloy and better welding performance.
  • the weight percentage of each raw material is: Zn: 7, Ag: 0.5, Bi: 2.5, In: 0.5, P.-0.015, and the balance is Sn.
  • the solidus temperature of the obtained alloy was 193.04 ⁇ , and the liquidus temperature was 201.85 ⁇ , and the spreading rate was
  • the weight percentage of each raw material is: Zn: 8, Ag: 0.8, Bi: 1, In : 2, P: 0.01, and the balance is Sn.
  • the solid phase temperature of the obtained alloy was 191.69 ⁇ , the liquidus temperature was 195.07 ⁇ , and the spreading rate was 57.1%.
  • the weight percentage of each raw material is: Zn: 10, Ag: 0, Bi: 1, In : 0, P: 0.015, and the balance is Sn.
  • the solid phase temperature of the obtained alloy was 195, 72 ° C, the liquidus temperature was 197.71 ° C, and the spreading rate was 60.8%.
  • the weight percentage of each raw material is: Zn: 9, Ag: 0, Bi: 2.5, In: 1.5, P: 0.01, and the balance is Sn.
  • the solid phase temperature of the obtained alloy was 191.55 ° C, the liquidus temperature was 194.7 ° C, and the spreading rate was 67.6%.
  • the weight percentage of each raw material was: Zn: 11.5, Ag: 1.98, Bi: 1.5, In: 4, P: 0.015, and the amount of ruthenium was Sn.
  • the solid phase temperature of the obtained alloy was 192.84 ⁇ , the liquidus temperature was 195.6 ⁇ , and the spreading rate was 58.0%.
  • the weight percentage of each raw material is: Zn: 5, Ag: 0.5, Bi: 1, In : 0, P: 0.02, and the balance is Sn.
  • the solid phase temperature of the obtained alloy was 197.09 ° C, the liquidus temperature was 198.63 ° C, and the spreading rate was 60.4%.
  • the weight percentage of each raw material is: Z 6, Ag: 0.8, Bi: 1.5, In: 0.5, P: 0, and the balance is Sn.
  • the solid phase temperature of the obtained alloy was 194.73 ° C, the liquidus temperature was 197.19 ° C, and the spreading rate was 61.3%.
  • the weight percentage of each raw material is: Zn: 7, Ag: 1, Bi: 2, In: 1, P: 0.005, and the balance is Sn.
  • the solid phase temperature of the obtained alloy was 193.20 ⁇ , the liquidus temperature was 195.99 ° C, and the spreading rate was 61.6%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Description

一种低熔点无铅焊料合金 技术领域
本发明涉及一种低熔点无铅焊料合金， 适用于电信、 航天、 汽车等各领域的电子组 装与封装及电子、 电气设备、 通讯器材的制备， 属于电子材料、 电子制备技术领域。 背景技术
Sn-Pb合金作为现代电子工业的主要封接材料，在电子部件的装配上占着主导地位。 虽然 Sn-Pb合金具有优异的润湿性及焊接性、 导电性、 力学性能、 成本低等特点， 但是 由于 Pb及 Pb化合物具有毒性， 使用不当会污染环境且损害工人的身体健康， 随着环境 保护法规的日趋完善和严格， 禁止使用铅的呼声日益髙涨。
因此， 各国纷纷出台有关禁止含铅焊料在电子产业中使用的法令。 2000年 6月： 美 国 IPCLead- FreeRoadmap第 4版发表，建议美国企业界于 2001年推出无铅化电子产品， 200 年实现全面无铅化； 欧洲则在推动无铅立法上采取了更为积极的态度， 2003年 2 月 13 日， 欧盟在其 《官方公报》上公布 《关于在电子电气设备中禁止使用某些有害物 质 指 令 》 ， 正 式 批 准 WEEE (WasteElectricalandElectronicEquipment) 和 Rolls (RestrictionofHa?ardousSubstances)的官方指令生效，强制要求自 2006年 7月 1日起， 在欧洲市场上销售的电子产品必须为无铅的电子产品； 亚洲方面， 日本政府从 2003年 1月开始全面推行无铅化， 并以 "无铅"牌阻止或限制美、 中、 韩、 台湾地区及 欧洲有铅电子产品的进口； 中国政府已于 2003年 3月由信息产业部拟定《电子信息产 品生产污染防治管理法》 自 2006年 7月 1日禁止电子产品含铅。
在当前的的无铅焊料中 Sn-Ag-Cu系合金具有较好的应用前景， 得到了美国 NEMI、 英国 DTI、 Soldertec等的推荐。 对于 Sn-Ag-Cu系焊料合金来说， 其综合性能比较优越， 但它也具有润湿性较差， 合金组织粗大、 分布不均匀等缺点， 其最大的缺点在于具有太 高的熔化温度， 髙达 220 °C。 所以如果使用 Sn- Ag- Cu合金， 就需要改造现有的生产 设备， 也牵涉到电子元器件及基板的耐热性差而导致可靠性降低等质量问题， 从而增加成本。 发明内容
本发明的目的是制备一种低熔点无铅焊料合金， 使焊料具有较低的熔化温度， 接近 Sn- Pb共晶合金的熔点 183Ό , 从而比 Sn- Zn共晶具有更好的焊接性能， 以取 代 Sn- Pb合金。
本发明提出的低瑢点无铅焊料合金， 其中各化学成分的重量百分比组成为- Zn 4〜12
Ag 0〜2. 5
Bi 0. 5〜2. 5
In 0〜5· 0 P 0·005〜0.02
余量为 Sn。
具有上述组成的无铅焊料可以通过一般方法浇铸制造， 即称重金属原料， 并 在坩埚或熔锅中在空气中加热并搅拌。 但是， 在空气中熔化原料金属， 原料金属 及合金中的杂质或非金属物与空气发生反应， 其结果是可溶性气体， 诸如可溶性 氮或氧存留在焊料合金中， 降低悍接性能。 因此， 本发明的无铅含量合金最好在 真空中或者在惰性气体中冶炼。
本发明的无铅焊料合金可以通过现有技术中已知的一般制作方法获得各种物 理形式， 如膏、 粉、 块、 棒、 球和丝等， 进而进行多种焊接工艺， 如再流焊、 波 峰焊和手工焊等， 满足多种需要。
利用本发明方法制备的低熔点无铅焊料合金， 其优点一是降低了焊料合金的熔 点， 一般都小于 200°C， 在 190°C左右或更低； 二是合金的固液相线差可达 以下， 可 避免焊点分离缺陷； 三是合金组织均匀， 其微观结构组织微细化， 使合金强度提高， 与 其他材料焊接后， 焊点强度提髙 1/3以上； 四是焊料合金的铺展率可达到与原 Pb— Sn共 晶合金相仿； 五是焊料合金易于加工成材， 如棒、 丝、 粉料 （可达 1微米左右）、 膏等， 可用于各种焊接方法的焊料 （棒、 焊丝、 焊球、 印刷浆料等）。 具体实施方式
本发明提出的低熔点无铅焊料合金，其中各化学成分的重量百分比组成为： Z 4〜 12, Ag: 0〜2. 5， Bi : 0. 5〜2. 5， In: 0〜5. 0， P: 0. 005〜0. 02， 余量为 Sn。
本发明的焊料合金中， Zn和 Ag可以与 Sn基体形成 Sn- Zn、 Sn- Ag共晶以降低焊料 的熔点、提高焊料的力学性能， 尤其 Sn- Ag系焊料与传统 Sn-Pb共晶相比有着优异的抗 蠕变疲劳性能。 如果 Ag的加入量少于 0. 5%， 这些作用就将不明显。 加入 5. 0%以上的 Ag会使焊料合金的液相线温度急剧升高，导致钎焊温度的升高从而使电子元器件可能会 遭受热损伤。 本发明中 Ag的含量优选为 0-2. 5%。 Zn的含量如果过小或者过大， 则熔 化温度范围（熔程)过宽， 因此本发明中 Zn的含量限制在 4〜12%。添加大量的 Bi或 In 可以降低合金的熔点， 但同时也会带来大量的问题。 添加 Bi将使得合金变得很硬并且 脆， 则合金将无法制作成线状焊条， 而当使用该合金进行悍接时， 焊点就会因为承受不 住微小的冲击而开裂。 本发明中 Bi的含量限制在 0. 5-2. 5%。 由于 In成本昂贵， 所以 添加大量的 In也不合适。 本发明中 In的含量限制在 0-5. 0%。 若在合金中掺入 P， 则 在焊接时， P会在熔融的合金表面形成一层薄膜， 从而阻止焊料直接接触周围的空气而 达到防止氧化的目的。 当 P的含量小于 0. 001 %时， 这一性能就不明显了。 当 P的含量 超过 1 %时， 合金的可焊性就会变差。 一般 P的含量为 0. 005- 0. 02%。
以下介绍本发明的实施例， 各实施例的制备方法为： 按配比（重量百分比）称重金 属原料， 加入炉中进行多次冶炼， 浇注后即得 Sn-Zn-Ag-Bi-In-P无铅焊料合金。 可替 代现有的 Sn-Pb合金， 具有接近 Sn-Pb合金的熔点以及较好的焊接性能。 实施例 1
各原料的重量百分比为： Zn: 7, Ag: 0.5， Bi: 2.5， In ： 0.5, P.- 0.015， 余量 为 Sn。 所得合金的固相线温度为 193.04Ό， 液相线温度为 201.85Ό， 铺展率为
77.2%。
实施例 2
各原料的重量百分比为： Zn: 8, Ag: 0.8, Bi: 1， In ： 2， P: 0.01， 余量为 Sn。 所得合金的固相线温度为 191.69Ό， 液相线温度为 195.07Ό, 铺展率为 57.1%。
实施例 3
各原料的重量百分比为： Zn: 10， Ag: 0, Bi: 1， In ： 0， P: 0.015， 余量为 Sn。 所得合金的固相线温度为 195， 72°C, 液相线温度为 197.71°C， 铺展率为 60.8%。
实施例 4
各原料的重量百分比为： Zn: 9， Ag: 0， Bi: 2.5, In ： 1.5， P: 0.01, 余量为 Sn。 所得合金的固相线温度为 191.55°C， 液相线温度为 194.7°C， 铺展率为 67.6%。
实施例 5
各原料的重量百分比为： Zn: 11.5, Ag: 1.98， Bi: 1.5, In ： 4， P: 0.015， 佘 量为 Sn。 所得合金的固相线温度为 192.84Ό, 液相线温度为 195.6Ό， 铺展率为 58.0%。
实施例 6
各原料的重量百分比为： Zn: 5， Ag: 0.5， Bi: 1， In ： 0， P: 0.02, 余量为 Sn。 所得合金的固相线温度为 197.09°C， 液相线温度为 198.63°C, 铺展率为 60.4%。
实施例 7
各原料的重量百分比为： Z 6， Ag: 0.8, Bi: 1.5, In ： 0.5， P: 0, 余量为 Sn。 所得合金的固相线温度为 194.73°C， 液相线温度为 197.19°C, 铺展率为 61.3%。
实施例 8
各原料的重量百分比为： Zn: 7, Ag: 1， Bi: 2, In ： 1， P: 0.005, 余量为 Sn。 所得合金的固相线温度为 193.20Ό, 液相线温度为 195.99°C， 铺展率为 61.6%。

Claims

权利要求书
1、'一种低熔点无铅焊料合金， 其特征在于该无铅焊料合金中各化学成分的重量 百分比组成为：
Zn 4〜12
Ag 0〜2. 5
Bi 0. 5~2. 5
In 0〜5. 0
P 0. 005〜0. 02
余量为 Sn。
PCT/CN2006/001942 2005-08-02 2006-08-02 Alliage de brasage sans plomb a point de fusion bas WO2007014529A1 (fr)

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JP2008524346A JP2009502512A (ja) 2005-08-02 2006-08-02 一種低融点無鉛はんだ合金

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CNB2005100873827A CN100494436C (zh) 2005-08-02 2005-08-02 一种低熔点无铅焊料合金
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CN102409299B (zh) * 2011-09-07 2014-08-06 三峡大学 一种氧化物陶瓷溅射靶的制备方法
CN102581506A (zh) * 2012-01-19 2012-07-18 天津大学 一种锡铋银系无铅焊料
CN102922164A (zh) * 2012-11-01 2013-02-13 青岛英太克锡业科技有限公司 一种用于软钎焊焊锡丝的Sn-Zn焊料及其制备方法
CN103042315B (zh) * 2013-01-22 2015-05-27 马莒生 耐热耐湿低熔点无铅焊料合金
KR101595950B1 (ko) * 2014-01-22 2016-02-19 한국기계연구원 황을 함유하는 솔더 합금 및 이의 제조방법
CN105499830A (zh) * 2016-03-04 2016-04-20 保定爱廸新能源股份有限公司 光伏焊带用Sn-Zn系无铅多元合金及其制备方法
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