CN100453245C - Lead-free tin-based soft solder - Google Patents
Lead-free tin-based soft solder Download PDFInfo
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- CN100453245C CN100453245C CNB2006100498474A CN200610049847A CN100453245C CN 100453245 C CN100453245 C CN 100453245C CN B2006100498474 A CNB2006100498474 A CN B2006100498474A CN 200610049847 A CN200610049847 A CN 200610049847A CN 100453245 C CN100453245 C CN 100453245C
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 86
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 abstract description 20
- 238000005476 soldering Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 description 51
- 239000000956 alloy Substances 0.000 description 51
- 238000002844 melting Methods 0.000 description 30
- 230000008018 melting Effects 0.000 description 30
- 239000010949 copper Substances 0.000 description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 229910020888 Sn-Cu Inorganic materials 0.000 description 15
- 229910019204 Sn—Cu Inorganic materials 0.000 description 15
- 229910020830 Sn-Bi Inorganic materials 0.000 description 12
- 229910018728 Sn—Bi Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 229910020938 Sn-Ni Inorganic materials 0.000 description 10
- 229910008937 Sn—Ni Inorganic materials 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229910009038 Sn—P Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 241001062472 Stokellia anisodon Species 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- 229910020994 Sn-Zn Inorganic materials 0.000 description 2
- 229910009069 Sn—Zn Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910020836 Sn-Ag Inorganic materials 0.000 description 1
- 229910020988 Sn—Ag Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- BSPSZRDIBCCYNN-UHFFFAOYSA-N phosphanylidynetin Chemical compound [Sn]#P BSPSZRDIBCCYNN-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
对焊接对象浸焊过程中溶蚀度低，可焊性好，强度和抗氧化性能高的无铅锡基软焊料，有以下四项，每项以其总质量计由下述质量百分数的组分组成：1、4.0-8.5%Cu，0.1-2.6%Bi，0.01-1.2%Ni，余量为Sn；2、4.0-8.5%Cu，0.1-2.6%Bi，0.01-1.2%Ni，0.001-0.15%P，余量为Sn；3、4.0-8.5%Cu，0.1-2.6%Bi，0.01-1.2%Ni，0.001-0.3%RE，余量为Sn；4、4.0-8.5%Cu，0.1-2.6%Bi，0.01-1.2%Ni，0.001-0.15%P，0.001-0.3%RE，余量为Sn。本发明适用于电子行业无铅化组装和封装。Lead-free tin-based soft solder with low solubility, good solderability, high strength and high oxidation resistance during the dip soldering process of the soldering object, has the following four items, each of which is composed of the following mass percentage components based on the total mass Composition: 1. 4.0-8.5% Cu, 0.1-2.6% Bi, 0.01-1.2% Ni, the balance being Sn; 2. 4.0-8.5% Cu, 0.1-2.6% Bi, 0.01-1.2% Ni, 0.001-0.15 %P, the balance is Sn; 3, 4.0-8.5%Cu, 0.1-2.6%Bi, 0.01-1.2%Ni, 0.001-0.3%RE, the balance is Sn; 4, 4.0-8.5%Cu, 0.1-2.6 %Bi, 0.01-1.2%Ni, 0.001-0.15%P, 0.001-0.3%RE, the balance is Sn. The invention is suitable for lead-free assembly and packaging in the electronic industry.
Description
本发明涉及焊料合金，特别是无铅焊料合金，主要用于电子行业的无铅化组装和封装。The invention relates to a solder alloy, especially a lead-free solder alloy, which is mainly used for lead-free assembly and packaging in the electronic industry.
背景技术 Background technique
电子行业用高频变压器是由线状的铜线卷绕而成，变压器线轴的卷绕开始处和卷绕终了处的端部引线需要与卷轴下端设置的端子接脚等电极相连接。传统的连接方式是采用锡铅焊锡进行浸焊。然而近几年来，人们越来越关注铅对环境的污染和对身体健康的损害，许多国家已相继出台了一系列法令和法规来防止电子产品所带来的生态问题，限制铅在电子产品中的使用。在无铅化绿色制造这一大趋势下，变压器端部引线也开始了无铅封接。High-frequency transformers used in the electronics industry are wound from linear copper wires, and the lead wires at the start and end of the winding of the transformer spool need to be connected to the terminal pins and other electrodes at the lower end of the spool. The traditional connection method is to use tin-lead solder for dip soldering. However, in recent years, people have paid more and more attention to the pollution of lead to the environment and the damage to their health. Many countries have successively issued a series of laws and regulations to prevent the ecological problems caused by electronic products and limit the use of lead in electronic products. usage of. Under the general trend of lead-free green manufacturing, lead-free sealing of transformer end leads has also begun.
目前已开发出的无铅焊料主要有Sn-Ag，Sn-Cu，Sn-Zn和Sn-Ag-Cu等，并通过添加Ag、Cu、P、Ni、In、Bi等元素获得不同性能的系列产品。如千住金属工业株式会社的JS3027441专利和艾奥瓦州立大学的US5527628专利，分别公开了各自的Sn-Ag-Cu系列无铅焊料；松下电器产业株式会社的CN1087994C专利和北京工业大学的CN1586793A专利申请公开了各自开发的Sn-Zn系列无铅焊料；千住金属工业株式会社的CN1496780A专利申请公开了一种Sn-Cu系列无铅焊料；韩国三星电机株式会社的CN1040302C、CN1040303C专利和CN1139607A专利申请公开了Sn-Bi系列无铅焊料等。The lead-free solders that have been developed so far mainly include Sn-Ag, Sn-Cu, Sn-Zn and Sn-Ag-Cu, etc., and a series of different properties can be obtained by adding elements such as Ag, Cu, P, Ni, In, Bi, etc. product. For example, the JS3027441 patent of Senju Metal Industry Co., Ltd. and the US5527628 patent of Iowa State University disclose their respective Sn-Ag-Cu series lead-free solders; the CN1087994C patent of Matsushita Electric Industrial Co., Ltd. and the CN1586793A patent application of Beijing University of Technology Disclosed the Sn-Zn series lead-free solder that develops respectively; The CN1496780A patent application of Senju Metal Industry Co., Ltd. discloses a kind of Sn-Cu series lead-free solder; Sn-Bi series lead-free solder, etc.
高频变压器铜线表面覆有绝缘涂层，浸焊过程中需要400℃的焊接温度来去除浸渍在熔融焊料中的铜引线表面涂层。由于浸焊温度较高，目前适用于变压器引线焊接的无铅焊料只有Sn-Cu焊料。Sn-Cu无铅焊料虽然在焊接性、物理和力学性能等方面能满足封装工艺，然而该焊料在浸焊过程中存在对铜引线的溶蚀程度较大这一明显缺点，即在浸焊过程中作为母材的铜引线会大量溶解到熔融的锡液中，从而导致引线线径变细程度较大，电子零件的引线断线事故率较高。这种溶蚀所导致的断线现象在细引线(直径小于0.1mm)浸锡过程中尤为严重。The surface of the high-frequency transformer copper wire is covered with an insulating coating, and a welding temperature of 400°C is required during the dip soldering process to remove the surface coating of the copper wire immersed in the molten solder. Due to the high soldering temperature, currently the only lead-free solder suitable for transformer lead soldering is Sn-Cu solder. Although the Sn-Cu lead-free solder can satisfy the packaging process in terms of solderability, physical and mechanical properties, etc., the solder has the obvious disadvantage of a large degree of corrosion to the copper leads during the dip soldering process, that is, during the dip soldering process A large amount of copper leads as the base material will be dissolved into the molten tin solution, resulting in a large reduction in the diameter of the lead wires, and a high rate of lead wire breakage accidents in electronic parts. The disconnection phenomenon caused by this corrosion is especially serious in the tin immersion process of thin leads (diameter less than 0.1mm).
发明内容 Contents of the invention
本发明要解决已知技术中的无铅焊料对铜引线溶蚀过大这一问题，为此提供本发明的无铅锡基软焊料，这种焊料对铜引线溶蚀程度较低，并具有低成本，高强度和良好润湿性的特点。The present invention will solve the problem that the lead-free solder in the known technology corrodes the copper lead too much, and provides the lead-free tin-based soft solder of the present invention for this reason. This solder has a low degree of corrosion to the copper lead and has a low cost. , high strength and good wettability characteristics.
为解决上述问题，本发明分为以下数种焊料。In order to solve the above-mentioned problems, the present invention is divided into the following several types of solders.
其一特殊之处是以该焊料总质量计它由以下质量百分数的组分组成：One of its special features is that it consists of the following components in mass percentages based on the total mass of the solder:
Cu 4.0-8.5％Cu 4.0-8.5%
Bi 0.1-2.6％Bi 0.1-2.6%
Ni 0.01-1.2％Ni 0.01-1.2%
Sn 余量。Sn margin.
其二特殊之处是以该焊料总质量计它由以下质量百分数的组分组成：The second special feature is that it consists of the following components in mass percentages based on the total mass of the solder:
Cu 4.0-8.5％Cu 4.0-8.5%
Bi 0.1-2.6％Bi 0.1-2.6%
Ni 0.01-1.2％Ni 0.01-1.2%
P 0.001-0.15％P 0.001-0.15%
Sn 余量。Sn margin.
其三特殊之处是以该焊料总质量计它由以下质量百分数的组分组成：The third special feature is that it consists of the following components in mass percentages based on the total mass of the solder:
Cu 4.0-8.5％Cu 4.0-8.5%
Bi 0.1-2.6％Bi 0.1-2.6%
Ni 0.01-1.2％Ni 0.01-1.2%
RE 0.001-0.3％RE 0.001-0.3%
Sn 余量。Sn margin.
其四特殊之处是以该焊料总质量计它由以下质量百分数的组分组成：Its fourth special feature is that it consists of the following components in mass percentages based on the total mass of the solder:
Cu 4.0-8.5％Cu 4.0-8.5%
Bi 0.1-2.6％Bi 0.1-2.6%
Ni 0.01-1.2％Ni 0.01-1.2%
P 0.001-0.15％P 0.001-0.15%
RE 0.001-0.3％RE 0.001-0.3%
Sn 余量。Sn margin.
添加Cu元素可显著降低焊料对铜引线的溶蚀程度，Cu含量小于4.0％时其作用不明显；而Cu含量大于8.5％时，会导致熔融焊料熔点过高，黏度太大，不仅弱化了焊料的润湿性，还易导致引线端部沾锡太多而肥大变粗，发生垂下的柱状现象。本发明无铅锡基软焊料Cu含量选择在4.0-8.5％范围内。Adding Cu element can significantly reduce the corrosion degree of solder to copper leads. When the Cu content is less than 4.0%, the effect is not obvious; when the Cu content is greater than 8.5%, the melting point of the molten solder will be too high and the viscosity will be too high, which not only weakens the solder. Wettability, it is also easy to cause the end of the lead to be stained with too much tin, which will become thicker and thicker, and the phenomenon of hanging columns will occur. The content of Cu in the lead-free tin-based soft solder of the present invention is selected within the range of 4.0-8.5%.
添加元素Bi可显著降低焊料熔化温度，并提高焊料的润湿性。Bi含量小于0.1％时，其作用不明显；然而Bi含量大于2.6％时，会导致焊料塑性变差。本发明无铅锡基软焊料Bi含量选择在0.1-2.6％范围内。Adding the element Bi can significantly reduce the melting temperature of the solder and improve the wettability of the solder. When the Bi content is less than 0.1%, its effect is not obvious; however, when the Bi content is greater than 2.6%, the plasticity of the solder will be deteriorated. The content of Bi in the lead-free tin-based soft solder of the invention is selected within the range of 0.1-2.6%.
Ni与Cu可无限固溶，添加Ni元素既能细化焊料合金组织，又能提高焊料的塑性。Ni含量小于0.01％时，其作用不明显；然而Ni含量大于1.2％时，焊料熔点高，黏度大，不仅弱化了焊料的润湿性，还易导致引线端部沾锡太多而肥大变粗。本发明无铅锡基软焊料Ni含量选择在0.01-1.2％范围内。Ni and Cu can be dissolved indefinitely, and the addition of Ni can not only refine the structure of the solder alloy, but also improve the plasticity of the solder. When the Ni content is less than 0.01%, its effect is not obvious; however, when the Ni content is greater than 1.2%, the solder melting point is high and the viscosity is high, which not only weakens the wettability of the solder, but also easily leads to too much tin on the end of the lead and becomes thicker. . The content of Ni in the lead-free tin-based soft solder of the invention is selected within the range of 0.01-1.2%.
添加元素P可提高焊料的抗氧化性能，降低熔融焊料的产渣量。P含量小于0.001％时，其作用不明显；而P含量大于0.15％时，焊料塑性较差。本发明无铅锡基软焊料P含量选择在0.001-0.15％范围内。Adding element P can improve the oxidation resistance of solder and reduce the slag production of molten solder. When the P content is less than 0.001%, its effect is not obvious; and when the P content is greater than 0.15%, the plasticity of the solder is poor. The content of P in the lead-free tin-based soft solder of the present invention is selected within the range of 0.001-0.15%.
添加RE元素能细化焊料合金的组织，提高焊料的力学性能。RE含量少于0.001％时，其作用不明显；然而RE含量超过0.3％时，RE易偏聚于晶界，导致合金力学性能较差。本发明无铅锡基软焊料RE含量选择在0.001-0.3％范围内。The addition of RE elements can refine the structure of the solder alloy and improve the mechanical properties of the solder. When the RE content is less than 0.001%, its effect is not obvious; however, when the RE content exceeds 0.3%, RE tends to segregate to the grain boundaries, resulting in poor mechanical properties of the alloy. The content of RE in the lead-free tin-based soft solder of the present invention is selected within the range of 0.001-0.3%.
本发明无铅锡基软焊料，经对以下本发明实施例焊料的测试与计算表明，其对变压器端部引线的溶蚀程度低，可焊性好，强度和抗氧化性能高，能大幅度提高变压器封装产品的成品率。The lead-free tin-based soft solder of the present invention shows through the test and calculation of the following examples of solder of the present invention that it has low corrosion degree to the lead wires at the end of the transformer, good solderability, high strength and oxidation resistance, and can greatly improve Yield rate of transformer packaging products.
具体实施方式 Detailed ways
下面通过具体的实施例进一步说明本发明的无铅锡基软焊料。The lead-free tin-based soft solder of the present invention is further illustrated below through specific examples.
实施例1Example 1
将40.0Kg的Sn和10.0Kg的Cu放入氧化铝坩锅，置入中频炉内熔炼，熔炼温度800℃，保温2小时，充分搅拌后出炉，冷却，制成含Cu20％的Sn-Cu中间合金。Put 40.0Kg of Sn and 10.0Kg of Cu into an alumina crucible, put it into an intermediate frequency furnace for melting, the melting temperature is 800°C, keep it warm for 2 hours, fully stir it, take it out of the furnace, and cool it to make a Sn-Cu intermediate containing 20% Cu. alloy.
将30.0Kg的Sn和20.0Kg的Bi放入氧化铝坩锅，置入中频炉内熔炼，熔炼温度400℃，保温2小时，充分搅拌后出炉，冷却，制成含Bi40％的Sn-Bi中间合金。Put 30.0Kg of Sn and 20.0Kg of Bi into an alumina crucible, put it into an intermediate frequency furnace for melting, the melting temperature is 400°C, keep it warm for 2 hours, fully stir it, take it out of the furnace, and cool it to make a Sn-Bi intermediate containing 40% Bi alloy.
将48.0Kg的Sn和2Kg的Ni放入氧化铝坩锅，置入真空中频感应熔炼炉内熔炼，熔炼温度为800℃，保温2小时，充分搅拌后出炉，冷却，制成含Ni4％的Sn-Ni中间合金。Put 48.0Kg of Sn and 2Kg of Ni into an alumina crucible, put it into a vacuum medium-frequency induction melting furnace for melting, the melting temperature is 800°C, keep it warm for 2 hours, fully stir it, take it out of the furnace, and cool it to make Sn containing 4% Ni. -Ni master alloy.
将49.5Kg的Sn放入氧化铝坩锅中熔炼，熔炼温度为500℃；锡熔化后，用周边带有小孔的石墨钟罩将0.5Kg的P压入锡液中，并不断搅拌；保温8小时，充分搅拌后出炉，冷却，制成含磷1％的锡磷中间合金。Put 49.5Kg of Sn into an alumina crucible for melting at 500°C; after the tin is melted, press 0.5Kg of P into the molten tin with a graphite bell jar with small holes around it, and keep stirring; After 8 hours, fully stir it and take it out of the furnace, cool it down, and make a tin-phosphorus master alloy containing 1% phosphorus.
将48.0Kg的Sn和2.0Kg的RE放入氧化铝坩锅，置入真空中频感应熔炼炉内熔炼，熔炼温度为1000℃，保温2小时，充分搅拌后出炉，冷却，制成含RE4％的Sn-RE中间合金。Put 48.0Kg of Sn and 2.0Kg of RE into an alumina crucible, put it into a vacuum medium frequency induction melting furnace for melting, the melting temperature is 1000°C, keep it warm for 2 hours, fully stir it, take it out of the furnace, and cool it to make RE4% Sn-RE master alloy.
取上述Sn-Cu中间合金1.025Kg，Sn-Bi中间合金0.138Kg，Sn-Ni中间合金0.125Kg和纯锡4.225Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Take 1.025Kg of the above-mentioned Sn-Cu master alloy, 0.138Kg of Sn-Bi master alloy, 0.125Kg of Sn-Ni master alloy and 4.225Kg of pure tin, put them into a stainless steel pot for melting, the melting temperature is 600°C, and the holding time is 1 hour. After being fully stirred, it is released from the furnace and cast on a steel electrode mold to obtain a lead-free tin-based soft solder bar.
实施例2Example 2
取实施例1Sn-Cu中间合金1.275Kg，Sn-Bi中间合金0.025Kg，Sn-Ni中间合金0.750Kg和纯锡3.587Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Take Example 1 Sn-Cu master alloy 1.275Kg, Sn-Bi master alloy 0.025Kg, Sn-Ni master alloy 0.750Kg and pure tin 3.587Kg, put it into a stainless steel pot for melting, the melting temperature is 600°C, and the holding time is 1 hour , out of the oven after fully stirring, and cast on a steel electrode mold to obtain lead-free tin-based soft solder bars.
实施例3Example 3
取实施例1Sn-Cu中间合金1.550Kg，Sn-Bi中间合金0.188Kg，Sn-Ni中间合金0.375Kg，Sn-P中间合金0.375Kg和纯锡3.288Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.550Kg, Sn-Bi master alloy 0.188Kg, Sn-Ni master alloy 0.375Kg, Sn-P master alloy 0.375Kg and pure tin 3.288Kg, put into stainless steel pot and smelt, melting temperature is 600°C, heat preservation time is 1 hour, fully stirred, then out of the furnace, cast on a steel electrode mold to obtain lead-free tin-based soft solder bar.
实施例4Example 4
取实施例1Sn-Cu中间合金1.150Kg，Sn-Bi中间合金0.063Kg，Sn-Ni中间合金0.025Kg，Sn-P中间合金0.700Kg和纯锡3.638Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.150Kg, Sn-Bi master alloy 0.063Kg, Sn-Ni master alloy 0.025Kg, Sn-P master alloy 0.700Kg and pure tin 3.638Kg, put into stainless steel pot and smelt, melting temperature is 600°C, heat preservation time is 1 hour, fully stirred, then out of the furnace, cast on a steel electrode mold to obtain lead-free tin-based soft solder bar.
实施例5Example 5
取实施例1Sn-Cu中间合金1.800Kg，Sn-Bi中间合金0.188Kg，Sn-Ni中间合金0.875Kg，Sn-P中间合金0.010Kg，Sn-RE中间合金0.013Kg和纯锡3.015Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.800Kg, Sn-Bi master alloy 0.188Kg, Sn-Ni master alloy 0.875Kg, Sn-P master alloy 0.010Kg, Sn-RE master alloy 0.013Kg and pure tin 3.015Kg, insert Melting in a stainless steel pot, the melting temperature is 600°C, and the holding time is 1 hour. After fully stirring, it is released from the furnace and cast on a steel electrode mold to obtain lead-free tin-based soft solder bars.
实施例6Example 6
取实施例1Sn-Cu中间合金2.100Kg，Sn-Bi中间合金0.238Kg，Sn-Ni中间合金0.500Kg，Sn-P中间合金0.250Kg，Sn-RE中间合金0.188Kg和纯锡2.775Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 2.100Kg, Sn-Bi master alloy 0.238Kg, Sn-Ni master alloy 0.500Kg, Sn-P master alloy 0.250Kg, Sn-RE master alloy 0.188Kg and pure tin 2.775Kg, insert Melting in a stainless steel pot, the melting temperature is 600°C, and the holding time is 1 hour. After fully stirring, it is released from the furnace and cast on a steel electrode mold to obtain lead-free tin-based soft solder bars.
实施例7Example 7
取实施例1Sn-Cu中间合金1.550Kg，Sn-Bi中间合金0.163Kg，Sn-Ni中间合金1.375Kg，Sn-RE中间合金3.8g和纯锡2.684Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.550Kg, Sn-Bi master alloy 0.163Kg, Sn-Ni master alloy 1.375Kg, Sn-RE master alloy 3.8g and pure tin 2.684Kg, put into stainless steel pot and smelt, melting temperature is 600°C, heat preservation time is 1 hour, fully stirred, then out of the furnace, cast on a steel electrode mold to obtain lead-free tin-based soft solder bar.
实施例8Example 8
取实施例1Sn-Cu中间合金1.800Kg，Sn-Bi中间合金0.138Kg，Sn-Ni中间合金0.375Kg，Sn-RE中间合金0.125Kg和纯锡3.463Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.800Kg, Sn-Bi master alloy 0.138Kg, Sn-Ni master alloy 0.375Kg, Sn-RE master alloy 0.125Kg and pure tin 3.463Kg, put into stainless steel pot and smelt, melting temperature is 600°C, heat preservation time is 1 hour, fully stirred, then out of the furnace, cast on a steel electrode mold to obtain lead-free tin-based soft solder bar.
实施例9Example 9
取实施例1Sn-Cu中间合金1.275Kg，Sn-Bi中间合金0.300Kg，Sn-Ni中间合金0.188Kg，Sn-P中间合金0.500Kg，Sn-RE中间合金0.075Kg和纯锡3.300Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.275Kg, Sn-Bi master alloy 0.300Kg, Sn-Ni master alloy 0.188Kg, Sn-P master alloy 0.500Kg, Sn-RE master alloy 0.075Kg and pure tin 3.300Kg, insert Melting in a stainless steel pot, the melting temperature is 600°C, and the holding time is 1 hour. After fully stirring, it is released from the furnace and cast on a steel electrode mold to obtain lead-free tin-based soft solder bars.
实施例10Example 10
取实施例1Sn-Cu中间合金1.150Kg，Sn-Bi中间合金0.063Kg，Sn-Ni中间合金0.125Kg，Sn-P中间合金0.500Kg，Sn-RE中间合金0.313Kg和纯锡3.425Kg，置入不锈钢锅内熔炼，熔炼温度为600℃，保温时间为1小时，充分搅拌后出炉，浇铸在钢制焊条模具上，获得无铅锡基软焊料条。Get embodiment 1 Sn-Cu master alloy 1.150Kg, Sn-Bi master alloy 0.063Kg, Sn-Ni master alloy 0.125Kg, Sn-P master alloy 0.500Kg, Sn-RE master alloy 0.313Kg and pure tin 3.425Kg, insert Melting in a stainless steel pot, the melting temperature is 600°C, and the holding time is 1 hour. After fully stirring, it is released from the furnace and cast on a steel electrode mold to obtain lead-free tin-based soft solder bars.
选用目前变压器铜线端部引线浸焊使用的Sn-0.7Cu和Sn-3.0Cu无铅焊料作为对比，实施例和对比例的成份见表1所示。The Sn-0.7Cu and Sn-3.0Cu lead-free solders currently used for dip soldering of transformer copper wire end leads are selected as a comparison, and the ingredients of the examples and comparative examples are shown in Table 1.
表1焊料组分与含量Table 1 Solder composition and content
为评价本发明的焊料对铜引线的溶蚀程度，进行了溶蚀测试实验。并用剩铜率作为评价无铅焊料对基板溶蚀程度的评价指标：剩铜率(％)＝浸焊后的Cu线直径/Cu线原始直径，采用千分尺测量铜线直径。剩铜率测试工艺为：直径为0.100mm的Cu线在400℃下浸焊3秒，浸焊长度为4mm，测试结果见表2。由结果可见，本发明无铅焊料的剩铜率远高于对比例，因而本申请无铅焊料具有极佳的抗溶蚀能力。In order to evaluate the corrosion degree of the solder of the present invention to the copper lead, a corrosion test experiment was carried out. And use the remaining copper rate as the evaluation index for evaluating the corrosion degree of the substrate by the lead-free solder: remaining copper rate (%)=Cu wire diameter/Cu wire original diameter after dipping soldering, adopt a micrometer to measure the copper wire diameter. The test process for the remaining copper rate is: a Cu wire with a diameter of 0.100mm is dipped and soldered at 400°C for 3 seconds, and the length of the dipped solder is 4mm. The test results are shown in Table 2. It can be seen from the results that the copper remaining rate of the lead-free solder of the present invention is much higher than that of the comparative example, so the lead-free solder of the present application has excellent corrosion resistance.
表2溶蚀性测试结果Table 2 Corrosion test results
按GB11364-89《钎料铺展性及添缝性试验方法》国家标准进行了扩展率测试，铺展基板为0.2mm厚的纯铜薄板。各焊料扩展率测试工艺均相同，测试温度为400℃，时间为10s，并采用相同的助焊剂，测试结果见表3。由表3可见，本发明的焊料其扩展率略高于对比例，即对铜线具有良好的润湿性能和焊接性。According to the national standard of GB11364-89 "Test Method for Spreadability and Joint Filling of Solder", the expansion rate test is carried out, and the spreading substrate is a pure copper sheet with a thickness of 0.2mm. The test process of each solder expansion rate is the same, the test temperature is 400°C, the test time is 10s, and the same flux is used. The test results are shown in Table 3. It can be seen from Table 3 that the expansion rate of the solder of the present invention is slightly higher than that of the comparative example, that is, it has good wettability and weldability to copper wires.
根据JIS试验标准测试焊料拉伸强度，试验温度为25℃，测试结果见表3。由表3可见，本发明焊料的拉伸强度均高于对比例，满足焊接工艺对焊料的强度要求。The tensile strength of the solder was tested according to the JIS test standard, and the test temperature was 25°C. The test results are shown in Table 3. It can be seen from Table 3 that the tensile strength of the solder of the present invention is higher than that of the comparative examples, meeting the strength requirements of the soldering process for the solder.
表3焊料性能测试结果Table 3 Solder performance test results
为评价本发明无铅焊料的抗氧化性能，对表1中各实施例和对比例进行了产渣量测试：将各实施例和对比例焊料50g在400℃下保温20小时，然后刮下液态焊料表面的氧化膜，并用分析天平称氧化膜的质量，测试结果见表4。由结果可见，本申请无铅焊料产渣率均比Sn-0.7Cu和Sn-3.0Cu焊料低得多，这说明本发明无铅焊料具有良好的抗氧化性能，可以显著降低焊料使用者的生产成本。In order to evaluate the oxidation resistance of the lead-free solder of the present invention, the slag production test was carried out to each embodiment and comparative examples in Table 1: each embodiment and comparative example solder 50g were incubated at 400 ℃ for 20 hours, then scraped off the liquid The oxide film on the surface of the solder, and the quality of the oxide film was weighed with an analytical balance. The test results are shown in Table 4. As can be seen from the results, the slag production rate of the lead-free solder of the present application is much lower than that of Sn-0.7Cu and Sn-3.0Cu solder, which shows that the lead-free solder of the present invention has good oxidation resistance and can significantly reduce the production of solder users. cost.
表4焊料在400℃下的产渣量测试结果Table 4 Test results of slag production of solder at 400°C
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| CN105290653A (en) * | 2015-11-30 | 2016-02-03 | 苏州龙腾万里化工科技有限公司 | Manufacturing method for rosin soldering tin bar |
| CN105290639A (en) * | 2015-11-30 | 2016-02-03 | 苏州龙腾万里化工科技有限公司 | Manufacturing method for copper-added soldering tin bar |
| CN105382442A (en) * | 2015-11-30 | 2016-03-09 | 苏州龙腾万里化工科技有限公司 | Copper-added soldering tin bar |
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| CN1198117A (en) * | 1995-09-29 | 1998-11-04 | 松下电器产业株式会社 | Lead-Free Solder Alloys |
| JP2002018589A (en) * | 2000-07-03 | 2002-01-22 | Senju Metal Ind Co Ltd | Lead-free solder alloy |
| US6365097B1 (en) * | 1999-01-29 | 2002-04-02 | Fuji Electric Co., Ltd. | Solder alloy |
| CN1390672A (en) * | 2002-05-10 | 2003-01-15 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
| CN1400081A (en) * | 2001-06-28 | 2003-03-05 | 千住金属工业株式会社 | Lead-Free Solder Alloys |
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| CN1198117A (en) * | 1995-09-29 | 1998-11-04 | 松下电器产业株式会社 | Lead-Free Solder Alloys |
| US6365097B1 (en) * | 1999-01-29 | 2002-04-02 | Fuji Electric Co., Ltd. | Solder alloy |
| JP2002018589A (en) * | 2000-07-03 | 2002-01-22 | Senju Metal Ind Co Ltd | 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 |
| CN1390672A (en) * | 2002-05-10 | 2003-01-15 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
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