CN100351035C - Lead free solder - Google Patents
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- CN100351035C CN100351035C CNB2005100612992A CN200510061299A CN100351035C CN 100351035 C CN100351035 C CN 100351035C CN B2005100612992 A CNB2005100612992 A CN B2005100612992A CN 200510061299 A CN200510061299 A CN 200510061299A CN 100351035 C CN100351035 C CN 100351035C
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Abstract
The present invention relates to lead-free solder with the advantages of low cost, good wettability and high strength and plasticity. Firstly, the present invention has the following component mass percent based on the total mass of the solder: 0.1 to 0.3 % of Bi, 0.05 to 1.0 % of Sb, 0.001 to 0.1 % of Ce, and the rest of Sn; secondly, the present invention can also have the following component mass percent based on the total mass of the solder: 0.1 to 0.3 % of Bi, 0.05 to 1.0 % of Sb, 0.001 to 0.1 % of Ce, 0.1 to 0.5 % of Ag, and the rest of Sn; thirdly, the present invention can also have the following component mass percent based on the total mass of the solder: 0.1 to 0.3 % of Bi, 0.05 to 1.0 % of Sb, 0.001 to 0.1 % of Ce, 0.1 to 0.5 % of Ag, 0.1 to 0.8 % of Cu, and the rest of Sn. The invention is suitable for lead-free assembly and seal in electronic industry.
Description
Technical field
The present invention relates to solder alloy, leadless welding alloy particularly is mainly used in the no-lead assembling and the encapsulation of electron trade.
Background technology
People more and more pay close attention to plumbous to the pollution of environment with to healthy infringement.In recent years, countries in the world put into effect a series of decrees in succession and rules are prevented and treated the ecological problem that electronic product brings, the plumbous use in electronic product of restriction.Under this main trend of unleaded green manufacturing, many countries have begun to increase input and have researched and developed lead-free solder, and actively promote its application.
The lead-free solder of having developed at present mainly contains Sn-Ag, Sn-Cu, and Sn-Zn and Sn-Ag-Cu etc., and by adding the series of products that elements such as Ag, Cu, P, Ni, In, Bi obtain different performance.US5527628 patent as the state university of JS3027441 patent and Iowa of Senju Metal Industry Co., Ltd discloses SnAgCu series leadless scolder separately respectively; The CN1087994C patent of Panasonic Electric Equipment Industrial Co.,Ltd and the CN1586793A patent application of Beijing University of Technology disclose the tin zinc series leadless scolder of exploitation separately; The CN1496780A patent application of Senju Metal Industry Co., Ltd discloses a kind of tin copper series leadless scolder; The CN1040302C of Korea S Samsung Electro-Mechanics Co., Ltd, CN1040303C patent and CN1139607A patent application disclose tin bismuth series leadless scolder etc.Though Sn-Cu scolder cost is low, its wettability is relatively poor.The wettability of Sn-Ag scolder is more better than Sn-Cu scolder, but still not high (its rate of spread＜75%); And scolder contains noble metal silver, and cost is higher.Though Sn-Zn scolder fusing point and cost are all lower, owing to contain Zn, scolder corrosion resistance and non-oxidizability extreme difference, wetability is bad, needs active stronger solder flux and nitrogen protection in the welding process, and Joint Reliability is relatively poor.Present Sn-Bi series solder fusing point is too low, and the scope of application is limited; And scolder plasticity is relatively poor, is difficult to carry out machinings such as wire drawing.Compare with the Sn-Ag scolder with Sn-Cu, the liquidus temperature of Sn-Ag-Cu lead-free solder is lower, and the freezing range is little, and wetability increases; The intensity of this series leadless scolder is higher, and plasticity can satisfy the machining requirement, thereby this scolder is a most competitive present leadless welding alloy.Yet the shortcoming of Sn-Ag-Cu scolder is: because the silver content height, cost is higher; And the wettability of this scolder still not good (rate of spread is 75-80%).
Summary of the invention
Lead-free solder or wetability that the present invention will solve in the known technology are poor, or intensity and plasticity are lower, or the cost problem of higher, and lead-free solder of the present invention is provided for this reason, this scolder cost is low, has good wettability, higher intensity and plasticity.
For addressing the above problem, how many present invention is divided into three kinds of scolders with component.
The one special character is that it is made up of the component of following mass percent in this scolder gross mass:
Bi 0.1-3.0％
Sb 0.05-1.0％
Ce 0.001-0.1％
The Sn surplus
Its two special character is that it is made up of the component of following mass percent in this scolder gross mass:
Bi 0.1-3.0％
Sb 0.05-1.0％
Ce 0.001-0.1％
Ag 0.1-0.5％
The Sn surplus
Its three special character is that it is made up of the component of following mass percent in this scolder gross mass:
Bi 0.1-3.0％
Sb 0.05-1.0％
Ce 0.001-0.1％
Ag 0.1-0.5％
Cu 0.1-0.8％
The Sn surplus
Leadless welding alloy composition of the present invention and quality percentage composition thereof are determined according to following reason:
Add bismuth additions and can reduce the solder fusing temperature, improve wettability.Bi content is less than at 0.1% o'clock, and its effect is not obvious.Yet Bi content surpasses at 3.0% o'clock, and alloy plasticity is relatively poor, is difficult to carry out machinings such as wire drawing.Lead-free solder Bi content of the present invention is chosen in the 0.1-3.0% scope.
Infinitely solid solution of Sb and Bi, thereby add a small amount of Sb and can improve scolder intensity.Sb content is less than at 0.05% o'clock, and these effects are not obvious; Yet Sb content surpasses at 1.0% o'clock, solder hardens, and the plasticity school is poor, is difficult to carry out machinings such as wire drawing.Sb content is chosen in the 0.05-1.0% scope in the leadless welding alloy of the present invention.
Add the tissue of alloying element Ce energy refinement solder alloy, improve the mechanical property of scolder.Ce content is less than at 0.001% o'clock, and its effect is not obvious; Yet Ce content surpasses at 0.1% o'clock, and Ce easily gathers partially in crystal boundary, causes alloy mechanical property relatively poor.Lead-free solder Ce content of the present invention is chosen in the 0.001-0.1% scope.
Add alloying element Ag and can reduce the scolder fusing point, and further improve the intensity of scolder by compound between the tin silver metal that generates the disperse distribution.When Ag content was less than 0.1%, its effect was not obvious; Yet Ag content was greater than 0.5% o'clock, and solder alloy plasticity is relatively poor, be difficult to carry out machining, and Ag content too much can cause the rapid rising of production cost.Lead-free solder Ag content of the present invention is chosen in the 0.1-0.5% scope.
Add alloying element cu and can reduce the scolder fusing point, and can suppress the corrosion of copper lead-in wire in the immersed solder process.Yet Cu content is less than at 0.1% o'clock, and its effect is not obvious; And Cu content surpasses at 0.8% o'clock, can generate a large amount of tin copper intermetallic compounds, causes scolder plasticity relatively poor, is difficult to carry out machinings such as wire drawing.Lead-free solder Cu content of the present invention is chosen in the 0.1-0.8% scope.
Lead-free solder of the present invention shows through test and calculating to following embodiment of the invention scolder, its intensity height, and percentage elongation is big, and fusion temperature is low and molten temperature region is little, and cost is low.
The specific embodiment
Further specify lead-free solder of the present invention below by specific embodiment.
Embodiment 1
The Sn of 30.0Kg and the Bi of 20.0Kg are put into alumina crucible, and insert melting in the intermediate frequency furnace, 400 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and cool off, and make the tin bismuth intermediate alloy of bismuth-containing 40%.The Sn of 45.0Kg and the Sb of 5.0Kg are put into alumina crucible, and insert melting in the intermediate frequency furnace, 400 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and the tin antimony intermediate alloy that contains antimony 10% is made in cooling.The Sn of 48.0Kg and the Ce of 2.0Kg are put into alumina crucible, and insert melting in the vacuum medium frequency induction melting furnace, smelting temperature is 1000 ℃, is incubated 2 hours, comes out of the stove after fully stirring, and the tin cerium intermediate alloy that contains cerium 4% is made in cooling.
Get above-mentioned tin bismuth intermediate alloy 0.019Kg, tin antimony intermediate alloy 0.035Kg, tin cerium intermediate alloy 0.0025Kg and pure tin 4.944Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 2
Get embodiment 1 tin bismuth intermediate alloy 0.019Kg, tin antimony intermediate alloy 0.035Kg, tin cerium intermediate alloy 0.063Kg and pure tin 4.884Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 3
Get embodiment 1 tin bismuth intermediate alloy 0.194Kg, tin antimony intermediate alloy 0.260Kg, tin cerium intermediate alloy 0.088Kg and pure tin 4.459Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 4
Get embodiment 1 tin bismuth intermediate alloy 0.338Kg, tin antimony intermediate alloy 0.475Kg, tin cerium intermediate alloy 0.113Kg and pure tin 4.075Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 5
Get embodiment 1 tin bismuth intermediate alloy 0.106Kg, tin antimony intermediate alloy 0.100Kg, tin cerium intermediate alloy 0.088Kg and pure tin 4.706Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 6
The Sn of 40.0Kg and the Ag of 10.0Kg are put into alumina crucible, and insert melting in the intermediate frequency furnace, smelting temperature is 800 ℃, and temperature retention time is 2 hours, comes out of the stove after fully stirring, and cools off, and makes the tin silver intermediate alloy of argentiferous 20%.
Get above-mentioned tin silver intermediate alloy 0.038Kg, get embodiment 1 tin bismuth intermediate alloy 0.019Kg, tin antimony intermediate alloy 0.035Kg, tin cerium intermediate alloy 0.0025Kg and pure tin 4.906Kg insert melting in the stainless-steel pan, and smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 7
Get embodiment 1 tin bismuth intermediate alloy 0.019Kg, tin antimony intermediate alloy 0.035Kg, tin cerium intermediate alloy 0.063Kg, get embodiment 6 tin silver intermediate alloy 0.038Kg and pure tin 4.846Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 8
Get embodiment 1 tin bismuth intermediate alloy 0.194Kg, tin antimony intermediate alloy 0.260Kg, tin cerium intermediate alloy 0.088Kg, get embodiment 6 tin silver intermediate alloy 0.075Kg and pure tin 4.384Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 9
Get embodiment 1 tin bismuth intermediate alloy 0.338Kg, tin antimony intermediate alloy 0.475Kg, tin cerium intermediate alloy 0.113Kg, get embodiment 6 tin silver intermediate alloy 0.113Kg and pure tin 3.963Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 10
Get embodiment 1 tin bismuth intermediate alloy 0.263Kg, tin antimony intermediate alloy 0.050Kg, tin cerium intermediate alloy 0.100Kg, get embodiment 6 tin silver intermediate alloy 0.100Kg and pure tin 4.487Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, temperature retention time is 1.5 hours, come out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 11
The Sn of 40.0Kg and the Cu of 10.0Kg are put into alumina crucible, and insert melting in the intermediate frequency furnace, 800 ℃ of smelting temperatures are incubated 2 hours, come out of the stove after fully stirring, and cool off, and make the tin copper intermediate alloy of cupric 20%.
Get above-mentioned tin copper intermediate alloy 0.038Kg, get embodiment 1 tin bismuth intermediate alloy 0.019Kg, tin antimony intermediate alloy 0.035Kg, tin cerium intermediate alloy 0.0025Kg gets embodiment 6 tin silver intermediate alloy 0.038Kg and pure tin 4.869Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 12
Get embodiment 1 tin bismuth intermediate alloy 0.019Kg, tin antimony intermediate alloy 0.035Kg, tin cerium intermediate alloy 0.063Kg gets embodiment 6 tin silver intermediate alloy 0.038Kg, gets embodiment 11 tin copper intermediate alloy 0.038Kg and pure tin 4.809Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 13
Get embodiment 1 tin bismuth intermediate alloy 0.194Kg, tin antimony intermediate alloy 0.260Kg, tin cerium intermediate alloy 0.088Kg gets embodiment 6 tin silver intermediate alloy 0.075Kg, gets embodiment 11 tin copper intermediate alloy 0.113Kg and pure tin 4.271Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 14
Get embodiment 1 tin bismuth intermediate alloy 0.338Kg, tin antimony intermediate alloy 0.475Kg, tin cerium intermediate alloy 0.113Kg gets embodiment 6 tin silver intermediate alloy 0.113Kg, gets embodiment 11 tin copper intermediate alloy 0.188Kg and pure tin 3.775Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Embodiment 15
Get embodiment 1 tin bismuth intermediate alloy 0.250Kg, tin antimony intermediate alloy 0.360Kg, tin cerium intermediate alloy 0.100Kg gets embodiment 6 tin silver intermediate alloy 0.100Kg, gets embodiment 11 tin copper intermediate alloy 0.150Kg and pure tin 4.040Kg, insert melting in the stainless-steel pan, smelting temperature is 550 ℃, and temperature retention time is 1.5 hours, comes out of the stove after fully stirring, cast on the steel welding rod mould, obtain the lead-free solder bar.
Select for use present electronics assembling and encapsulation to go up and use more Sn-3.5Ag, Sn-0.7Cu and Sn-3.0Ag-0.5Cu lead-free solder as a comparison, their composition is shown in Table 1.
Table 1 solder compositions and content
| Embodiment and Comparative Examples | Component and content (wt%) | |||||
| Bi | Sb | Ag | Ce | Cu | Sn | |
| Embodiment 1 | 0.15 | 0.07 | - | 0.002 | - | Surplus |
| Embodiment 2 | 0.15 | 0.07 | - | 0.05 | - | Surplus |
| Embodiment 3 | 1.55 | 0.52 | - | 0.07 | - | Surplus |
| Embodiment 4 | 2.70 | 0.95 | - | 0.09 | - | Surplus |
| Embodiment 5 | 0.85 | 0.20 | - | 0.07 | - | Surplus |
| Embodiment 6 | 0.15 | 0.07 | 0.15 | 0.002 | - | Surplus |
| Embodiment 7 | 0.15 | 0.07 | 0.15 | 0.05 | - | Surplus |
| Embodiment 8 | 1.55 | 0.52 | 0.30 | 0.07 | - | Surplus |
| Embodiment 9 | 2.70 | 0.95 | 0.45 | 0.09 | - | Surplus |
| Embodiment 10 | 2.10 | 0.10 | 0.40 | 0.08 | - | Surplus |
| Embodiment 11 | 0.15 | 0.07 | 0.15 | 0.002 | 0.15 | Surplus |
| Embodiment 12 | 0.15 | 0.07 | 0.15 | 0.05 | 0.15 | Surplus |
| Embodiment 13 | 1.55 | 0.52 | 0.30 | 0.07 | 0.45 | Surplus |
| Embodiment 14 | 2.70 | 0.95 | 0.45 | 0.09 | 0.75 | Surplus |
| Embodiment 15 | 2.00 | 0.72 | 0.40 | 0.08 | 0.60 | Surplus |
| Comparative Examples 1 | - | - | 3.5 | - | - | Surplus |
| Comparative Examples 2 | - | - | - | - | 0.7 | Surplus |
| Comparative Examples 3 | - | - | 3.0 | - | 0.5 | Surplus |
Carried out rate of spread test by GB11364-89 " solder spreadability and add seam property test method " national standard, sprawling substrate is the thick red copper sheet of 0.15mm.Each scolder rate of spread test technology is all identical, and adopts identical scaling powder (the diethylamine hydrochloric acid configuration by 25g rosin, 75g isopropyl acetone and 0.39g forms), and test result sees Table 2.By table 2 as seen, the lead-free solder rate of spread of the present invention is a little more than Comparative Examples 3, much larger than Comparative Examples 1 and Comparative Examples 2.
According to JIS test standard test scolder mechanical property, test temperature is 25 ℃, and test result sees Table 2.By table 2 as seen, the intensity of lead-free solder of the present invention is higher, and percentage elongation is all greater than 20%.Thereby lead-free solder of the present invention both satisfied the requirement of strength of welding procedure to scolder, had good plasticity again, was easy to be processed to multiple shape to satisfy different welding demands.From table 2 also as seen, the intensity of the embodiment of the invention 3, embodiment 8, embodiment 10, embodiment 13 and embodiment 15 and plasticity all are higher than Comparative Examples 1; Intensity and the plasticity of the embodiment of the invention 3, embodiment 5, embodiment 10, embodiment 13 and embodiment 15 all are higher than Comparative Examples 2; Intensity and the plasticity of the embodiment of the invention 3, embodiment 10 and embodiment 13 all are higher than Comparative Examples 3.
Adopt differential thermal analyzer to test the fusion temperature of each embodiment and Comparative Examples, test result sees Table 2.By table 2 as seen, lead-free solder fusion temperature of the present invention is low, and molten temperature region is little, can guarantee fusion welding rapid solidification at short notice, reduce soldered fitting and finish that cause is vibrated and the possibility that ftractures can satisfy the encapsulation requirement of electronic material at process of setting.
Table 2 solder performance test result
| Embodiment and Comparative Examples | Fusion temperature (℃) | The rate of spread (%) | Hot strength (MPa) | Percentage elongation (%) | |
| Solidus temperature (℃) | Liquidus temperature (℃) | ||||
| Embodiment 1 | 232.6 | 78.4 | 27.8 | 35.5 | |
| Embodiment 2 | 233.3 | 78.6 | 29.4 | 39.1 | |
| Embodiment 3 | 232.3 | 79.7 | 56.3 | 26.9 | |
| Embodiment 4 | 231.9 | 80.7 | 68.3 | 20.1 | |
| Embodiment 5 | 232.8 | 79.3 | 40.0 | 42.0 | |
| Embodiment 6 | 226.0 | 233.1 | 79.1 | 29.1 | 23.5 |
| Embodiment 7 | 226.0 | 232.5 | 79.6 | 34.4 | 25.7 |
| Embodiment 8 | 221.3 | 231.1 | 79.6 | 57.3 | 22.9 |
| Embodiment 9 | 216.0 | 229.8 | 81.0 | 72.3 | 20.5 |
| Embodiment 10 | 216.1 | 228.7 | 80.9 | 64.3 | 26.8 |
| Embodiment 11 | 218.4 | 229.8 | 79.4 | 31.7 | 40.8 |
| Embodiment 12 | 218.7 | 229.3 | 79.9 | 36.0 | 45.5 |
| Embodiment 13 | 214.4 | 225.0 | 80.2 | 68.7 | 27.9 |
| Embodiment 14 | 210.9 | 222.3 | 81.9 | 81.6 | 21.0 |
| Embodiment 15 | 212.1 | 223.3 | 80.8 | 74.0 | 23.8 |
| Comparative Examples 1 | 221.0 | 72.6 | 54.6 | 22.5 | |
| Comparative Examples 2 | 227.0 | 71.3 | 38.4 | 23.6 | |
| Comparative Examples 3 | 217.0 | 221.0 | 77.1 | 47.5 | 25.2 |
As reference, the relative cost of each embodiment and Comparative Examples is shown in Table 3 with the cost of Sn-37Pb.Relative cost is calculated as follows:
The price of each metal is as the criterion to go up the metal price of announcing on September 30th, 2005 " metal quotation net ": Sn: 74000 yuan per ton; Ag: 2110000 yuan per ton; Cu: 36000 yuan per ton; Bi: 85000 yuan per ton; Sb: 32000 yuan per ton; Ce: 65000 yuan per ton; Pb: 9200 yuan per ton.By table 3 as seen, lead-free solder cost of the present invention and Comparative Examples 2 (Sn-0.7Cu is the minimum scolder of cost in the lead-free solder commonly used at present) cost is suitable, and much lower than Comparative Examples 1 (Sn-3.5Ag) and Comparative Examples 3 (Sn-3.0Ag-0.5Cu) cost.
The relative cost contrast of table 3 embodiment and Comparative Examples
| Embodiment and Comparative Examples | Relative cost |
| Embodiment 1 | 1.48 |
| Embodiment 2 | 1.48 |
| Embodiment 3 | 1.48 |
| Embodiment 4 | 1.48 |
| Embodiment 5 | 1.48 |
| Embodiment 6 | 1.54 |
| Embodiment 7 | 1.54 |
| Embodiment 8 | 1.60 |
| Embodiment 9 | 1.66 |
| Embodiment 10 | 1.65 |
| Embodiment 11 | 1.54 |
| Embodiment 12 | 1.54 |
| Embodiment 13 | 1.60 |
| Embodiment 14 | 1.66 |
| Embodiment 15 | 1.64 |
| Comparative Examples 1 | 2.90 |
| Comparative Examples 2 | 1.47 |
| Comparative Examples 3 | 2.70 |
| Sn-37Pb | 1 |
The remarkable advantage of lead-free solder of the present invention is: having under good mechanical property, wettability and the prerequisite than low melting temperature, have extremely low cost.
Claims (3)
1, a kind of lead-free solder is characterized in that it is made up of the component of following mass percent in this scolder gross mass:
Bi 0.1-3.0％
Sb 0.05-1.0％
Ce 0.001-0.1％
The Sn surplus.
2, a kind of lead-free solder is characterized in that it is made up of the component of following mass percent in this scolder gross mass:
Bi 0.1-3.0％
Sb 0.05-1.0％
Ce 0.001-0.1％
Ag 0.1-0.5％
The Sn surplus.
3, a kind of lead-free solder is characterized in that it is made up of the component of following mass percent in this scolder gross mass:
Bi 0.1-3.0％
Sb 0.05-1.0％
Ce 0.001-0.1％
Ag 0.1-0.5％
Cu 0.1-0.8％
The Sn surplus.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101214591B (en) * | 2008-01-18 | 2010-11-24 | 重庆工学院 | Low silver hypoeutectic Sn-Cu-Ag lead-free solder for electronic micro connection |
| CN101549441B (en) * | 2008-04-01 | 2011-06-29 | 东莞市中实焊锡有限公司 | Lead-free solder |
| CN105290641A (en) * | 2015-11-30 | 2016-02-03 | 苏州龙腾万里化工科技有限公司 | Cleaning-free soldering tin bar |
| CN109894768B (en) * | 2019-03-29 | 2021-06-18 | 东莞市千岛金属锡品有限公司 | Preparation method of low-temperature lead-free alloy solder |
| CN111843279A (en) * | 2020-07-22 | 2020-10-30 | 昆山市宏嘉焊锡制造有限公司 | High-temperature oxidation-resistant SnSbCu lead-free solder |
| CN113070606A (en) * | 2021-04-15 | 2021-07-06 | 云南锡业锡材有限公司 | Sn-Ag-Cu high-performance lead-free solder and preparation method thereof |
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