CN1721124A - Leadless solder - Google Patents

Leadless solder Download PDF

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Publication number
CN1721124A
CN1721124A CN 200510011704 CN200510011704A CN1721124A CN 1721124 A CN1721124 A CN 1721124A CN 200510011704 CN200510011704 CN 200510011704 CN 200510011704 A CN200510011704 A CN 200510011704A CN 1721124 A CN1721124 A CN 1721124A
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China
Prior art keywords
tin
cerium
silver
copper
alloy ingot
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Granted
Application number
CN 200510011704
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Chinese (zh)
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CN1301179C (en
Inventor
马鑫
邓和升
杜昆
苏明斌
杨嘉骥
杨增安
冼陈列
胡智信
顾小龙
戴国水
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHENZHOU GOLD ARROW SOLDER Co Ltd
Guangzhou Research Institute of Non Ferrous Metals
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Individual
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Priority to CNB200510011704XA priority Critical patent/CN1301179C/en
Publication of CN1721124A publication Critical patent/CN1721124A/en
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Publication of CN1301179C publication Critical patent/CN1301179C/en
Expired - Fee Related legal-status Critical Current
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Abstract

The present invention relates to solder without lead, particular solder contained copper, silver and cerium and without lead and tin, and characterized in that, smelt refined tin, cerium, silver ingot, and refined copper; cast tin-cerium intermediate alloy ingot with cerium 4%, tin-silver intermediate alloy ingot with silver 30% and tin-copper intermediate alloy ingot with copper 30%; add three alloy ingots into manganese alloy pan and put into MF furnace for fusion to cast into solder bar and obtain the product. It is with high purity, low metal loss, even metallic phase, and more finely; it increases wettability, elongation and welding performance; decrease melting point, improves welding spot shearing force, tension force and QFP lead wire 45Deg tension force of chip component; good quality and benefit to environmental protection.

Description

Lead-free solder
Technical field
The present invention relates to the lead-free welding material of a kind of lead-free solder, particularly cupric, silver and cerium, belong to the tin soldering alloys field.
Technical background
Along with developing rapidly the requirement of electronic product of electronics industry is more and more higher, the used scolder kind of present electronic product is a lot, but majority still uses the tin-lead alloy scolder, because tin-kupper solder is leaded to have pollution to environment, therefore two instructions of European Union's issue, forbid electronic product, using leaded tin solder from July 1st, 2006, existing lead-free solder majority is Xi-Yin, tin-copper, tin-silver-copper, tin-zinc-indium-bismuth, tin-antimony-Yin-indium, tin-zinc-nickel etc. are formed, what also have minority is that Xi-Yin-mishmetal is formed, the weak point of above-mentioned lead-free welding material is the fusing point height that has, the wetability that has is little, the crystallization that has is thicker, the composition multiplex (MUX) who the has complicated cost height of planting.
Summary of the invention
Purpose of the present invention provides a kind of lead-free solder that fusing point is low, wetability good, cost is low that has for the shortcoming that overcomes above-mentioned prior art with deficiency just, thereby the welding material of high-quality is provided for the processing and manufacturing of electronic product.
The objective of the invention is to be achieved through the following technical solutions:
Lead-free solder is characterized in that what its employing following weight percentages was also made as follows
Copper 0.3~3.0%, silver 0.5~6.0%, cerium 0.005~0.20%, surplus are tin,
A) be to add crucible at 96: 4 and insert vacuum melting furnace and carry out melting and be warming up to 1000 ℃ the refined tin of stanniferous 99.95% and the metallic cerium that contains cerium 99.99% by both weight ratio, be incubated 2 hours, stirred 30 minutes, and came out of the stove, cool off and cast the tin cerium intermediate alloy ingot that contains cerium 4%;
(b) be to add crucible at 70: 30 and insert the intermediate frequency furnace melting the silver ingot of the refined tin of stanniferous 99.95% and argentiferous 99.99% by both weight ratio, vacuum nitrogen filling gas, be warming up to 1200 ℃, be incubated 3 hours, come out of the stove, cool off the tin silver intermediate alloy ingot of casting argentiferous 30%;
(c) be to add crucible at 70: 30 and insert the intermediate frequency furnace melting the smart copper of the refined tin of stanniferous 99.95% and cupric 99.95% by both weight ratio, vacuum nitrogen filling gas, be warming up to 900 ℃, be incubated 3 hours, come out of the stove, cool off the tin copper intermediate alloy ingot of casting cupric 30%;
D) get 0.125~5.0 part of the tin cerium intermediate alloy ingot of (a), (b) 1.67~20.0 parts of tin silver intermediate alloy ingot and (c) 1.0~10.0 parts of Xiang Xitong intermediate alloy ingot and add 77.42~90.0 parts of the not enough tin amounts of surplus tin, add in the manganese alloy pot simultaneously and insert the intermediate frequency furnace melting, vacuum nitrogen filling gas, be warming up to 450 ℃, come out of the stove, cool off and be cast into the lead-free solder rod, obtain product of the present invention.
Described raw material weight percentage is:
Copper 0.5~1.0%, cerium 0.01~0.1%, silver 3.0~3.5%, surplus are tin.
The raw material that method of the present invention adopts is the tin slab of stanniferous 99.95%, the copper ingot of cupric 99.95%, the cerium ingot that contains cerium 99.99%, the silver ingot of argentiferous 99.95% is the market sale modular product, in the strict control of blending process, the cerium that adds in this product is a rare earth element, 789 ℃ of fusing points, 3426 ℃ of boiling points, density 6.77g/cm 3, it is the grey active metal, easily oxidation loses light and translates in air, heating flame is soluble in acid, is alloy material, but its deoxidation, desulfurization, evenly crystal grain thinning, improve mechanical performance and oxidation resistance, can reduce fusing point,
Product of the present invention detects through Ministry of Information Industry proprietary material quality supervision and test center, and its result is as follows:
1, solder joint stretching, shearing test, slice component are welded some shearing tests, the QFP 45 ° of tension tests that go between, and testing result sees Table 1
The stretching of table 1 solder joint, slice component solder joint shearing test, the QFP 45 ° of tension test testing results that go between
Sample number into spectrum Solder joint stretching (N) Slice component solder joint shearing test (N) The QFP 45 ° of tension tests (N) that go between
1# Measured value 204.2 197.8 30.3 23.1 24.9 26.2 21.4
240.5 209.3 27.9 28.5 21.4 23.6 21.7
240.9 26.8 23.5 25.3
Average 218.5 27.3 23.5
2# Measured value 230.8 233.8 29.6 37.0 21.5 24.1 20.8
194.4 227.9 27.6 20.3 28.3 23.7 25.6
213.4 32.8 27.4 20.3
Average 220.1 31.5 22.7
2, wetability
Testing result sees Table 2
Table 2 wetability testing result
Sample number into spectrum Wetting time started t 0(S) Wetting rise time t 1(S) Wetting time t (S) Maximum wetting power F max(((mN))) ())) Final wetting power F end(mN)
1# 1 0.4 0.5 0.9 0.52 0.51
2 0.5 0.3 0.8 0.65 0.60
3 0.6 0.3 0.9 0.74 0.49
4 0.5 0.4 0.9 0.43 0.45
5 0.4 0.4 0.8 0.67 0.50
Mean value 0.5 0.4 0.9 0.60 0.51
2# 1 0.8 0.3 1.1 0.51 0.49
2 0.8 0.4 0.8 0.65 0.53
3 0.6 0.5 1.1 0.61 0.59
4 0.8 0.4 1.0 0.59 0.49
5 0.6 0.3 0.9 0.65 0.62
Mean value 0.7 0.4 1.0 0.60 0.54
3, chemical composition detects
Testing result sees Table 3
Table 3 chemical composition testing result
Test item Sample number into spectrum
1# 2#
Sn(%) 96.40 96.36
Ag(%) 2.97 2.98
Cu(%) 0.57 0.58
Ce(%) 0.010 0.076
Pb(%) 0.015 0.015
Sb(%) 0.013 0.011
Fe(%) 0.003 0.003
Zn(%) <0.0003 <0.0003
Bi(%) 0.006 0.006
AI(%) <0.002 <0.002
As(%) <0.003 <0.003
Cd(%) <0.0005 <0.0005
4, fusing point, metallographic
Testing result sees Table 4
Table 4 rate of spread, fusing point, metallographic testing result
Test item Testing result
1# 2#
The rate of spread (%) 78.0 77.6
Fusing point (℃) 219 219
Rate of spread % 78.0 77.6
Metallographic Metallographic structure is even
Conclusion: testing result shows that the sample metallographic structure is even, and performance indications are good, can be used as lead-free solder product new varieties.
5, performance relatively
Table 5 performance relatively
Project Import lead-free solder SnAgCu Lead-free solder SnAgCuCe of the present invention
Elongation (%) 78 78.4
Wetability (mN) 61 61
Fusing point (℃) 219 217
Slice component solder joint shearing test (N) 27.1 31.5
Solder joint tension test (N)) (()) 219.9 228.6
The QFP 45 ° of tension tests (N) that go between 23.3 23.5
Metallographic (amplifying 200 times) Crystallization is thicker Crystallization is even
Owing to take technique scheme to make the technology of the present invention compared with the prior art have following advantage and effect:
(a) the material purity height of this method employing, the technical process metal loss is low,
(b) lead-free solder of the present invention is owing to adopt cerium to make the rate of spread be raised to 78.4% by 78%, and fusing point is reduced to 217 ℃ by 219 ℃; Slice component solder joint shearing test is brought up to 31.5N by 27.1N; The solder joint tension test is high to 228.6N by 219.9/N, and 45 ° of tension tests of QFP lead-in wire are brought up to 23.5N by 23.3N, and metallographic is more even, more refinement,
(c) good product quality belongs to environment-friendly products, low price.
The specific embodiment
Embodiment 1
The refined tin 96kg of stanniferous 99.95% and the metallic cerium 4kg that contains cerium 99.99% are added crucible insert vacuum melting furnace and carry out melting, be warming up to 1000 ℃, be incubated 2 hours, stirred 30 minutes, come out of the stove, cool off and cast the tin cerium intermediate alloy ingot that contains cerium 4%; The refined tin 70kg of stanniferous 99.95% and the silver ingot 30kg adding crucible of argentiferous 99.99% are inserted the intermediate frequency furnace melting, and vacuum nitrogen filling gas is warming up to 1200 ℃, is incubated 3 hours, comes out of the stove, cools off the tin silver intermediate alloy ingot of casting argentiferous 30%; The refined tin 70kg of stanniferous 99.95% and the smart copper 30kg adding crucible of cupric 99.95% are inserted the intermediate frequency furnace melting, and vacuum nitrogen filling gas is warming up to 900 ℃, is incubated 3 hours, comes out of the stove, cools off the tin copper intermediate alloy ingot of casting cupric 30%; Get above-mentioned tin cerium intermediate alloy ingot 0.125kg, tin silver intermediate alloy ingot 20.0kg, tin copper intermediate alloy ingot 1.0kg and add the not enough tin amount 78.875kg of surplus tin, add manganese alloy melting pot and insert the intermediate frequency furnace melting, vacuum nitrogen filling gas, be warming up to 450 ℃, come out of the stove, cool off and be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.005%, silver 6.0%, copper 0.3%, tin 93.695% of the present invention.
Embodiment 2
Press the method for embodiment 1 and make three kinds of intermediate alloys, get tin-cerium alloy ingot 0.25kg, sn-ag alloy ingot 16.7kg, gun-metal ingot 1.67kg and add the not enough tin amount 81.38kg of surplus tin, add the fusing of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.01%, silver 5.0%, copper 0.5%, tin 94.49% of the present invention.
Embodiment 3
Press the method for embodiment 1 and make three kinds of intermediate alloys, get tin-cerium alloy ingot 1.25kg, sn-ag alloy ingot 13.33kg, gun-metal ingot 3.33kg and add the not enough tin amount 82.09kg of surplus tin, add the melting of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.05%, silver 4.0%, copper 1.0%, tin 94.95% of the present invention.
Embodiment 4
Press the method for embodiment 1 and make three kinds of intermediate alloys, get tin-cerium alloy ingot 2.5kg, sn-ag alloy ingot 6.67kg, gun-metal ingot 6.67kg and add the not enough tin amount 84.16kg of surplus tin, add the melting of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.1%, silver 2.0%, copper 2.0%, tin 95.9% of the present invention.
Embodiment 5
Press the method for embodiment 1 and make three kinds of intermediate alloys, the not enough tin amount 82.92kg that gets tin-cerium alloy ingot 3.75kg, sn-ag alloy ingot 3..33kg, gun-metal ingot 10kg and add surplus tin adds the melting of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.15%, silver 1.00%, copper 3.0%, tin 95.85% of the present invention.
Embodiment 6
Press the method for embodiment 1 and make three kinds of intermediate alloys, the not enough tin amount 90kg that gets tin-cerium alloy ingot 5kg, sn-ag alloy ingot 1.67kg, gun-metal ingot 3.33kg and add surplus tin adds the melting of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.2%, silver 0.5%, copper 1.0%, tin 98.3% of the present invention.
Embodiment 7
Press the method for embodiment 1 and make three kinds of intermediate alloys, the not enough tin amount 77.42kg that gets tin-cerium alloy ingot 0.25kg, sn-ag alloy ingot 20kg, gun-metal ingot 2.33kg and add surplus tin adds the melting of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.01%, silver 6.0%, copper 0.7%, tin 93.29% of the present invention.
Embodiment 8
Press the method for embodiment 1 and make three kinds of intermediate alloys, get tin-cerium alloy ingot 2.5kg, sn-ag alloy ingot 10kg, gun-metal ingot 2.0kg and add the not enough tin amount 85.5kg of surplus tin, add the melting of manganese alloy melting pot, be cast into the lead-free solder rod, obtain the lead-free solder product of making for raw material by cerium 0.1%, silver 3.0%, copper 0.6%, tin 96.3% of the present invention.

Claims (2)

1, lead-free solder is characterized in that what its employing following weight percentages was also made as follows:
Copper 0.3~3.0%, silver 0.5~6.0%, cerium 0.005~0.20%, surplus are tin,
(a) be to add crucible at 96: 4 and insert vacuum melting furnace and carry out melting and be warming up to 1000 ℃ the refined tin of stanniferous 99.95% and the metallic cerium that contains cerium 99.99% by both weight ratio, be incubated 2 hours, stirred 30 minutes, and came out of the stove, cool off and cast the tin cerium intermediate alloy ingot that contains cerium 4%;
(b) be to add crucible at 70: 30 and insert the intermediate frequency furnace melting the silver ingot of the refined tin of stanniferous 99.95% and argentiferous 99.99% by both weight ratio, vacuum nitrogen filling gas, be warming up to 1200 ℃, be incubated 3 hours, come out of the stove, cool off the tin silver intermediate alloy ingot of casting argentiferous 30%;
(c) be to add crucible at 70: 30 and insert the intermediate frequency furnace melting the smart copper of the refined tin of stanniferous 99.95% and cupric 99.95% by both weight ratio, vacuum nitrogen filling gas, be warming up to 900 ℃, be incubated 3 hours, come out of the stove, cool off the tin copper intermediate alloy ingot of casting cupric 30%;
D) get 0.125~5.0 part of the tin cerium intermediate alloy ingot of (a), (b) 1.67~20.0 parts of tin silver intermediate alloy ingot and (c) 1.0~10.0 parts of Xiang Xitong intermediate alloy ingot and add 77.42~90.0 parts of the not enough tin amounts of surplus tin, add in the manganese alloy pot simultaneously and insert the intermediate frequency furnace melting, vacuum nitrogen filling gas, be warming up to 450 ℃, come out of the stove, cool off and be cast into the lead-free solder rod, obtain product of the present invention.
2, lead-free solder according to claim 1 is characterized in that described raw material weight percentage is:
Copper 0.5~1.0%, cerium 0.01~0.1%, silver 3.0~3.5%, surplus are tin.
CNB200510011704XA 2005-05-11 2005-05-11 Leadless solder Expired - Fee Related CN1301179C (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105290640A (en) * 2015-11-30 2016-02-03 苏州龙腾万里化工科技有限公司 Lead-free soldering tin bar
CN109128569A (en) * 2018-10-08 2019-01-04 深圳市上煌实业有限公司 A kind of middle low-temperature lead-free solder and preparation method thereof
CN111347193A (en) * 2020-04-16 2020-06-30 深圳市博士达焊锡制品有限公司 High-reliability solder paste and preparation method thereof
CN111590233A (en) * 2020-06-11 2020-08-28 中山翰华锡业有限公司 High-weldability environment-friendly superfine solder wire for intelligent manipulator welding and preparation method thereof
CN112779431A (en) * 2020-12-25 2021-05-11 有研亿金新材料有限公司 Method for improving sputtering property of palladium, silver and copper
CN114289927A (en) * 2021-12-28 2022-04-08 上海大学 Lead-free solder
CN114434040A (en) * 2021-01-15 2022-05-06 重庆理工大学 Dissimilar material interconnected zinc alloy mixed solder powder and connecting method
CN114700651A (en) * 2020-06-11 2022-07-05 中山翰华锡业有限公司 Heat-resistant environment-friendly superfine solder wire applied to intelligent manipulator welding and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101780607B (en) * 2010-03-17 2012-05-09 华南理工大学 Lead-free solder for electronic packaging, assembling and soldering and preparation method thereof

Family Cites Families (5)

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Publication number Priority date Publication date Assignee Title
GB8807730D0 (en) * 1988-03-31 1988-05-05 Cookson Group Plc Low toxicity soldering compositions
US5833921A (en) * 1997-09-26 1998-11-10 Ford Motor Company Lead-free, low-temperature solder compositions
CN1234498C (en) * 2002-09-06 2006-01-04 薛松柏 Lead-free solder
US20040151616A1 (en) * 2003-02-04 2004-08-05 Sabarese Daniel M. Lead-free alloys, composition thereof, methods of preparation and uses for soldering and babbitting
CN1265934C (en) * 2003-12-26 2006-07-26 杨嘉骥 Anti-oxidation lead-free solder and its preparing method

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105290640A (en) * 2015-11-30 2016-02-03 苏州龙腾万里化工科技有限公司 Lead-free soldering tin bar
CN109128569A (en) * 2018-10-08 2019-01-04 深圳市上煌实业有限公司 A kind of middle low-temperature lead-free solder and preparation method thereof
CN111347193A (en) * 2020-04-16 2020-06-30 深圳市博士达焊锡制品有限公司 High-reliability solder paste and preparation method thereof
CN111590233A (en) * 2020-06-11 2020-08-28 中山翰华锡业有限公司 High-weldability environment-friendly superfine solder wire for intelligent manipulator welding and preparation method thereof
CN111590233B (en) * 2020-06-11 2021-12-31 中山翰华锡业有限公司 High-weldability environment-friendly superfine solder wire for intelligent manipulator welding and preparation method thereof
CN114700651A (en) * 2020-06-11 2022-07-05 中山翰华锡业有限公司 Heat-resistant environment-friendly superfine solder wire applied to intelligent manipulator welding and preparation method thereof
CN114700651B (en) * 2020-06-11 2024-04-05 中山翰华锡业有限公司 Heat-resistant environment-friendly superfine soldering tin wire applied to intelligent manipulator welding and preparation method thereof
CN112779431A (en) * 2020-12-25 2021-05-11 有研亿金新材料有限公司 Method for improving sputtering property of palladium, silver and copper
CN112779431B (en) * 2020-12-25 2022-04-05 有研亿金新材料有限公司 Method for improving sputtering property of palladium, silver and copper
CN114434040A (en) * 2021-01-15 2022-05-06 重庆理工大学 Dissimilar material interconnected zinc alloy mixed solder powder and connecting method
CN114289927A (en) * 2021-12-28 2022-04-08 上海大学 Lead-free solder

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