CN102489892A - SnZn-based lead-free brazing filler metal containing Cr - Google Patents
SnZn-based lead-free brazing filler metal containing Cr Download PDFInfo
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- CN102489892A CN102489892A CN2011104271206A CN201110427120A CN102489892A CN 102489892 A CN102489892 A CN 102489892A CN 2011104271206 A CN2011104271206 A CN 2011104271206A CN 201110427120 A CN201110427120 A CN 201110427120A CN 102489892 A CN102489892 A CN 102489892A
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Abstract
The invention belongs to the field of welding material, and particularly relates to a SnZn-based lead-free brazing filler metal containing Cr suitable for reflow soldering and wave soldering in electronic packing. The SnZn-based lead-free brazing filler metal comprises 0.01 to 0.1 percent by weight of Ni, 0.001 to 0.01 percent by weight of P, 0.05 to 0.2 percent by weight of Nd, 0.1 to 0.5 percent by weight of In, 0.01 to 0.5 percent by weight of Cr, 1 to 5 percent by weight of Bi, 7 to 11 percent by weight of Zn, and Sn in balancing amount; and the weight percentage sum of all the components is 100%. The SnZn-based lead-free brazing filler metal has excellent antioxygenic property, wettability and mechanical property, the melting point is equal to that of a conventional SnPb brazing filler metal, copper precipitation is not required, the SnZn-based lead-free brazing filler metal is suitable for reflow soldering and wave soldering, traditional brazing packing devices and electronic components.
Description
Technical field
The invention belongs to field of welding material, be specifically related to a kind of SnZn base leadless solder that is applicable to a kind of Cr of containing of Reflow Soldering and wave-soldering in the Electronic Packaging.
Background technology
The increase of Along with people's environmental consciousness, the electronic interconnection material is unleaded to be globalization tendency.But existing lead-free brazing causes brazing temperature to increase because fusing point is higher than traditional Sn-Pb solder, and this must cause the fire damage of electronic devices and components and wiring board, brings the compatibility issue of existing equipment and lead-free brazing.Particularly to heat sensitive components and parts, owing to there is not suitable lead-free brazing to use, present stage also has to use the Sn-Pb solder, can not accomplish unleadedly fully, and this will work the mischief and human body is caused murder by poisoning environment.Therefore, necessary exploitation low-melting point leadless solder.
In the process of the substitute of seeking traditional Sn-Pb solder, the lead-free brazing that present stage is able to use aborning has Sn-3.0Ag-0.5Cu, Sn-0.3Ag-0.7Cu and Sn-0.7Cu.Their fusing point is between 217-227 ℃; Compare with traditional Sn-37Pb solder (Tm=183 ℃); Its fusing point has raise similar 40 ℃, therefore must cause brazing temperature to improve, and this just has higher requirement to the temperature tolerance of electronic devices and components, wiring board material; Owing to the brazing process parameter window narrows, existing brazing equipment need be upgraded or bought again, has increased brazing cost simultaneously.In addition, because these lead-free brazings contain more noble metal silver, material cost is higher.
The Sn-9Zn lead-free brazing since fusing point (Tm=198 ℃) near the fusing point of Sn-37Pb solder, and have excellent mechanical property and good and economic and be considered to one of potential substitute of Sn-Pb solder.But also there are shortcomings such as oxidation resistance is poor, wettability is low in traditional Sn-9Zn lead-free brazing.
In view of this, a kind of low-melting point leadless solder of necessary exploitation with excellent non-oxidizability, wettability and mechanical performance.
Summary of the invention
The objective of the invention is to; Deficiency to prior art; The Sn-Zn base leadless solder that is applicable to a kind of Cr of containing of Reflow Soldering and wave-soldering in the Electronic Packaging is provided, to overcome that traditional Sn-9Zn lead-free brazing oxidation resistance is poor, wettability is low and shortcoming such as shear strength is low.
The present invention mainly realizes through following technical scheme:
A kind of SnZn base leadless solder that contains Cr; The chemical composition of said solder is: the Cr of the Nd of the Ni of 0.01-0.1wt%, the P of 0.001-0.01wt%, 0.05-0.2wt%, the In of 0.1-0.5wt%, 0.01-0.5wt%, the Bi of 1-5wt%, the Zn of 7-11wt%; Surplus is Sn, the percentage by weight of each component and be 100%.
The present invention has added the element Ni of 0.01-0.1wt% in the SnZn solder.Because the copper and tin reaction forms intermetallic compound Cu
6Sn
5And Cu
3Sn, these intermetallic compounds have very high fusing point, have a strong impact on the flowability of solder, and can form the protrusion of needle-like after the welding, cause short circuit.Nickel can dissolve each other with copper, and adding nickel can suppress copper and in molten solder, dissolve, and reduces the dissolution velocity and the intermetallic compound that reduce copper and tin of copper to molten solder, suppresses the reaction of copper and tin, the possibility of reduction short circuit.Simultaneously, nickel and tin form intermetallic compound, improve the mechanical strength of alloy.When but nickel content is excessive, can improve the liquidus temperature of solder, cause under specific welding temperature, the mobile limit of molten solder is poor.Therefore, nickel content is controlled at 0.01-0.1wt%.
The present invention has added the element P of 0.001-0.01wt% in the SnZn solder.Because the Zn character in the SnZn solder is more active, oxidized easily in brazing filler metal alloy smelting and brazing process, cause the wetability of solder to descend, the rate of spread descends, and is easy to generate a large amount of scruffs, causes failure welding.The present invention has added the element P of 0.001-0.01wt% in the SnZn solder; Because the kelvin effect of element P forms the continuous collection film protective layer of one deck on the molten solder surface, can effectively hinder solder and contact with ambient air; Slow down the oxidation of solder, improve the solder wetting performance.
The content of element P must suitably when element P addition is very few, be not enough to form continuous collection film protective layer on the solder surface, causes the wetability of solder not enough.Otherwise; When element P addition is too much; Because the solubility of element P in solder is less, is easy to form dystectic second phase or field trash, thereby influences some physical properties of brazing filler metal alloy; Like liquid physical properties such as viscosity, flowabilities, and microscopic structure after solidifying and mechanical property etc.Suitable addition should remain between the 0.001-0.01wt%, and promptly addition is enough to not produce dystectic second phase or field trash simultaneously again at the surperficial continuous and fine and close collection film protective layer of one deck that forms of molten solder.
The present invention has added the element Nd of 0.05-0.2wt% in the SnZn solder.The effect of element Nd is the wetting power that improves solder, shortens wetting time.Addition element Nd promotes the forming core of solder in process of setting, and the thick rich Sn in the alloy graining tissue is inhibited mutually, and the tissue of solder is played a part homogenizing, crystal grain thinning, thereby the mechanical property and the creep-resistant property of raising solder.
The present invention has added the element In of 0.1-0.5wt% in the SnZn solder.Because traditional SnPb solder fusing point is 183 ℃, and the fusing point of SnZn9 is 198 ℃.Still exceed more than 10 ℃ than SnPb fusing point, more approaching in order to make SnZn of the present invention base solder with the fusing point of traditional SnPb solder, therefore need the fusing point of reduction SnZn solder.The effect that the present invention adds In is the fusing point that reduces solder, the formation that slows down oxidation, resistance to corrosion and the scruff of Zn.But after adding In in the solder, in microstructure, formed irregular needle-like dendrite, thereby reduced the mechanical strength of solder, reduced the bond strength of solder joint, because also added the element Bi of certain percentage composition among the present invention.
The present invention has added the element Cr of 0.01-0.5wt% in the SnZn solder.Chromium plays a key effect in stainless steel is made, because have outstanding antioxygenic property and decay resistance after adding chromium in the stainless steel.The interpolation of chromium has promoted mechanical performance, antioxygenic property and the decay resistance of SnZn solder greatly.Because chromium element and zinc element can form the very strong ZnCr intermetallic compound of stability, can reduce the activity of zinc element, improve solder antioxygenic property and decay resistance, and can improve the mechanical performances such as elongation of solder.
The present invention has added the element Bi of 1-5wt% in the SnZn solder.The interpolation of bismuth greatly reduces the surface tension of SnZn molten solder, has also improved the wetting power and shortening wetting time of solder.Add an amount of bismuth and can also suppress the formation of needle-like dendrite, make solder have suitable solidus temperature and liquidus temperature, and improved the mechanical strength of solder.
The SnZn base leadless solder that the present invention contains Cr has the following advantages:
The first, SnZn base leadless solder of the present invention has excellent antioxygenic property and wettability, and fusing point is suitable with traditional SnPb solder fusing point, and copper is not analysed, and is applicable to wave-soldering and Reflow Soldering, and traditional soldering packaging system and electronic devices and components;
The second, the present invention has been owing to added element Cr, when promoting SnZn solder antioxygenic property and wettability, bigger improvement the mechanical performance of SnZn solder, solder intensity is further improved;
The 3rd, SnZn base leadless solder of the present invention is compared with traditional lead-free brazing, does not contain noble metal silver, and is with low cost.Reduce the brazing filler metal alloy number of elements, improve the operability of smelting, promote efficient, and further optimize the solder constituent content, improve solder performance, the demand of adapted to leadlessization more.
Preferably, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.01wt%, the P of 0.001wt%, 0.05wt%, the In of 0.1wt%, 0.01wt%, the Bi of 1wt%, the Zn of 8wt% and the Sn of 90.829wt%.
Preferably, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.03wt%, the P of 0.002wt%, 0.1wt%, the In of 0.02wt%, 0.1wt%, the Bi of 2wt%, the Zn of 8wt% and the Sn of 89.748wt%.
Preferably, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.05wt%, the P of 0.01wt%, 0.15wt%, the In of 0.3wt%, 0.3wt%, the Bi of 3wt%, the Zn of 9wt% and the Sn of 87.19wt%.
Preferably, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.1wt%, the P of 0.004wt%, 0.2wt%, the In of 0.5wt%, 0.5wt%, the Bi of 5wt%, the Zn of 9wt% and the Sn of 84.696wt%.
The specific embodiment
Embodiment 1
A kind of SnZn base leadless solder that contains Cr, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.01wt%, the P of 0.001wt%, 0.05wt%, the In of 0.1wt%, 0.01wt%, the Bi of 1wt%, the Zn of 8wt% and the Sn of 90.829wt%.
Embodiment 2
A kind of SnZn base leadless solder that contains Cr, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.03wt%, the P of 0.002wt%, 0.1wt%, the In of 0.02wt%, 0.1wt%, the Bi of 2wt%, the Zn of 8wt% and the Sn of 89.748wt%.
Embodiment 3
A kind of SnZn base leadless solder that contains Cr, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.05wt%, the P of 0.01wt%, 0.15wt%, the In of 0.3wt%, 0.3wt%, the Bi of 3wt%, the Zn of 9wt% and the Sn of 87.19wt%.
Embodiment 4
A kind of SnZn base leadless solder that contains Cr, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.1wt%, the P of 0.004wt%, 0.2wt%, the In of 0.5wt%, 0.5wt%, the Bi of 5wt%, the Zn of 9wt% and the Sn of 84.696wt%.
Embodiment 5
A kind of SnZn base leadless solder that contains Cr, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.1wt%, the P of 0.01wt%, 0.2wt%, the In of 0.5wt%, 0.5wt%, the Bi of 5wt%, the Zn of 7wt% and the Sn of 86.69wt%.
Embodiment 6
A kind of SnZn base leadless solder that contains Cr, the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.1wt%, the P of 0.01wt%, 0.1wt%, the In of 0.25wt%, 0.25wt%, the Bi of 1wt%, the Zn of 11wt% and the Sn of 87.29wt%.
Comparative Examples 1
A kind of SnZn solder, the chemical composition of said solder is: the Zn of 9wt%, the Sn of 91wt%.
Comparative Examples 2
A kind of lead-free anti-oxidation rare-earth-contg SnZn solder, the chemical composition of said solder is: the In of the P of the Cu of 0.5wt%, the Ni of 0.5wt%, 0.1wt%, the Er of 0.5wt%, 0.005wt%, the Bi of 2wt%, the Sb of 2wt%, the Zn of 9wt% and the Sn of 85.395wt%.
The solder of embodiment 1 to 6 and Comparative Examples 1 and 2 is carried out liquidus temperature, solidus temperature, shear strength and the rate of spread assess, the gained result sees table 1.
The assessment result of the solder of table 1 embodiment 1 to 6 and Comparative Examples 1 and 2
| Solder | Liquidus temperature/℃ | Solidus temperature/℃ | Shear strength/MPa | The rate of spread/% |
| Embodiment 1 | 192.2 | 195.3 | 60.2 | 83.1 |
| Embodiment 2 | 191.3 | 193.7 | 61.3 | 85.3 |
| Embodiment 3 | 189.5 | 192.8 | 62.8 | 85.8 |
| Embodiment 4 | 189.1 | 192.2 | 64.5 | 82.6 |
| Embodiment 5 | 193.5 | 196.8 | 59.8 | 82.1 |
| Embodiment 6 | 193.8 | 197.1 | 59.5 | 81.9 |
| Comparative Examples 1 | 197 | 201 | 45.5 | 62 |
| Comparative Examples 2 | 189.2 | 192.5 | 59.8 | 79.8 |
Wherein, the liquidus curve of solder and solidus temperature record through slow cooling curve.Can find out that from table 1 the pure SnZn solder of the embodiment of the invention 1 to 6 and Comparative Examples 1 is compared, fusing point further reduces, and has the fusion temperature scope close with the SnPb solder, is fit to traditional soldering processes condition and requirement of components and parts heatproof at present.And compare with the lead-free anti-oxidation rare-earth-contg SnZn solder in the Comparative Examples 2, liquidus curve and solidus all do not have significant difference.
The rate of spread can be used for weighing the size of solder oxidation resistance.Because the oxidation resistance of solder is big, then solder oxidized degree in welding process is just low, and then the wetting and spreading ability of solder is just strong, and the rate of spread is just big, otherwise the rate of spread is just little.The rate of spread in the table 1 is to measure according to measurement requirement and step among " People's Republic of China's electron trade standard " SJ/T11186-1998 (tin lead plaster shape solder general specification) and " State Standard of the People's Republic of China " GB/T9491-2002 (liquid flux is used in soldering).Can find out from table 1; The pure SnZn solder of the embodiment of the invention 1 to 6 and Comparative Examples 1, the lead-free anti-oxidation rare-earth-contg SnZn solder in the Comparative Examples 2 are compared; The rate of spread is significantly improved, and that is to say, solder of the present invention has stronger oxidation resistance and wettability.
Shear strength is measured on cutter.Can find out from table 1; The solder shear strength of addition element Ni obviously promotes than the shear strength of the pure SnZn solder of Comparative Examples 1; Also be improved with the lead-free anti-oxidation rare-earth-contg SnZn solder shear strength in the Comparative Examples 2, this shows that solder of the present invention has mechanical performance preferably.
In sum, the present invention's SnZn base leadless solder of containing Cr has excellent non-oxidizability, wettability and mechanical performance.
According to the announcement and the instruction of above-mentioned specification, those skilled in the art according to the invention can also carry out suitable change and modification to above-mentioned embodiment.Therefore, the specific embodiment that discloses and describe above the present invention is not limited to also should fall in the protection domain of claim of the present invention modifications more of the present invention and change.In addition, although used some specific terms in this specification, these terms are explanation for ease just, the present invention is not constituted any restriction.
Claims (5)
1. SnZn base leadless solder that contains Cr; It is characterized in that; The chemical composition of said solder is: the Cr of the Nd of the Ni of 0.01-0.1wt%, the P of 0.001-0.01wt%, 0.05-0.2wt%, the In of 0.1-0.5wt%, 0.01-0.5wt%, the Bi of 1-5wt%, the Zn of 7-11wt%; Surplus is Sn, the percentage by weight of each component and be 100%.
2. the SnZn base leadless solder that contains Cr according to claim 1; It is characterized in that the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.01wt%, the P of 0.001wt%, 0.05wt%, the In of 0.1wt%, 0.01wt%, the Bi of 1wt%, the Zn of 8wt% and the Sn of 90.829wt%.
3. the SnZn base leadless solder that contains Cr according to claim 1; It is characterized in that the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.03wt%, the P of 0.002wt%, 0.1wt%, the In of 0.02wt%, 0.1wt%, the Bi of 2wt%, the Zn of 8wt% and the Sn of 89.748wt%.
4. the SnZn base leadless solder that contains Cr according to claim 1; It is characterized in that the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.05wt%, the P of 0.01wt%, 0.15wt%, the In of 0.3wt%, 0.3wt%, the Bi of 3wt%, the Zn of 9wt% and the Sn of 87.19wt%.
5. the SnZn base leadless solder that contains Cr according to claim 1; It is characterized in that the chemical composition of said solder is: the Cr of the Nd of the Ni of 0.1wt%, the P of 0.004wt%, 0.2wt%, the In of 0.5wt%, 0.5wt%, the Bi of 5wt%, the Zn of 9wt% and the Sn of 84.696wt%.
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| CN2011104271206A CN102489892A (en) | 2010-12-31 | 2011-12-20 | SnZn-based lead-free brazing filler metal containing Cr |
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| CN201010616266.0 | 2010-12-31 | ||
| CN201010616266 | 2010-12-31 | ||
| CN2011104271206A CN102489892A (en) | 2010-12-31 | 2011-12-20 | SnZn-based lead-free brazing filler metal containing Cr |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103240541A (en) * | 2013-05-13 | 2013-08-14 | 金封焊宝有限责任公司 | Tin zinc multi-element alloy solder for soldering copper and aluminum and preparation method thereof |
| CN103801852A (en) * | 2012-11-12 | 2014-05-21 | 恒硕科技股份有限公司 | High-strength silver-free and lead-free soldering tin |
| CN103934590A (en) * | 2014-04-13 | 2014-07-23 | 北京工业大学 | ZnAlMgIn high temperature lead-free solder |
| CN109943751A (en) * | 2019-05-10 | 2019-06-28 | 云南锡业集团（控股）有限责任公司研发中心 | A kind of low-temperature lead-free solder and its gravity casting method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103801852A (en) * | 2012-11-12 | 2014-05-21 | 恒硕科技股份有限公司 | High-strength silver-free and lead-free soldering tin |
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| CN103934590A (en) * | 2014-04-13 | 2014-07-23 | 北京工业大学 | ZnAlMgIn high temperature lead-free solder |
| CN103934590B (en) * | 2014-04-13 | 2016-08-17 | 北京工业大学 | A kind of ZnAlMgIn high-temp leadless solder |
| CN109943751A (en) * | 2019-05-10 | 2019-06-28 | 云南锡业集团（控股）有限责任公司研发中心 | A kind of low-temperature lead-free solder and its gravity casting method |
| CN109943751B (en) * | 2019-05-10 | 2021-03-12 | 云南锡业集团（控股）有限责任公司研发中心 | Low-temperature lead-free solder and gravity casting method thereof |
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Application publication date: 20120613 |