CN102974953A - Tin-copper-cobalt (Sn-Cu-Co) lead-free solder containing ferrum (Fe) and neodymium (Nd) - Google Patents
Tin-copper-cobalt (Sn-Cu-Co) lead-free solder containing ferrum (Fe) and neodymium (Nd) Download PDFInfo
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- CN102974953A CN102974953A CN2012105443524A CN201210544352A CN102974953A CN 102974953 A CN102974953 A CN 102974953A CN 2012105443524 A CN2012105443524 A CN 2012105443524A CN 201210544352 A CN201210544352 A CN 201210544352A CN 102974953 A CN102974953 A CN 102974953A
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Abstract
The invention provides tin-copper-cobalt (Sn-Cu-Co) lead-free solder containing ferrum (Fe) and neodymium (Nd), and the solder belongs to a braze welding material in the fields of metal materials and metallurgy. Chemical components (in mass percentage) are as follows: 0.3 percent to 1.5 percent of Cu, 0.05 percent to 2.5 percent of Co, 0.002 percent to 0.1 percent of Fe, and 0.01 percent to 0.2 percent of Nd, and the rest is Sn. The solder has good moistening performance, can effectively suppress the growth of the thickness of chemicals among brazing seam interface metal, so that the reliability of a braze welding connector is greatly improved, and the solder can be used for wave soldering, reflow soldering and other soldering methods in the electronic industry.
Description
Technical field
The present invention relates to the Sn-Cu-Co lead-free brazing of a kind of Fe of containing and Nd, belong to the brazing material of class of metal materials and field of metallurgy.Being mainly used in assembling and the encapsulation of electron trade components and parts, is that a kind of brazing property (such as wettability) is good, novel green, the environment-friendly type lead-free solder of solder joint (brazed seam) good mechanical performance.
Background technology
Along with RoHS(The Restriction of the Use of certain Hazardous Substance in Electrical and Electronic Equipment) the coming into force of instruction, the research and development lead-free brazing is the focus of electron trade technical staff research with the problem that substitutes tin-lead solder always.At present representative lead-free brazing has the alloy systems such as Sn-Ag-Cu, Sn-Zn, Sn-Cu, Sn-Cu-Ni, has his own strong points, but compares with tin-lead solder, is still having a certain distance aspect solder cost, the solder fusing point etc.The Sn-Cu-Ni brazing filler metal is owing to have preferably combination property, and moderate cost has a good application prospect, and has begun to use on wave-soldering.But, find that in use along with the prolongation of time, the thickness of compound has progressively the trend that increases, thickens between the brazed seam interface metal of Sn-Cu-Ni solder, thereby may reduce " reliability " of soldered fitting.Therefore, this problem that the Sn-Cu-Ni solder exists still needs Improvement.
Developed " lead-free brazing that contains cerium " (Chinese invention patent on the basis of the external Sn-Cu-Ni solder of recent year, CN1792539), " a kind of anti-molten copper tin copper lead free brazing material alloy " (Chinese invention patent, CN102554490A), " a kind of SAC cobalt lead-free brazing " (Chinese invention patent, CN102091882A) and " containing V; the Sn-Cu-Ni lead-free brazing of Nd and Ge " (Chinese invention patent, the Sn-Cu of multiple " multicomponent alloy system " such as CN101885119A), the Sn-Cu-Ni solder, the Sn-Cu of they and binary or ternary, the Sn-Cu-Ni alloy phase makes moderate progress than in some performance, but the grown in thickness of compound between the brazed seam interface metal, the research aspect that thickens not yet relates to, therefore, for Sn-Cu, " reliability " problem of Sn-Cu-Ni solder brazing joint still needs further research, improve.This invention " the Sn-Cu-Co lead-free brazing that contains Fe and Nd " is namely finished under this technical background.
Summary of the invention
The purpose of this invention is to provide a kind of good wettability that has, can effectively suppress the growth of compound thickness between the brazed seam interface metal, thereby improve widely " reliability " of soldered fitting and be applicable to the Sn-Cu-Co series leadless solder of the welding methods such as electron trade wave-soldering and reflow welding.
To achieve the object of the present invention, the Sn-Cu-Co lead-free brazing that contains Fe and Nd of the present invention through the chemical composition of determining after optimizing by the mass percent proportioning is: 0.3～1.5% Cu, 0.05～2.5% Co, 0.002 ~ 0.1% Fe, 0.01～0.2% Nd, surplus is Sn; Wherein the addition mass ratio of Co and Fe satisfies Co ︰ Fe=24～26 ︰ 1.
Adopt conventional method to prepare solder; namely use commercially available tin slab, neodymium metal, cathode copper, ferrocobalt; various raw metals are proportioning on demand, adds during smelting through optimizing screening definite commercially available " coverture " or adopting " inert gas " protection to smelt, cast, and can obtain bar.By extruding, drawing, namely obtain a material (also can add scaling powder, make " flux-cored wire ").The Pb element is as " impurity element " in the raw material such as tin slab, cathode copper, overall control (is stipulated Pb≤0.1wt.%) to satisfy the regulation meet State Standard of the People's Republic of China GB/T 20422-2006 " lead-free brazing " in the standard in Pb≤0.1 wt.% scope.
Consider the high and very easily oxidation of neodymium metal fusing point, also neodymium metal can be smelted into intermediate alloy in advance according to need of production, with the form adding of Sn-Nd, to guarantee the accuracy of neodymium metal composition in solder.
Solder even tissue of the present invention is easy to be processed into various shapes, such as strip, bar-shaped, thread, soldered ball, to adapt to the needs of different working conditions.
Description of drawings
Fig. 1 does not add the Sn-Cu-Co brazed seam interface topography of Fe and Nd;
Fig. 2 adds the Sn-Cu-Co brazed seam interface topography of Fe and Nd;
The Sn-Nd intermetallic compound that forms when Fig. 3 adds 0.25% Nd;
The relation curve of Fig. 4 Sn-0.3 Cu-2.5Co and Sn-0.3 Cu-2.5 Co-0.1 Fe-0.2Nd timeliness 1200 hours rear interface intermetallic compounds gross thickness and aging time (ordinate among the figure " IMC " is the english abbreviation of general " intermetallic compound " in the industry, lower with);
The relation curve of Fig. 5 Sn-1.1Cu-0.25 Co and Sn-1.1Cu-0.25 Co-0.01 Fe-0.12 Nd timeliness 1200 hours rear interface intermetallic compounds gross thickness and aging time;
The relation curve of Fig. 6 Sn-1.0Cu-0.2 Co and Sn-1.0Cu-0.2 Co-0.008 Fe-0.05Nd timeliness 1200 hours rear interface intermetallic compounds gross thickness and aging time;
The relation curve of Fig. 7 Sn-0.8 Cu-0.5Co and Sn-0.8 Cu-0.5Co-0.02 Fe-0.02Nd timeliness 1200 hours rear interface intermetallic compounds gross thickness and aging time;
The relation curve of Fig. 8 Sn-1.5Cu-0.05Co and Sn-1.5Cu-0.05Co-0.002 Fe-0.01Nd timeliness 1200 hours rear interface intermetallic compounds gross thickness and aging time.
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Specific embodiments
Compare with former studies, creativeness of the present invention is:
1) found effectively to suppress the Fe element that compound thickness increases between the brazed seam interface metal.
In process of the test of the present invention, research finds that Fe joins in the Sn-Cu-Co lead-free brazing, can effectively suppress the growth rate of compound thickness between Sn-Cu-Co lead-free brazing brazed seam interface metal.Further research finds that if add simultaneously Fe and Nd element, Fe is more remarkable to the inhibitory action of " growth rate of compound thickness between the brazed seam interface metal " of Sn-Cu-Co lead-free brazing.
Research is in the past unanimously thought, the adding of Fe element, the significantly wettability of " deterioration " Sn-Pb solder and lead-free brazing.Therefore, no matter be GB/T 3131-2001 " tin-lead solder " or GB/T 20422-2006 " lead-free brazing ", all with the Fe element as " impurity element ", require its content of control in 0.02%.
In the present invention, the research discovery, when Fe joins in the Sn-Cu-Co lead-free brazing, although can worsen the wettability of solder,, can be by adding simultaneously its negative effect of rare earth element nd " counteracting ".Even (exceeded 5 times of GB/T 3131-2001 " tin-lead solder ", GB/T 20422-2006 " lead-free brazing " standard gauge definite values) when the addition of Fe reaches 0.1%, the Sn-Cu-Co lead-free brazing that contains Fe and Nd still has good wettability.Yet the Fe of adding 0.002～0.1% to the inhibitory action that compound thickness between the brazed seam interface metal increases, but is very significant (referring to accompanying drawing 4～Fig. 8).Can find out from Fig. 4～Fig. 8, added the Sn-Cu-Co lead-free brazing of Fe and Nd element, the prolongation of compound gross thickness and aging time is (in the test between the brazed seam interface metal, generally acknowledge in the industry with aging time and come analog component service time) although all be the relation of " grow up, thickening ", but, added compound gross thickness between the Sn-Cu-Co lead-free brazing brazed seam interface metal of Fe and Nd element all less than the gross thickness of the Sn-Cu-Co lead-free brazing that does not add Fe and Nd element.Illustrate and add Fe and Nd element, really has the effect that compound thickness increases between the brazed seam interface metal that suppresses, thereby can reduce the risk that causes crack initiation, grows up, makes at last solder joint (brazed seam) to ftracture because of growing up of intermetallic compound, improve the reliability of solder joint (brazed seam).
Generally acknowledge because existing research is consistent, prolongation along with solder joint working time (as: components and parts service time), compound thickness can constantly increase (thickening) between the brazed seam interface metal, intermetallic compound can constantly be grown up, thereby Joint Strength is descended gradually, finally cause solder joint to destroy or inefficacy.Therefore, Chinese scholars is found by large quantity research, in the Sn-Cu lead-free brazing, add Ni or Co element, has the effect that compound thickness increases between the brazed seam interface metal that suppresses, thereby can reduce the risk that causes crack initiation, grows up, makes at last solder joint (brazed seam) to ftracture because of growing up of intermetallic compound, improve the reliability of solder joint (brazed seam).
The present inventor studies discovery, and Fe and Co or Ni element belong to the VIII family element in " periodic table of elements " together, analyzes from chemical theory, and Fe should tool and Co or the same or analogous effect of Ni element.Therefore, find by lot of experiments that the addition of Fe (mass percent) has the effect that compound thickness increases between the brazed seam interface metal that suppresses 0.002～0.1% the time really.
2) interpolation scope and the proportionate relationship of verification experimental verification and preferred Co and Fe
Found that by " sequential experiment design " method Fe joins in the Sn-Cu-Co lead-free brazing suppressing the rule that affects that compound thickness increases between the brazed seam interface metal, and tentatively determined interpolation scope and the proportionate relationship of Co and Fe.Namely in the scope of addition (mass percent) 0.002 ~ 0.1% of Fe, when the addition mass ratio of Co and Fe satisfied Co ︰ Fe=25 ︰ 1, neoteric lead-free brazing had good solder joint (or brazed seam) " reliability ".Can effectively suppress the growth of compound thickness between the brazed seam interface metal, thereby can reduce the risk that causes crack initiation, grows up, makes at last solder joint (brazed seam) to ftracture because of growing up of intermetallic compound, improve the reliability of solder joint (brazed seam).
(intermetallic compound thickness is at micron order because the size of weld thickness is little, generally at several micron between tens microns), measure error is large, therefore, the accurate ratio that existing research means can't be assessed Co ︰ Fe exactly (for example, when Co ︰ Fe=24 ︰ 1 or Co ︰ Fe=26 ︰ 1, whether Fe will significantly die down to the inhibitory action that compound thickness increases between the brazed seam interface metal in the Sn-Cu-Co lead-free brazing), therefore, " optimization " proportion of providing of the present invention proposes according to the experiment interpolation scope of " sequential experiment design " method.
3) optimized the interpolation scope of rare earth element nd
Compare with the existing lead-free brazing that adds rare earth element, in the alloy system that the present invention relates to, " favourable " interpolation scope of rare earth element nd is very narrow, only in 0.01～0.2% scope.Unlike other many lead-free brazings that contain rare earth element, can be low to moderate 0.001%, up to 1%.Primary Study shows, the adding of iron, so that rare earth element nd does not have due effect less than 0.01% the time, and the addition of Nd is greater than after 0.2%, the appearance of " rare-earth phase " under the existence condition of Fe, can have a negative impact (referring to accompanying drawing 3 to neoteric solder wetting performance, after the addition of Nd reaches 0.25%, " rare-earth phase " that occurs in the Sn-0.3Cu-2.5Ni-0.1 Fe-0.25Nd lead-free brazing).
According to the quality proportioning of " the Sn-Cu-Co lead-free brazing that contains Fe and Nd " of the present invention, narration the specific embodiment of the present invention is as follows.
Embodiment one
A kind of Sn-Cu-Co lead-free brazing that contains Fe and Nd is pressed the mass percent proportioning, and its composition is: 0.3% Cu, and 2.5% Co, 0.1% Fe, 0.2% Nd, surplus is Sn.
" the Sn-Cu-Co lead-free brazing that contains Fe and Nd " solidus temperature that the mentioned component proportioning obtains is about 228 ℃, and liquidus temperature (has all been considered test error) about 246 ℃.Cooperate commercially available RMA brazing flux to have good wettability at copper plate, brazed seam tensile strength reaches 40MPa ± 10MPa.
Fig. 4 shows that timeliness is after 1200 hours, and the Sn-Cu-Co lead-free brazing that has added Fe and Nd is less by about 30% than compound gross thickness between the lead-free brazing brazed seam interface metal of not adding Fe and Nd, illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment two
A kind of Sn-Cu-Co lead-free brazing that contains Fe and Nd is pressed the mass percent proportioning, and its composition is: 1.1% Cu, and 0.25% Co, 0.01% Fe, 0.12% Nd, surplus is Sn.
" the Sn-Cu-Co lead-free brazing that contains Fe and Nd " solidus temperature that the mentioned component proportioning obtains is about 228 ℃, and liquidus temperature (has all been considered test error) about 240 ℃.Cooperate commercially available RMA brazing flux to have good wettability at copper plate, brazed seam tensile strength reaches 40MPa ± 10MPa.
Fig. 5 shows that timeliness is after 1200 hours, and the Sn-Cu-Co lead-free brazing that has added Fe and Nd is less by about 30% than compound gross thickness between the lead-free brazing brazed seam interface metal of not adding Fe and Nd, illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment three
A kind of Sn-Cu-Co lead-free brazing that contains Fe and Nd is pressed the mass percent proportioning, and its composition is: 1.0% Cu, and 0.2% Co, 0.008% Fe, 0.05% Nd, surplus is Sn.
" the Sn-Cu-Co lead-free brazing that contains Fe and Nd " solidus temperature that the mentioned component proportioning obtains is about 228 ℃, and liquidus temperature (has all been considered test error) about 240 ℃.Cooperate commercially available RMA brazing flux to have good wettability at copper plate, brazed seam tensile strength reaches 40MPa ± 10MPa.
Fig. 6 shows that timeliness is after 1200 hours, and the Sn-Cu-Co lead-free brazing that has added Fe and Nd is less by about 30% than compound gross thickness between the lead-free brazing brazed seam interface metal of not adding Fe and Nd, illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment four
A kind of Sn-Cu-Co lead-free brazing that contains Fe and Nd is pressed the mass percent proportioning, and its composition is: 0.8% Cu, and 0.5% Co, 0.02% Fe, 0.02% Nd, surplus is Sn.
" the Sn-Cu-Co lead-free brazing that contains Fe and Nd " solidus temperature that the mentioned component proportioning obtains is about 226 ℃, and liquidus temperature (has all been considered test error) about 245 ℃.Cooperate commercially available RMA brazing flux to have good wettability at copper plate, brazed seam tensile strength reaches 40MPa ± 10MPa.
Fig. 7 shows that timeliness is after 1200 hours, and the Sn-Cu-Co lead-free brazing that has added Fe and Nd is less by about 30% than compound gross thickness between the lead-free brazing brazed seam interface metal of not adding Fe and Nd, illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Embodiment five
A kind of Sn-Cu-Co lead-free brazing that contains Fe and Nd is pressed the mass percent proportioning, and its composition is: 1.5% Cu, and 0.05% Co, 0.002% Fe, 0.01% Nd, surplus is Sn.
" the Sn-Cu-Co lead-free brazing that contains Fe and Nd " solidus temperature that the mentioned component proportioning obtains is about 230 ℃, and liquidus temperature (has all been considered test error) about 248 ℃.Cooperate commercially available RMA brazing flux to have good wettability at copper plate, brazed seam tensile strength reaches 40MPa ± 10MPa.
Fig. 8 shows that timeliness is after 1200 hours, and the Sn-Cu-Co lead-free brazing that has added Fe and Nd is less by about 30% than compound gross thickness between the lead-free brazing brazed seam interface metal of not adding Fe and Nd, illustrates that the reliability of solder joint (brazed seam) is significantly improved.
Claims (2)
1. Sn-Cu-Co lead-free brazing that contains Fe and Nd, it is characterized in that: composition by the mass percent proportioning is: 0.3～1.5% Cu, 0.05～2.5% Co, 0.002～0.1% Fe, 0.01～0.2% Nd, surplus is Sn; Wherein the addition mass ratio of Co and Fe satisfies Co ︰ Fe=24～26 ︰ 1.
2. the Sn-Cu-Co lead-free brazing that contains Fe and Nd according to claim 1, it is characterized in that: the optimum addition mass ratio of Co and Fe satisfies Co ︰ Fe=25 ︰ 1.
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| CN201210544352.4A CN102974953B (en) | 2012-12-17 | 2012-12-17 | Tin-copper-cobalt (Sn-Cu-Co) lead-free solder containing ferrum (Fe) and neodymium (Nd) |
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| CN201210544352.4A CN102974953B (en) | 2012-12-17 | 2012-12-17 | Tin-copper-cobalt (Sn-Cu-Co) lead-free solder containing ferrum (Fe) and neodymium (Nd) |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018589A (en) * | 2000-07-03 | 2002-01-22 | Senju Metal Ind Co Ltd | Lead-free solder alloy |
| CN1799756A (en) * | 2006-01-12 | 2006-07-12 | 上海大学 | Sn-Co-Cu tri-elemental lead-free solder |
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN101342643A (en) * | 2008-09-03 | 2009-01-14 | 东南大学 | Oxidation resistant lead-free solder containing rare earth neodymium |
| CN101579790A (en) * | 2009-06-03 | 2009-11-18 | 南京航空航天大学 | Sn-Ag-Cu lead-free solder containing Nd, Li, As and In |
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2012
- 2012-12-17 CN CN201210544352.4A patent/CN102974953B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018589A (en) * | 2000-07-03 | 2002-01-22 | Senju Metal Ind Co Ltd | Lead-free solder alloy |
| CN101132881A (en) * | 2004-12-01 | 2008-02-27 | 爱尔发加热有限公司 | Solder alloy |
| CN1799756A (en) * | 2006-01-12 | 2006-07-12 | 上海大学 | Sn-Co-Cu tri-elemental lead-free solder |
| CN101342643A (en) * | 2008-09-03 | 2009-01-14 | 东南大学 | Oxidation resistant lead-free solder containing rare earth neodymium |
| CN101579790A (en) * | 2009-06-03 | 2009-11-18 | 南京航空航天大学 | Sn-Ag-Cu lead-free solder containing Nd, Li, As and In |
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