CN102513720A - High-performance tin-based solder alloy and preparation method thereof - Google Patents
High-performance tin-based solder alloy and preparation method thereof Download PDFInfo
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- CN102513720A CN102513720A CN2011104376176A CN201110437617A CN102513720A CN 102513720 A CN102513720 A CN 102513720A CN 2011104376176 A CN2011104376176 A CN 2011104376176A CN 201110437617 A CN201110437617 A CN 201110437617A CN 102513720 A CN102513720 A CN 102513720A
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Abstract
The invention discloses high-performance tin-based solder alloy, which comprises a tin-based solder body, refractory hard dispersion strengthening phase particles and 0.01wt%-2wt% of doped elements, wherein the doped elements include one or multiple of Fe, Ni, Y, Ag, Ti, Zr, Hf and Sb. Due to the added doped elements, interface bonding property between the tin-based solder body and the refractory hard dispersion strengthening phase particles is improved, aggregation of the strengthening phase particles in remelting is reduced, and the mechanical property is improved accordingly. The invention further discloses a preparation method of the high-performance tin-based solder alloy, which combines the powder metallurgy preparation process with the ultrasonic-assistant casting process so that the strengthening phase particles are high in dispersion and uniform in distribution, solves the problem that the strengthening phase particles are difficult to be added when in use of the ultrasonic-assistant casting process individually, the mechanical property of the tin-based solder alloy is improved, and the performance of the solder can keep stable basically after the solder is remelted.
Description
Technical field
The present invention relates to a kind of tin-based solder alloy, especially a kind of high-performance granule reinforced tin base solder alloy.The invention still further relates to the preparation method of high-performance tin-based solder alloy.
Background technology
Along with electronic product to the developing rapidly of volume microminiaturization and function integrated direction, make them propose requirements at the higher level to the reliability of existing encapsulating material.Particle strengthens very promising a kind of electronic package material that solder is considered to improve solder performance at present; Through in the solder matrix, adding hard infusibility second phase (like pottery and refractory metal particle), can be implemented in the intensity and effective serviceability temperature interval that increase substantially solder under the less prerequisite that influences solder fusing point and toughness.
For general particle strengthened alloy, the key of its performance boost was to reduce as far as possible the particle diameter of enhanced granule and lets them be uniformly distributed in the metallic matrix.Yet for particle strengthens solder, owing to when reality is used, also need pass through the remelting of different temperatures and time, so it has proposed higher requirement to the stability of particle wild phase in molten solder.Avoiding the particle wild phase in molten solder, to take place to reunite with separating is the key point that improves the composite soldering welding spot reliability.When the composite soldering remelting; The porosity in the reunion of particle wild phase and the particle diameter of wild phase, the solder and the interfacial combined function of wild phase and solder matrix are relevant; Particle diameter is more little, porosity is high more, interfacial combined function is poor more, and then the particle wild phase is reunited in molten solder more easily.The separation that particle strengthens mainly receives the influence of wild phase density and particle diameter, and concrete relation is: the separating rate of wild phase is directly proportional with the difference of wild phase and solder matrix density, square is inversely proportional to the particle diameter of wild phase.For the nano particle wild phase that even dispersion distributes, it is very slow that the separating rate of wild phase will become, and when common solder reflow welding, the separation of nano particle wild phase almost can be ignored.Yet,, and accelerate the separation of wild phase in case when existing bubble or solder and wild phase binding ability relatively poor in the solder, the nanometer wild phase will very easily be reunited.
Mechanical alloying method and powder metallurgy process are the particles reiforced metal-base composition preparation methods of using always; Adopt its enhanced granule of composite of this kind method preparation can reach the good spread; Yet the composite soldering porosity of this method preparation is high; In the reflow process of solder; Pore in the molten solder will promote dimension to receive the reunion of particle wild phase and the strengthening effect of reduction particle wild phase; In addition, the wild phase after the reunion will separate in the liquid solder of fusion more easily, thus the strengthening effect of the wild phase of further decaying.Moreover; Because ceramic enhancement phase generally has lower interfacial combined function; For low-melting tin-based solder alloy; For example: tinbase series alloys such as Sn-Ag-Cu, Sn-Cu, Sn-Ag, Sn-Pb, Sn-Bi and Sn-Zn be difficult to improve the binding ability between brazing filler metal alloy and the wild phase through the method for mechanical alloying, and this also will cause the reunion of wild phase.
Adopt the method for ultrasonic auxiliary light-alloy casting that more research and report have been arranged, ultrasonic through in alloy graining process, continuing, ultrasonic cavitation and flow stirring action can play good uniform formation, crystal grain thinning effect; In addition; In molten alloy, contain the second not molten phase time; Ultrasonic second-phase dispersion is evenly distributed; Can also promote the liquid matrix and not molten second wetting between mutually, make melt second when alloy melting, play nucleating agent effect, crystal grain thinning also strengthens alloy mechanical property.For the tin-based solder alloy, because this alloy has bigger density (about 6.5g/cm
3), and lower (the about 3.5g/cm of particle wild phase density commonly used
3), therefore even if in the process of solder fusion, have ultrasonic or mechanical assistance stirs and also is difficult to the wild phase of capacity is joined in the solder matrix.Just because of this, not finding as yet at present has the people to adopt ultrasonic auxiliary method to prepare the granule reinforced tin base solder alloy, the tin-based solder alloy that the particle wild phase is reunited when also failing to obtain to overcome the brazing filler metal alloy remelting, mechanical property is improved significantly.
Summary of the invention
For solving the problem that above-mentioned prior art exists, the present invention provides a kind of high-performance tin-based solder alloy, and this tin-based solder alloy has the mechanical property and the decay resistance of obvious raising.The present invention also provides the preparation method of high-performance tin-based solder alloy.
The technical scheme that the present invention adopted is: a kind of high-performance tin-based solder alloy; Comprise that tin-based solder matrix and the dispersion-strengtherning of infusibility hard are mutually; Said high-performance tin-based solder alloy comprises that also weight percentage is 0.01%～2% doped chemical, and said doped chemical is one or more among Fe, Ni, Y, Ag, Ti, Zr, Hf, the Sb.
Preferably, the dispersion-strengtherning of said infusibility hard is SiC, TiO mutually
2, ZrO
2, Y
2O
3, MgO, Al
2O
3, TiB
2, CNTs (CNT, as follows) and Cu
6Sn
5In one or more, its weight percentage is 0.02%～2%.
Preferably, said tin-based solder matrix is Sn-Ag-Cu, Sn-Cu, Sn-Ag, Sn-Pb, Sn-Bi or Sn-Zn alloy.
The method of the aforesaid high-performance tin-based solder of preparation of the present invention alloy; The tin-based solder that wherein forms said tin-based solder matrix comprises the tin-based solder powder or is no less than the tin-based solder powder of tin-based solder matrix weight 10% and the as cast condition tin-based solder of remaining weight that said preparation method comprises the following step that carries out successively:
A1, said tin-based solder powder, infusibility hard dispersion-strengtherning phase powder and doped chemical powder and ethanol and/or brazing flux are mixed and made into pulpous state or paste mixture;
A2, prepared pulpous state or paste mixture are placed 50 ℃～100 ℃ following vacuum drying, cold moudling gets the composite alloy piece under 400MPa～700MPa pressure then;
A3, place container to be melted into melt fully as cast condition tin-based solder, composite alloy piece, and make melt temperature be higher than 10 ℃～200 ℃ of the liquidus temperatures of said tin-based solder;
A4, melt is applied ultrasonic vibration 1～20 time, each ultrasonic vibration time is 5～300 seconds, is 5～60 second ultrasonic blanking time when applying twice when above, and cast molding gets high-performance tin-based solder alloy then.
As further improvement, ball-milling method is adopted in the mixing in the said steps A 1, and milling atmosphere is Ar, and ratio of grinding media to material is 5: 1～20: 1, and rotating speed is 100rpm～300rmp, and the ball milling time is 1～10 hour; Perhaps directly adopt craft or mechanical agitation to mix, mixing time is 5～60 minutes.
As further improvement, when applying ultrasonic vibration in the said steps A 4 ultrasonic amplitude transformer stretched into and directly put on melt in the melt, perhaps ultrasonic amplitude transformer is applied ultrasonic vibration in container side or bottom.
As further improvement, when the tin-based solder that forms said tin-based solder matrix comprised the as cast condition tin-based solder, said steps A 3 comprised step by step following: make the fusing fully in container of as cast condition tin-based solder earlier, and then adding composite alloy piece makes it to melt.
As further improvement, the average grain diameter of said infusibility hard dispersion-strengtherning phase powder is 30～2000nm, more preferably 60～1000nm; The average grain diameter of said tin-based solder powder is 1～500 μ m, more preferably 1～200 μ m.
In addition; Under preparation method's of the present invention design; A kind of preparation method who does not contain the high-performance tin-based solder alloy of doped chemical also is provided; Said high-performance tin-based solder alloy comprise tin-based solder matrix and weight percentage be 0.02%～2% infusibility hard dispersion-strengtherning mutually, said tin-based solder matrix is Sn-Ag-Cu, Sn-Cu, Sn-Ag, Sn-Pb, Sn-Bi or Sn-Zn alloy, the dispersion-strengtherning of said infusibility hard is SiC, TiO mutually
2, ZrO
2, Y
2O
3, MgO, Al
2O
3, TiB
2, CNTs and Cu
6Sn
5In one or more; The tin-based solder that forms said tin-based solder matrix comprises the tin-based solder powder or is no less than the tin-based solder powder of tin-based solder matrix weight 10% and the as cast condition tin-based solder of remaining weight that said preparation method comprises the following step that carries out successively:
B1, powder and ethanol and/or brazing flux are mixed and made into pulpous state or paste mixture mutually with said tin-based solder powder and the dispersion-strengtherning of infusibility hard;
B2, prepared pulpous state or paste mixture are placed 50 ℃～100 ℃ following vacuum drying, cold moudling gets the composite alloy piece under 400MPa～700MPa pressure then;
B3, place container to be melted into melt fully as cast condition tin-based solder, composite alloy piece, and make melt temperature be higher than 10 ℃～200 ℃ of the liquidus temperatures of said tin-based solder;
B4, melt is applied ultrasonic vibration 1～20 time, each ultrasonic vibration time is 5～300 seconds, and be 5～60 seconds ultrasonic blanking time, and cast molding gets high-performance tin-based solder alloy then.
High-performance tin-based solder alloy of the present invention has improved the interfacial combined function between tin-based solder matrix and the particle wild phase through the adding of doping phase, reduce the reunion of particle wild phase when remelting, thereby mechanical property is improved; The adding of the phase of mixing has in addition also improved the decay resistance of tin-based solder alloy.
Powder metallurgy is prepared process to the preparation method of high-performance tin-based solder alloy of the present invention and ultrasonic auxiliary fusion-casting process combines particle wild phase, doped chemical highly dispersed are evenly distributed; The method that powder metallurgy combines with ultrasonication has also overcome the problem that the ultrasonic casting method of simple employing is difficult to add the particle wild phase, has realized containing the preparation of big mass percent particle wild phase composite soldering; Cavitation ultrasonic when the solder fusion can be adsorbed the air film at nanometer enhanced granule interface completely, thereby promotes the distribution of particle wild phase, promotes wetting the carrying out with interfacial reaction in interface; Avoided tin-based solder alloy particle wild phase in follow-up remelting is used to reunite once more and avoided the existence of field trash in the solder; Thereby improved the mechanical property and the decay resistance of tin-based solder alloy, and its performance kept stable after the solder reflow.
The specific embodiment
Below in conjunction with embodiment the present invention is elaborated, can further be well understood to the present invention through these embodiment.But they are not to qualification of the present invention.
Preferred high-performance tin-based solder alloy of the present invention; Comprise that tin-based solder matrix and the dispersion-strengtherning of infusibility hard are 0.01%～2% doped chemical mutually with weight percentage, doped chemical is selected from one or more among Fe, Ni, Y, Ag, Ti, Zr, Hf, the Sb; The dispersion-strengtherning of infusibility hard is selected from SiC, TiO mutually
2, ZrO
2, Y
2O
3, MgO, Al
2O
3, TiB
2, CNTs and Cu
6Sn
5In one or more, its weight percentage is 0.02%～2%; The tin-based solder matrix is Sn-Ag-Cu, Sn-Cu, Sn-Ag, Sn-Pb, Sn-Bi or Sn-Zn alloy.The preferred content of doped chemical is 0.05～0.5%, and the preferred content of infusibility hard dispersion-strengtherning phase is 0.1～1%.
Can prepare high-performance tin-based solder alloy through the following step; The tin-based solder that wherein forms the tin-based solder matrix can all be the tin-based solder powder; Perhaps not only use the tin-based solder powder but also use the as cast condition tin-based solder, but the consumption of tin-based solder powder is no less than 10% of tin-based solder matrix weight.The following step carries out successively:
(1), tin-based solder powder, infusibility hard dispersion-strengtherning phase powder and doped chemical powder and ethanol and/or brazing flux are mixed and made into pulpous state or paste mixture; Wherein the average grain diameter of infusibility hard dispersion-strengtherning phase powder is preferably 30～2000nm, more preferably 60～1000nm; The average grain diameter of tin-based solder powder is preferably 1～500 μ m, 1～200 μ m more preferably, and the particle diameter of doped chemical powder does not have special demands; Brazing flux does not have special demands, adopts general product to get final product, and the consumption of ethanol and brazing flux is not special yet to be limited, and cubing is that 1/10 ~ 1/5 of mixed powder is good; Method of mixing does not have special demands yet, for example adopts ball-milling method, and milling atmosphere is Ar, and ratio of grinding media to material is 5: 1～20: 1, and rotating speed is 100rpm～300rmp, and the ball milling time is 1～10 hour; Perhaps directly adopt craft or mechanical agitation to mix, mixing time is 5～60 minutes.
(2), prepared pulpous state or paste mixture are placed 50 ℃～100 ℃ following vacuum drying, remove volatile matter, cold moudling gets the composite alloy piece under 400MPa～700MPa pressure then;
(3), place container to be melted into melt fully as cast condition tin-based solder, composite alloy piece, and make melt temperature be higher than 10 ℃～200 ℃ of the liquidus temperatures of tin-based solder; When tin-based solder comprises the as cast condition tin-based solder; Preferable methods is to make the fusing fully in container of as cast condition tin-based solder earlier; And then add the composite alloy piece and make it to melt and obtain melt, can prevent composite alloy piece over oxidation in melting process of cold moudling; Used container can be selected titanium alloy tin pot for use.
(4), ultrasonic amplitude transformer is stretched in the melt, the degree of depth that immerses melt is preferably 5～50mm, starts ultrasonic vibration behind preheating 3～10s; Stop vibration behind the ultrasonic vibration certain hour and in molten solder, extract ultrasonic amplitude transformer; Once more ultrasonic amplitude transformer is stretched in the molten solder behind the pause certain hour, after preheating, restart ultrasonic vibration, melt is applied ultrasonic vibration 1～20 time; Each ultrasonic vibration time is 5～300 seconds, and be 5～60 seconds ultrasonic blanking time; Preferred parameter is: supersonic frequency 15～70KHz,, the ultrasonic power value and the ratio that is applied melt volume of input is 5～200W/cm
3, 10～150 microns of ultrasonic amplitudes; Ultrasonic amplitude transformer can not stretch in the melt yet, but acts on container side or bottom, through container is applied ultrasonic vibration, again through container with ultrasonic indirect transfer to melt.Ultrasonication gets high-performance tin-based solder alloy with the melt cast molding after finishing.
In the process of step (3) and (4), all under vacuum or inert gas such as argon gas atmosphere, implement, be favourable to the oxidation of avoiding alloy.
Preparation method's step is not used doped chemical in (1), and other conditions and step are constant, can make the high-performance tin-based solder alloy that does not contain doped chemical.
Embodiment 1
The used material of this instance is: Sn-3.0Ag-0.5Cu (SAC305) tin-based solder powder, pure titanium metal powder and particle diameter that particle diameter is about 2 μ m are the SiC powder of 60nm.Tin pot material is pure titanium, is of a size of: 38mm * 35mm, once molten tin amount is 200g in the practical operation.The ultrasonic amplitude transformer material is titanium alloy (Ti-6Al-4V), and ultrasonic power is 1000W, and the ultrasonic vibration time is 120 seconds, and supersonic frequency is 20KHz, and the degree of depth that ultrasonic amplitude transformer immerses in the molten solder is 5mm.
Get SAC305 solder powder 199.4g, SiC powder 0.4g and pure titanium metal powder 0.2g, above-mentioned powder is poured into carried out ball milling in the ball grinder.Ratio of grinding media to material is 5:1, and ball grinder and abrading-ball material are zirconia, and ball-milling medium is the mixed liquor of brazing flux and alcohol, and the ball milling protective atmosphere is Ar, and the ball milling time is 1h, and rotational speed of ball-mill is 200rpm.The paste mixture that ball milling is good takes out the back dries in vacuum drying chamber, through cold pressing forming process powder is pressed into the composite alloy piece that average quality is 40g subsequently.
With gross mass is that the above-mentioned composite alloy piece of 200g is put into pure tin tin pot, will quickly heat up to 300 ℃ and keep constant temperature through the tin stove, makes the composite alloy piece be fused into melt fully; Ultrasonic amplitude transformer is stretched in the melt, and preheating was opened ultrasonic vibration after 5 seconds.Treat that ultrasonic vibration finishes ultrasonic vibration and ultrasonic amplitude transformer is extracted after 250 seconds, take out simultaneously the pure tin pot with melt cast in punching block, so far accomplish the preparation of tin-based solder alloy.Said process is all accomplished under the Ar protective atmosphere.
The SEM characterization result shows, tiny, the size homogeneous of microscopic structure particle in this tin-based solder alloy, is evenly distributed, and through this tissue kept stable after the uniform temperature remelting.Solder fusing point and micro-hardness testing result show: the fusing point of this novel brazing filler metal alloy is 217.2 ℃, and is suitable with common SAC305 fusing point (218 ℃); The average hardness of novel brazing filler metal alloy is 23.27HV, compares normal solder hardness (16.32HV), and this novel brazing filler metal alloy hardness has improved 42.59%.
Embodiment 2
The used material of this instance is: Sn-0.3Ag-0.7Cu casting alloy bar, Hf powder, particle diameter are about the Sn-0.3Ag-0.7Cu brazing filler metal alloy powder of 10 μ m and the ZrO that particle diameter is about 1 μ m
2Powder.Tin pot material is pure titanium, is of a size of: 38mm * 35mm, once molten tin amount is 200g in the practical operation.The ultrasonic amplitude transformer material is titanium alloy (Ti-6Al-4V), and ultrasonic power is 1200W, and supersonic frequency is 20KHz, and the degree of depth that ultrasonic amplitude transformer immerses in the molten solder is 5mm.
Get Sn-0.3Ag-0.7Cu solder powder 97.8 grams, ZrO
2Powder 2g and Hf powder (oil immersion Hf powder is weighed behind the vacuum drying) 0.2 gram is with carrying out ball milling in the above-mentioned importing ball grinder.Ratio of grinding media to material is 10:1, and ball grinder and abrading-ball material are zirconia, and ball-milling medium is the mixed liquor of brazing flux and alcohol, and the ball milling protective atmosphere is Ar, and the ball milling time is 2h, and rotational speed of ball-mill is 200rpm.Solder powder that ball milling is good takes out the back dries in vacuum drying chamber, subsequently through cold pressing forming process with the powder composite alloy piece that to be pressed into 5 average qualities be 20g.
With quality is that the Sn-0.3Ag-0.7Cu casting alloy bar of 100g is put into pure tin tin pot, through the tin stove solder is heated to 280 ℃ and keep constant temperature, and this moment, solder was in molten condition; The 100g composite alloy piece that adopts powder metallurgy process to make is inserted in the molten solder; Simultaneously ultrasonic amplitude transformer is stretched in the molten solder, preheating was opened ultrasonic vibration after 5 seconds, and the ultrasonic vibration time is 200 seconds; Extracting ultrasonic amplitude transformer after vibration finishes left standstill 10 seconds by molten solder; Stretch into ultrasonic amplitude transformer in the solder once more subsequently and open ultrasonic vibration, following step is consistent with ultrasonication for the first time, so has altogether reciprocal 3 times.Treat after ultrasonication for the third time finishes ultrasonic amplitude transformer to be extracted, take out the pure tin pot simultaneously molten solder is cast in the punching block, so far accomplish the preparation of high-performance tin-based solder alloy.Said process is all accomplished under the Ar protective atmosphere.
This tin-based solder alloy is carried out micro-hardness testing, and the result shows: the average hardness of novel solder is 25.67HV, compares normal solder hardness (14.61HV), and this novel solder hardness has improved 75.7%.
Embodiment 3
The used material of this instance is: Sn-0.3Ag-0.7Cu solder powder and the average caliber that Sn-0.3Ag-0.7Cu casting alloy bar, Ti powder, particle diameter are about 10 μ m for and length be respectively multi-walled carbon nano-tubes (CNTs) powder of 10nm and 10 μ m.Tin pot material is pure titanium, is of a size of: 38mm * 35mm, once molten tin amount is 200g in the practical operation.The ultrasonic amplitude transformer material is titanium alloy (Ti-6Al-4V), and ultrasonic power is 1200W, and supersonic frequency is 20KHz, and the degree of depth that ultrasonic amplitude transformer immerses in the molten solder is 5mm.
Get Sn-0.3Ag-0.7Cu solder powder 198.6 grams, CNTs powder 1 gram and Ti powder 0.4 gram, above-mentioned powder is poured into carried out ball milling in the ball grinder.Ratio of grinding media to material is 10:1, and ball grinder and abrading-ball material are zirconia, and ball-milling medium is the mixed liquor of brazing flux and alcohol, and the ball milling protective atmosphere is Ar, and the ball milling time is 2h, and rotational speed of ball-mill is 200rpm.The solder powder that ball milling is good takes out the back dries in vacuum drying chamber, through cold pressing forming process powder is pressed into the composite alloy piece that average quality is 40g subsequently.
With gross mass is that the above-mentioned composite alloy piece of 200g is put into pure tin tin pot, quickly heats up to 260 ℃ and keep constant temperature, and this moment, the composite alloy piece was in molten condition; Ultrasonic amplitude transformer is stretched in the melt; Preheating was opened ultrasonic vibration after 5 seconds; The ultrasonic vibration time is 30 seconds, extracts ultrasonic amplitude transformer after vibration finishes and leaves standstill 5 seconds by melt, stretches into ultrasonic amplitude transformer in the melt once more subsequently and opens ultrasonic vibration; Following step is consistent with ultrasonication for the first time, so has altogether reciprocal 8 times.Treat after the 8th ultrasonication finishes ultrasonic amplitude transformer to be extracted, take out the pure tin pot simultaneously the molten solder alloy is cast in the punching block, so far accomplish the preparation of high-performance tin-based solder alloy.Said process is all accomplished under the Ar protective atmosphere.
This tin-based solder alloy is carried out micro-hardness testing, and the result shows: the average hardness of novel solder is 23.82HV, compares normal solder hardness (14.61HV), and this novel solder hardness has improved 63.0%.
Embodiment 4
The used material of this instance is: SAC305 casting alloy bar, particle diameter are about the SAC305 tin-based solder powder of 2 μ m and the SiC powder that particle diameter is 700nm.Tin pot material is pure titanium, is of a size of: 38mm * 35mm, once molten tin amount is 200g in the practical operation.The ultrasonic amplitude transformer material is titanium alloy (Ti-6Al-4V), and ultrasonic power is 1200W, and supersonic frequency is 20KHz, and the degree of depth that ultrasonic amplitude transformer immerses in the molten solder is 5mm.
Get SAC305 solder powder 39g and SiC powder 1g, both are poured in the beaker, and carry out manual stirring, in the process that stirs, constantly add alcohol, to guarantee that mixing solder is in thick all the time through the stainless steel spoon.Stirring continued after 30 minutes, and as for drying in the vacuum drying chamber, the mixed-powder after will drying through cold pressing forming process subsequently is pressed into the composite soldering piece that quality is 40g with the beaker that fills solder.
With quality is that the SAC305 casting alloy bar of 160g is put into pure tin tin pot, through the tin stove solder is heated to 300 ℃ and keep constant temperature, and this moment, solder was in molten condition; The 40g composite soldering piece that adopts powder metallurgy process to make is inserted in the molten solder; And ultrasonic amplitude transformer stretched in the molten solder, preheating was opened ultrasonic vibration after 5 seconds, and the ultrasonic vibration time is 60 seconds; Extracting ultrasonic amplitude transformer after vibration finishes left standstill 20 seconds by molten solder; Stretch into ultrasonic amplitude transformer in the solder once more subsequently and open ultrasonic vibration, following step is consistent with ultrasonication for the first time, so has altogether reciprocal 3 times.Treat after ultrasonication for the third time finishes ultrasonic amplitude transformer to be extracted solder, take out the pure tin pot simultaneously molten solder is cast in the punching block, so far accomplish the preparation that particle strengthens composite soldering.Said process is all accomplished under the Ar protective atmosphere.
The SEM characterization result shows, tiny, the size homogeneous of microscopic structure particle in this compound solder alloy, is evenly distributed, and through this tissue kept stable after the uniform temperature remelting.Solder fusing point and micro-hardness testing result show: the fusing point of this novel solder is 216.8 ℃, and is suitable with common SAC305 fusing point (218 ℃); The average hardness of novel solder is 24.67HV, compares normal solder hardness (16.32HV), and this novel solder hardness has improved 51.16%.
Claims (9)
1. high-performance tin-based solder alloy; Comprise that tin-based solder matrix and the dispersion-strengtherning of infusibility hard are mutually; It is characterized in that: said high-performance tin-based solder alloy comprises that also weight percentage is 0.01%～2% doped chemical, and said doped chemical is one or more among Fe, Ni, Y, Ag, Ti, Zr, Hf, the Sb.
2. high-performance tin-based solder alloy according to claim 1 is characterized in that: the dispersion-strengtherning of said infusibility hard is SiC, TiO mutually
2, ZrO
2, Y
2O
3, MgO, Al
2O
3, TiB
2, CNTs and Cu
6Sn
5In one or more, its weight percentage is 0.02%～2%.
3. high-performance tin-based solder alloy according to claim 1 and 2 is characterized in that: said tin-based solder matrix is Sn-Ag-Cu, Sn-Cu, Sn-Ag, Sn-Pb, Sn-Bi or Sn-Zn alloy.
4. like the preparation method of claim 1,2 or 3 described high-performance tin-based solder alloys; It is characterized in that: the tin-based solder that forms said tin-based solder matrix comprises the tin-based solder powder or is no less than the tin-based solder powder of tin-based solder matrix weight 10% and the as cast condition tin-based solder of remaining weight that said preparation method comprises the following step that carries out successively:
A1, said tin-based solder powder, infusibility hard dispersion-strengtherning phase powder and doped chemical powder and ethanol and/or brazing flux are mixed and made into pulpous state or paste mixture;
A2, prepared pulpous state or paste mixture are placed 50 ℃～100 ℃ following vacuum drying, cold moudling gets the composite alloy piece under 400MPa～700MPa pressure then;
A3, place container to be melted into melt fully as cast condition tin-based solder, composite alloy piece, and make melt temperature be higher than 10 ℃～200 ℃ of the liquidus temperatures of said tin-based solder;
A4, melt is applied ultrasonic vibration 1～20 time, each ultrasonic vibration time is 5～300 seconds, is 5～60 second ultrasonic blanking time when applying twice when above, and cast molding gets high-performance tin-based solder alloy then.
5. the preparation method of high-performance tin-based solder alloy according to claim 4; It is characterized in that: ball-milling method is adopted in the mixing in the said steps A 1, and milling atmosphere is Ar, and ratio of grinding media to material is 5: 1～20: 1; Rotating speed is 100rpm～300rmp, and the ball milling time is 1～10 hour; Perhaps directly adopt craft or mechanical agitation to mix, mixing time is 5～60 minutes.
6. according to the preparation method of claim 4 or 5 described high-performance tin-based solder alloys; It is characterized in that: when applying ultrasonic vibration in the said steps A 4 ultrasonic amplitude transformer stretched into and directly put on melt in the melt, perhaps ultrasonic amplitude transformer is applied ultrasonic vibration in container side or bottom.
7. according to the preparation method of claim 4,5 or 6 described high-performance tin-based solder alloys; It is characterized in that: when the tin-based solder that forms said tin-based solder matrix comprises the as cast condition tin-based solder; Said steps A 3 comprises step by step following: make the fusing fully in container of as cast condition tin-based solder earlier, and then adding composite alloy piece makes it to melt.
8. according to the preparation method of claim 4 or 5 described high-performance tin-based solder alloys, it is characterized in that: the average grain diameter of said infusibility hard dispersion-strengtherning phase powder is 30～2000nm, and the average grain diameter of said tin-based solder powder is 1～500 μ m.
9. the preparation method of a high-performance tin-based solder alloy; Said high-performance tin-based solder alloy comprise tin-based solder matrix and weight percentage be 0.02%～2% infusibility hard dispersion-strengtherning mutually; Said tin-based solder matrix is Sn-Ag-Cu, Sn-Cu, Sn-Ag, Sn-Pb, Sn-Bi or Sn-Zn alloy, and the dispersion-strengtherning of said infusibility hard is SiC, TiO mutually
2, ZrO
2, Y
2O
3, MgO, Al
2O
3, TiB
2, CNTs and Cu
6Sn
5In one or more; It is characterized in that: the tin-based solder that forms said tin-based solder matrix comprises the tin-based solder powder or is no less than the tin-based solder powder of tin-based solder matrix weight 10% and the as cast condition tin-based solder of remaining weight that said preparation method comprises the following step that carries out successively:
B1, powder and ethanol and/or brazing flux are mixed and made into pulpous state or paste mixture mutually with said tin-based solder powder and the dispersion-strengtherning of infusibility hard;
B2, prepared pulpous state or paste mixture are placed 50 ℃～100 ℃ following vacuum drying, cold moudling gets the composite alloy piece under 400MPa～700MPa pressure then;
B3, place container to be melted into melt fully as cast condition tin-based solder, composite alloy piece, and make melt temperature be higher than 10 ℃～200 ℃ of the liquidus temperatures of said tin-based solder;
B4, melt is applied ultrasonic vibration 1～20 time, each ultrasonic vibration time is 5～300 seconds, and be 5～60 seconds ultrasonic blanking time, and cast molding gets high-performance tin-based solder alloy then.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110437617.6A CN102513720B (en) | 2011-12-23 | 2011-12-23 | High-performance tin-based solder alloy and preparation method thereof |
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|---|---|---|---|
| CN201110437617.6A CN102513720B (en) | 2011-12-23 | 2011-12-23 | High-performance tin-based solder alloy and preparation method thereof |
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| CN103170766A (en) * | 2013-03-27 | 2013-06-26 | 江苏盛之祥电子科技有限公司 | Preparation method of low-melting-point high-reliability lead-free solder |
| CN104827198A (en) * | 2015-04-28 | 2015-08-12 | 苏州永创达电子有限公司 | Soldering tin paste |
| CN106011515A (en) * | 2016-06-20 | 2016-10-12 | 山东建筑大学 | Method for preparing carbon nano tube powder enhanced tin-lead alloy |
| CN106132612A (en) * | 2014-10-17 | 2016-11-16 | 富士电机株式会社 | Leadless soft soldering method and solder article |
| CN106624431A (en) * | 2016-11-30 | 2017-05-10 | 安徽华众焊业有限公司 | Tin-zinc lead-free solder and preparation method thereof |
| CN107058784A (en) * | 2017-01-12 | 2017-08-18 | 哈尔滨工业大学 | Preparation method for the CNTs Sn solder with composite material of tin-coated welding strip |
| CN107052613A (en) * | 2016-11-30 | 2017-08-18 | 安徽华众焊业有限公司 | Low-melting point leadless solder and preparation method thereof |
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| CN108788537A (en) * | 2018-06-27 | 2018-11-13 | 深圳市福英达工业技术有限公司 | A kind of preparation method of weld-aiding cream |
| CN108971803A (en) * | 2018-08-17 | 2018-12-11 | 广州汉源新材料股份有限公司 | A kind of composite intensified solder and preparation method thereof |
| CN109590636A (en) * | 2018-12-11 | 2019-04-09 | 深圳市汉尔信电子科技有限公司 | A kind of nano combined solder of high Retention and preparation method thereof |
| CN109759740A (en) * | 2018-12-21 | 2019-05-17 | 广东中实金属有限公司 | A kind of high thermal conductivity solder suitable for power semiconductor device package |
| CN110303270A (en) * | 2019-07-30 | 2019-10-08 | 广东省焊接技术研究所（广东省中乌研究院） | Lead-free brazing, preparation method, its application, solder profile and electronic component |
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| CN115815872A (en) * | 2023-01-09 | 2023-03-21 | 广州汉源新材料股份有限公司 | Lead-free and antimony-free reinforced solder alloy and preparation method thereof |
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| CN106132612A (en) * | 2014-10-17 | 2016-11-16 | 富士电机株式会社 | Leadless soft soldering method and solder article |
| CN104827198A (en) * | 2015-04-28 | 2015-08-12 | 苏州永创达电子有限公司 | Soldering tin paste |
| CN106011515A (en) * | 2016-06-20 | 2016-10-12 | 山东建筑大学 | Method for preparing carbon nano tube powder enhanced tin-lead alloy |
| US10717158B2 (en) | 2016-08-19 | 2020-07-21 | Senju Metal Industry Co., Ltd. | Solder alloy for preventing Fe erosion, resin flux cored solder, wire solder, resin flux cored wire solder, flux coated solder, solder joint and soldering method |
| CN107052613A (en) * | 2016-11-30 | 2017-08-18 | 安徽华众焊业有限公司 | Low-melting point leadless solder and preparation method thereof |
| CN106624431A (en) * | 2016-11-30 | 2017-05-10 | 安徽华众焊业有限公司 | Tin-zinc lead-free solder and preparation method thereof |
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| EP3778107A4 (en) * | 2018-03-30 | 2021-12-15 | Senju Metal Industry Co., Ltd | Solder paste |
| US11633815B2 (en) | 2018-03-30 | 2023-04-25 | Senju Metal Industry Co., Ltd. | Solder paste |
| CN108788537A (en) * | 2018-06-27 | 2018-11-13 | 深圳市福英达工业技术有限公司 | A kind of preparation method of weld-aiding cream |
| CN108971803A (en) * | 2018-08-17 | 2018-12-11 | 广州汉源新材料股份有限公司 | A kind of composite intensified solder and preparation method thereof |
| CN109590636A (en) * | 2018-12-11 | 2019-04-09 | 深圳市汉尔信电子科技有限公司 | A kind of nano combined solder of high Retention and preparation method thereof |
| CN109590636B (en) * | 2018-12-11 | 2021-12-07 | 深圳市汉尔信电子科技有限公司 | High-retention-rate nano composite brazing filler metal and preparation method thereof |
| CN109759740A (en) * | 2018-12-21 | 2019-05-17 | 广东中实金属有限公司 | A kind of high thermal conductivity solder suitable for power semiconductor device package |
| CN110303270A (en) * | 2019-07-30 | 2019-10-08 | 广东省焊接技术研究所（广东省中乌研究院） | Lead-free brazing, preparation method, its application, solder profile and electronic component |
| CN112122826A (en) * | 2020-09-18 | 2020-12-25 | 衢州学院 | Soldering paste for brazing titanium-based composite material and silicon nitride ceramic, and method and application thereof |
| CN112342430A (en) * | 2020-10-12 | 2021-02-09 | 罗游 | Forming process of tin alloy |
| CN112342430B (en) * | 2020-10-12 | 2022-03-11 | 罗游 | Forming process of tin alloy |
| WO2023024363A1 (en) * | 2021-08-23 | 2023-03-02 | 天津大学 | Prediction method and system for critical floating time of reinforcing phase |
| CN113725185A (en) * | 2021-08-31 | 2021-11-30 | 江苏师范大学 | Sn-based brazing filler metal capable of realizing vertical chip stacking and bonding method thereof |
| CN113725185B (en) * | 2021-08-31 | 2024-03-29 | 江苏师范大学 | Sn-based solder capable of realizing vertical stacking of chips and bonding method thereof |
| CN114147388A (en) * | 2021-11-15 | 2022-03-08 | 西北工业大学 | Yttria-stabilized zirconia-based solid phase change composite solder and preparation method thereof |
| CN114523230A (en) * | 2022-03-07 | 2022-05-24 | 中机智能装备创新研究院(宁波)有限公司 | Preparation method and device of tin-based composite solder and tin-based composite solder |
| CN114523230B (en) * | 2022-03-07 | 2024-04-26 | 中国机械总院集团宁波智能机床研究院有限公司 | Preparation method and device of tin-based composite solder and tin-based composite solder |
| CN114559180A (en) * | 2022-03-21 | 2022-05-31 | 太原理工大学 | Silicon carbide particle reinforced magnesium alloy brazing filler metal and preparation method and application thereof |
| CN114559180B (en) * | 2022-03-21 | 2024-04-09 | 太原理工大学 | Silicon carbide particle reinforced magnesium alloy brazing filler metal and preparation method and application thereof |
| CN115647642A (en) * | 2022-11-05 | 2023-01-31 | 郑州机械研究所有限公司 | Low-melting alloy brazing filler metal powder and preparation method thereof |
| CN115815872A (en) * | 2023-01-09 | 2023-03-21 | 广州汉源新材料股份有限公司 | Lead-free and antimony-free reinforced solder alloy and preparation method thereof |
| CN115815872B (en) * | 2023-01-09 | 2023-06-27 | 广州汉源新材料股份有限公司 | Lead-free antimony-free reinforced solder alloy and preparation method thereof |
| CN116140863A (en) * | 2023-02-25 | 2023-05-23 | 东莞市千岛金属锡品有限公司 | High-heat-resistance lead-free tin bar and preparation method thereof |
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