CN107177752A - A kind of inexpensive dystectic leadless welding alloy and preparation method thereof - Google Patents
A kind of inexpensive dystectic leadless welding alloy and preparation method thereof Download PDFInfo
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- CN107177752A CN107177752A CN201710413022.4A CN201710413022A CN107177752A CN 107177752 A CN107177752 A CN 107177752A CN 201710413022 A CN201710413022 A CN 201710413022A CN 107177752 A CN107177752 A CN 107177752A
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- Prior art keywords
- dystectic
- inexpensive
- leadless welding
- welding alloy
- alloy
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
Abstract
A kind of inexpensive dystectic leadless welding alloy and preparation method thereof, wherein inexpensive dystectic leadless welding alloy includes：Main component, auxiliary components and surplus Sn, main component includes 12~25%Sb, 0.1~5%Cu, 0.01~0.5%Bi, 0.005~0.20%Ni, auxiliary components include being used to improve 0.0~0.20% microalloy of microcosmic crystal structure and for oxidation resistant 0.00~0.05% micro antioxidant.The inexpensive dystectic leadless welding alloy melting range of the present invention is at 241.5~299.2 DEG C, i.e. the melt temperature with more than 240 DEG C, and liquidus temperature is up to 299.2 DEG C；Lead as harmful matter is not contained simultaneously.
Description
Technical field
The present invention relates to high leadless welding alloy field, and in particular to a kind of inexpensive Gao Rong of Sn~Sb~Cu~Bi systems
Leadless welding alloy of point and preparation method thereof.
Background technology
It is both needed to use solder alloy in the military project at tip, medical treatment, semiconductor electronic industry, and conventional lead-free solders are closed
SAC305/SC07/SAC105/SAC0307 melting temperature is 217~227 DEG C in gold, SnSb5 melting temperature for 232~
240 DEG C, can not meet applicable requirement because fusing point is too low, therefore, at present in current industry can only using lead-containing alloy or it is high into
This leadless welding alloy containing noble metal.
But the lead of solder containing pb alloy belongs to heavy metal, and heavy metal lead is easy to accumulation in human body, suppresses protein
Normal chemical combination, easily encroaches on nervous system, causes amentia, and the particularly harm to infant is bigger, can influence IQ and just
Often development.Therefore the use of lead is forbidden in increasing national legislation in world wide.
In addition, the leadless welding alloy containing noble metal, it is known that Au~20Sn contain a high proportion of noble metal Au, cost is high
It is high；The patent CN104520062B such as announced is same containing 8~25% precious metals ag, and Ag cost prices are about Sn cost prices
28 times, 65 times of Sb cost price, cost and its costliness.
Therefore welding process requirement is being met：Fusing point>245 DEG C, tensile strength, creep properties, on the premise of microstructure,
The dystectic leadless welding alloy of low cost has good market prospects.
The content of the invention
There is provided the inexpensive dystectic lead-free solder of one kind in order to solve the above mentioned problem that prior art is present by the present invention
Alloy and preparation method thereof.
Above-mentioned purpose is realized, the invention provides the inexpensive dystectic leadless welding alloy of one kind, including it is main component, auxiliary
Component and surplus Sn are helped, cubage by weight percentage, the main component includes 12~25%Sb, 0.1~5%Cu,
0.01~0.5%Bi, 0.005~0.20%Ni, the auxiliary components include being used to improve the 0.0~0.20% of microcosmic crystal structure
Microalloy and for oxidation resistant 0.00~0.05% micro antioxidant.
As present invention further optimization technical scheme, the microalloy is one kind or several in Co, Mn, Al, Si
Kind.
As present invention further optimization technical scheme, cubage by weight percentage, the microalloy
Content and composition are as follows：
0.00~0.20% Co,
0.00~0.20% Mn,
0.00~0.20% Al,
0.00~0.20% Si.
As present invention further optimization technical scheme, the micro antioxidant is one kind or several in P, Ge, Ga
Kind.
As present invention further optimization technical scheme, cubage by weight percentage is described micro anti-oxidant
The content and composition of agent are as follows：
0.000~0.02% P,
0.002~0.02% Ge,
0.002~0.05% Ga.
Present invention also offers a kind of preparation method of inexpensive dystectic leadless welding alloy, comprise the following steps：
Part Sn is prepared with the other all main components and auxiliary components in addition to Sb components and intermediate alloy is smelted into, the master
The content of component, auxiliary components and surplus Sn is as described above described in inexpensive dystectic leadless welding alloy；
Remaining Sn and Sb are melted in the heating furnace of vacuum induction, its melting temperature is 380~450 DEG C, and is sufficiently stirred for
60~90 minutes；And
Intermediate alloy is added in the Sn and Sb that will dissolve and stir, is cooled down after being sufficiently stirred for, and is made by casting
The dystectic leadless welding alloy of low cost.
As present invention further optimization technical scheme, the microalloy is one kind or several in Co, Mn, Al, Si
Kind.
As present invention further optimization technical scheme, cubage by weight percentage, the microalloy
Content and composition are as follows：
0.00~0.20% Co,
0.00~0.20% Mn,
0.00~0.20% Al,
0.00~0.20% Si.
As present invention further optimization technical scheme, the micro antioxidant is one kind or several in P, Ge, Ga
Kind.
As present invention further optimization technical scheme, the preparation ratio and smelting temperature of intermediate alloy are respectively：
Sn~2%Al, 400~500 DEG C
Sn~5% Cu, 500~600 DEG C,
Sn~5% Ni, 900~1000 DEG C,
Sn~1% Co, 900~1000 DEG C,
Sn~3%Mn, 900~1000 DEG C,
Sn~3%Si, 400~500 DEG C,
Sn~5% P, 500~600 DEG C,
Sn~1% Ge, 600~700 DEG C,
Sn~1% Ga, 300~400 DEG C.
Inexpensive dystectic leadless welding alloy of the present invention and preparation method thereof can reach following beneficial effect：
Inexpensive dystectic leadless welding alloy of the present invention, by including main component, auxiliary components and surplus Sn, by weight
Measure percentage cubage, the main component include 12~25%Sb, 0.1~5%Cu, 0.01~0.5%Bi, 0.005~
0.20%Ni, the auxiliary components include being used to improve 0.0~0.20% microalloy of microcosmic crystal structure and for antioxygen
0.00~0.05% micro antioxidant changed so that the inexpensive dystectic leadless welding alloy melting range of the present invention
At 241.5~299.2 DEG C, i.e. the melt temperature with more than 240 DEG C, liquidus temperature is up to 299.2 DEG C；Do not contain simultaneously
Evil material lead, meets European Union RoHS requirements, can meet high-melting-point in Electronic Assemblies technique, the welding requirements of environmental protection；And this hair
Bright cost is relatively low, is applicable more extensive.
The preparation method of inexpensive dystectic leadless welding alloy of the present invention, by comprising the following steps：By part
Sn is prepared with the other all main components and auxiliary components in addition to Sb components and is smelted into intermediate alloy, the main component, auxiliary
Component and surplus Sn content are as described above described in inexpensive dystectic leadless welding alloy；By remaining Sn and Sb in vacuum
Melted in the heating furnace of sensing, its melting temperature is 380~450 DEG C, and is sufficiently stirred for 60~90 minutes；And will dissolve and stir
Mix in uniform Sn and Sb and add intermediate alloy, cooled down after being sufficiently stirred for, and be made inexpensive dystectic by casting
Leadless welding alloy so that inexpensive dystectic leadless welding alloy melting range exists made from the inventive method
241.5~299.2 DEG C, the i.e. melt temperature with more than 240 DEG C, liquidus temperature are up to 299.2 DEG C；Do not contain simultaneously harmful
Material lead, meets European Union RoHS requirements, can meet high-melting-point in Electronic Assemblies technique, the welding requirements of environmental protection；And the present invention
Cost is relatively low, is applicable more extensive.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is the DSC test charts of the inexpensive dystectic leadless welding alloy of the present invention；
Fig. 2 is the inexpensive dystectic microcosmic crystal structure figure of leadless welding alloy of the present invention.
The object of the invention is realized, functional characteristics and advantage will be described further referring to the drawings in conjunction with the embodiments.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described further.Drawn in preferred embodiment
Such as " on ", " under ", "left", "right", " centre " and " one " term, only understanding for ease of narration, and be not used to limit
The enforceable scope of the present invention, its relativeness is altered or modified, under without essence change technology contents, when being also considered as this hair
Bright enforceable category.
The invention provides the inexpensive dystectic leadless welding alloy of one kind, including main component, auxiliary components and remaining
Sn is measured, cubage by weight percentage, the main component includes 12~25%Sb, 0.1~5%Cu, 0.01~0.5%Bi,
0.005~0.20%Ni, the auxiliary components include being used to improve 0.0~0.20% microalloy and use of microcosmic crystal structure
In oxidation resistant 0.00~0.05% micro antioxidant.
Wherein Sb mainly possesses the inexpensive dystectic leadless welding alloy of the raising present invention（Can abbreviation solder alloy）'s
Solid liquid phase temperature, the dystectic intermetallic compound Sb2Sn3 of generation is combined by Sb and Sn.During Sb contents less than 12%,
Intermetallic compound is reduced, solidus reduction, it is impossible to reach and put forward dystectic purpose.During Sb contents higher than 25%, liquid can be extended
Liquidus temperature is interval, causes the failure welding of solder alloy, and weldering property declines.
Wherein Cu mainly generates Cu3Sn and Cu6Sn5, the generation for suppressing low melting point phase, improves the stretching of solder alloy
Intensity, when Cu content is more than 5%, alloys wet power declines.
Wherein Ni is mainly improvement crystal microscopic structure, makes the intermolecular consistency of solder higher, and improve tensile strength and
Creep properties.
Each optimizing components scope is such as in cubage by weight percentage, inexpensive dystectic leadless welding alloy
Under：
Sb optimization range is：12~20%, further optimization range is 12~15%；
Cu optimization range is：0.5~3%, further optimization range is：1.0~2.0%；
Bi optimization range is：0.01~0.3%, further optimization range is：0.05~0.15%；
Ni optimization range is：0.01~0.1%, further optimization range is：0.03~0.07%.
In specific implementation, the microalloy is the one or more in Co, Mn, Al, Si, and the micro antioxidant is
One or more in P, Ge, Ga.
Due to adding microalloy Co, can effectively suppress the formation of solder alloy thick phase in cooling procedure, so that carefully
Change crystal grain, lift the tensile strength and toughness of solder alloy；Microalloy Mn is added, the toughness of solder alloy can be lifted；Plus
Enter microalloy Si, the thermal fatigue life of solder alloy can be lifted；Microalloy Al is added, the life of thick low melting point phase can be made
Into being suppressed so that the joint bond strength of solder alloy is not easily deteriorated.
In specific implementation, cubage by weight percentage, the content and composition of the microalloy is as follows：
0.00~0.20% Co, its optimization range is 0.001~0.05%, and further optimization range is 0.001~0.01%；
0.00~0.20% Mn, its optimization range is 0.001~0.05%, and further optimization range is 0.001~0.01%；
0.00~0.20% Al, its optimization range is 0.000~0.005%, and further optimization range is 0.000~0.003%；
0.00~0.20% Si, its optimization range is 0.001~0.05%, and further optimization range is 0.001~0.01%.
In specific implementation, cubage by weight percentage, the content and composition of the micro antioxidant is as follows：
0.000~0.02% P,
0.002~0.02% Ge,
0.002~0.05% Ga.
Micro antioxidant can effectively prevent the oxidation of solder alloy, reduce the generation of oxidizing slag in manufacturing process, and
The wettability of solder alloy is lifted, micro antioxidant is by suppressing the metal being easily oxidised in the solidification of solder alloy
Appear in the surface of solder alloy to improve the effect of wetability so that Sb, Cu, Bi, Ni can rest on weldering in the fabrication process
Expect inside alloy, tissue miniaturization caused by heterogeneous nucleation is further promoted, also the elongation with solder alloy is big
The effect that width improves.
Present invention also offers a kind of preparation method of inexpensive dystectic leadless welding alloy, comprise the following steps：
Part Sn is prepared with the other all main components and auxiliary components in addition to Sb components and intermediate alloy is smelted into；
Remaining Sn and Sb are melted in the heating furnace of vacuum induction, to generate intermetallic compound Sb2Sn3, it melts temperature
Spend for 380~450 DEG C, and be sufficiently stirred for 60~90 minutes；And
The intermetallic compound Sb2Sn3 for dissolving and stirring is added into intermediate alloy, and cooled down after being sufficiently stirred for, and
Inexpensive dystectic leadless welding alloy is made by casting.
In specific implementation, the microalloy is the one or more in Co, Mn, Al, Si.
In specific implementation, cubage by weight percentage, the content and composition of the microalloy is as follows：
0.00~0.20% Co,
0.00~0.20% Mn,
0.00~0.20% Al,
0.00~0.20% Si.
In specific implementation, the micro antioxidant is the one or more in P, Ge, Ga.
In specific implementation, the preparation ratio and smelting temperature of intermediate alloy are respectively：
Sn~2%Al, 400~500 DEG C
Sn~5% Cu, 500~600 DEG C,
Sn~5% Ni, 900~1000 DEG C,
Sn~1% Co, 900~1000 DEG C,
Sn~3%Mn, 900~1000 DEG C,
Sn~3%Mn, 400~500 DEG C,
Sn~5% P, 500~600 DEG C,
Sn~1% Ge, 600~700 DEG C,
Sn~1% Ga, 300~400 DEG C.
Wherein Sn~2%Al is meant that, Sn and the Al cubage for preparing ratio by mass percentage, and Sn is 98%,
Al is 2%；Similarly, the Cu of Sn~5% is meant that, Sn and the Cu cubage for preparing ratio by mass percentage, and Sn is
95%, Cu are 5%；The Ni of Sn~5% is meant that, Sn and the Ni cubage for preparing ratio by mass percentage, and Sn is
95%, Ni are 5%；The Co of Sn~1% is meant that, Sn and the Co cubage for preparing ratio by mass percentage, and Sn is
99%, Co are 1%；Sn~3%Mn is meant that, Sn and the Mn cubage for preparing ratio by mass percentage, and Sn is 97%,
Mn is 3%；Sn~3%Si is meant that Sn and the Si cubage for preparing ratio by mass percentage, Sn are that 97%, Si is
3%；The P of Sn~5% is meant that Sn and the P cubage for preparing ratio by mass percentage, Sn are that 95%, P is 5%；Sn
~1% Ge is meant that Sn and the Ge cubage for preparing ratio by mass percentage, Sn are that 99%, Ge is 1%；Sn~
1% Ga is meant that Sn and the Ga cubage for preparing ratio by mass percentage, Sn are that 99%, Ga is 1%.
Herein it should be noted that, in above-mentioned steps by part Sn with addition to Sb components other all main components and auxiliary
Component is prepared and is smelted into intermediate alloy, and which part Sn specific consumption can be according to other all main components in addition to Sb components
And the content and above-mentioned intermediate alloy of auxiliary components prepare ratio-dependent.
In order to allow those skilled in the art to more fully understand and realize technical scheme, below by embodiment
The mode effect that is specifically described technical scheme and brings.
Embodiment 1
The dystectic leadless welding alloy of low cost includes following main component, auxiliary components and surplus Sn, by weight percentage
Cubage, main component composition and content are as follows：Sb15%, Cu1.5%, Bi0.1%, Ni0.05%；The auxiliary components include
For improving microcosmic crystal structure microalloy and for oxidation resistant micro antioxidant, the microalloy includes
Co0.05%, Mn0.1% and Si0.1%, the micro antioxidant include P0.05% and Ge0.1%, and surplus is then Sn.
The preparation method of above-mentioned inexpensive dystectic leadless welding alloy, comprises the following steps：
Part Sn is prepared with the other all main components and auxiliary components in addition to Sb components and intermediate alloy is smelted into；The step
Middle use Sn consumption can be according to the other all main components and the content of auxiliary components in addition to Sb components and above-mentioned middle conjunction
Golden prepares ratio-dependent.
Remaining Sn and Sb are melted in the heating furnace of vacuum induction, to generate intermetallic compound Sb2Sn3, it melts
It is 400 DEG C to solve temperature, and is sufficiently stirred for 80 minutes；And
The intermetallic compound Sb2Sn3 for dissolving and stirring is added into intermediate alloy, and cooled down after being sufficiently stirred for, and
Inexpensive dystectic leadless welding alloy is made by casting.
Inexpensive dystectic leadless welding alloy that the embodiment is obtained, using DSC differential scanning calorimeter butt welding
Expect that alloy is tested three times, such as Fig. 1（Fig. 1 is the DSC test charts of the inexpensive dystectic leadless welding alloy of the present invention）It is shown, its
Initial solidus temperature is respectively 242.42 DEG C, 241.50 DEG C, 241.55 DEG C；Its endothermic peak temperature is respectively 247.00 DEG C,
248.50℃、247.67℃；It is respectively 298.52 DEG C, 298.86 DEG C, 299.23 DEG C that it, which melts liquidus temperature,.The present embodiment
The dystectic leadless welding alloy of low cost has the melt temperature more than 240 DEG C, and liquidus temperature is up to 299.2 DEG C, so that
Dystectic welding requirements in Electronic Assemblies technique can be met.
Fig. 2 is the inexpensive dystectic microcosmic crystal structure figure of leadless welding alloy of the present invention, as shown in Fig. 2 to above-mentioned
The microstructure observed by X25, X40, X200 and X400 multiplication factor of inexpensive dystectic leadless welding alloy,
By Fig. 2 picture it is observed that using inexpensive dystectic leadless welding alloy made from the present embodiment, with densification
Molecular structure, its can be perfectly suitable for electronic welding requirement.
Although the foregoing describing the embodiment of the present invention, those skilled in the art should be appreciated that this
It is merely illustrative of, various changes or modifications can be made to present embodiment, without departing from the principle and essence of the present invention,
Protection scope of the present invention is only limited by the claims that follow.
Claims (10)
1. a kind of inexpensive dystectic leadless welding alloy, it is characterised in that including main component, auxiliary components and surplus
Sn, cubage by weight percentage, the main component includes 12~25%Sb, 0.1~5%Cu, 0.01~0.5%Bi,
0.005~0.20%Ni, the auxiliary components include being used to improve 0.0~0.20% microalloy and use of microcosmic crystal structure
In oxidation resistant 0.00~0.05% micro antioxidant.
2. according to inexpensive dystectic leadless welding alloy described in claim 1, it is characterised in that the microalloy is
One or more in Co, Mn, Al, Si.
3. according to inexpensive dystectic leadless welding alloy described in claim 2, it is characterised in that by weight percentage
Cubage, the content and composition of the microalloy is as follows：
0.00~0.20% Co,
0.00~0.20% Mn,
0.00~0.20% Al,
0.00~0.20% Si.
4. according to inexpensive dystectic leadless welding alloy described in any one of claims 1 to 3, it is characterised in that described
Micro antioxidant is the one or more in P, Ge, Ga.
5. according to inexpensive dystectic leadless welding alloy described in claim 4, it is characterised in that by weight percentage
Cubage, the content and composition of the micro antioxidant is as follows：
0.000~0.02% P,
0.002~0.02% Ge,
0.002~0.05% Ga.
6. a kind of preparation method of inexpensive dystectic leadless welding alloy, it is characterised in that comprise the following steps：
Part Sn is prepared with the other all main components and auxiliary components in addition to Sb components and intermediate alloy is smelted into, the master
The content of component, auxiliary components and surplus Sn is as described in the inexpensive dystectic leadless welding alloy of claim 1；
Remaining Sn and Sb are melted in the heating furnace of vacuum induction, to generate intermetallic compound Sb2Sn3, it melts temperature
Spend for 380~450 DEG C, and be sufficiently stirred for 60~90 minutes；
The intermetallic compound Sb2Sn3 for dissolving and stirring is added into intermediate alloy, and cooled down after being sufficiently stirred for, and
Inexpensive dystectic leadless welding alloy is made by casting.
7. according to the preparation method of inexpensive dystectic leadless welding alloy described in claim 6, it is characterised in that described
Microalloy is the one or more in Co, Mn, Al, Si.
8. according to the preparation method of inexpensive dystectic leadless welding alloy described in claim 7, it is characterised in that by weight
The cubage of percentage is measured, the content and composition of the microalloy are as follows：
0.00~0.20% Co,
0.00~0.20% Mn,
0.00~0.20% Al,
0.00~0.20% Si.
9. according to the preparation method of inexpensive dystectic leadless welding alloy described in any one of claim 6 to 8, its feature
It is, the micro antioxidant is the one or more in P, Ge, Ga.
10. according to the preparation method of inexpensive dystectic leadless welding alloy described in claim 9, it is characterised in that in
Between alloy preparation ratio and smelting temperature be respectively：
Sn~2%Al, 400~500 DEG C,
Sn~5% Cu, 500~600 DEG C,
Sn~5% Ni, 900~1000 DEG C,
Sn~1% Co, 900~1000 DEG C,
Sn~3%Mn, 900~1000 DEG C,
Sn~3%Si, 400~500 DEG C,
Sn~5% P, 500~600 DEG C,
Sn~1% Ge, 600~700 DEG C,
Sn~1% Ga, 300~400 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115259220A (en) * | 2022-07-25 | 2022-11-01 | 云南锡业锡化工材料有限责任公司 | Preparation method of antimony tristannate |
| CN115464299A (en) * | 2021-10-21 | 2022-12-13 | 上海华庆焊材技术股份有限公司 | Preformed lead-free soldering lug capable of reducing soldering cavity and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115464299A (en) * | 2021-10-21 | 2022-12-13 | 上海华庆焊材技术股份有限公司 | Preformed lead-free soldering lug capable of reducing soldering cavity and preparation method and application thereof |
| CN115259220A (en) * | 2022-07-25 | 2022-11-01 | 云南锡业锡化工材料有限责任公司 | Preparation method of antimony tristannate |
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