CN106181108B - A kind of SnBiZn series low-temperature leadless solder and preparation method thereof - Google Patents
A kind of SnBiZn series low-temperature leadless solder and preparation method thereof Download PDFInfo
- Publication number
- CN106181108B CN106181108B CN201610657055.9A CN201610657055A CN106181108B CN 106181108 B CN106181108 B CN 106181108B CN 201610657055 A CN201610657055 A CN 201610657055A CN 106181108 B CN106181108 B CN 106181108B
- Authority
- CN
- China
- Prior art keywords
- alloy
- solder
- weight percent
- snbizn
- series low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- B23K35/264—Bi 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
Abstract
The invention discloses a kind of SnBiZn series low-temperature leadless solders and preparation method thereof, belong to low temperature slicken solder technical field.The weight percent group of the lead-free solder becomes：Bi 45.5 56.2%, Zn 1.7 2.4%, remaining is Sn, and the weight percent of Bi and Zn meets relational expression b=0.0123a21.27a+34.652+c, wherein a are the weight percent of Bi, and b is the weight percent of Zn, and the value range of c is 0.2≤c≤0.2.The invention also discloses the preparation methods of the lead-free solder.The solder alloy of the present invention is eutectic or nearly eutectic structure, and fusing point is low, and has excellent mechanical property and welding spot reliability, is suitable for low temperature soft solder field.
Description
Technical field
The present invention relates to a kind of SnBiZn series low-temperature leadless solders and preparation method thereof, more particularly to a kind of soft for low temperature
The SnBiZn-X leadless welding alloys in soldering field and preparation method thereof belong to low temperature slicken solder technical field.
Background technology
Rapid development with the unleaded of electronic product and to frivolous, high function direction, master is to be used in current SMT
Lead-free solder SnAgCu systems (especially SAC305), it is new in reflow soldering process since solder melt point is higher (200 DEG C~230 DEG C)
The frivolous chip of type is very sensitive to temperature, and chip easily damages, thus low temperature tin solder (include but not limited to tin cream, tin silk,
Tin bar) demand of the market to solder be very urgent.SnBi systems solder is often applied to the field of low-temperature welding in the prior art
It closes, especially SnBi58 solders.However in the welding process due to the brittleness of Bi itself, especially Sn-Bi eutectic alloys, it organizes
Middle Sn and Cu substrates react to form Sn-Cu intermetallic compounds, the relative quantity of this regional area Sn is caused to reduce, and Bi is opposite to be contained
Amount increases, and SnBi alloys are biased to hypereutectic by eutectic system, and nascent Bi phases are precipitated, Bi phases segregation of coming into being at substrate,
Form rich Bi bands.The appearance of rich Bi bands, becomes the most weak region of entire solder joint, and the serious combination for affecting solder joint is strong
Degree, this makes the research of SnBi systems solder and use be constantly in state at a low tide.It is carried out both at home and abroad about this crisp problem of Bi
A series of researchs find that Trace Ag, Cu are added in Sn-Bi solders, can improve brittleness to a certain extent.Motorola is special
SnBi57Ag1 alloys disclosed in profit, Fuji patents US6, the SnBi35Ag1 alloys developed in 156,132, and
The solders such as the SnBiCu alloys of 200710121380.4 patent disclosures of CN200610089257.4/CN are to a certain extent
Segregation of the Bi elements near substrate in welding process of setting is inhibited, but cannot all be avoided completely at its weld interface Bi layers rich
The appearance of weak band, the problem of substantially unresolved welding spot reliability difference.
There are mainly two types of Sn-Bi-Zn solders in the prior art, a small amount of one is being added on the basis of SnZn lead-free solders
Bi elements, primarily to reducing the fusing point of SnZn solders, improving wetability and creep resistance, Bi content general controls are in weight
Below percentage 15%.It is another then be the addition Zn elements in SnBi solder alloys, primarily to improving solder and Cu electricity
The adhesive strength of interface between pole.CN 102615446A disclose a kind of solder Sn (tin) Bi (bismuth) Zn (zinc) solder, wherein
Include the Zn of Bi, 0.01-0.1wt% of 45-65%wt, the Sb and Sn of 0.3-0.8wt.The prior art is in SnBi solder alloys
On the basis of addition trace Zn element to improve alloy property, alloy is fundamentally the binary eutectic alloy weldering of traditional SnBi
Material does not solve the problems, such as that SnBi solder embrittlements are low, poor reliability fundamentally.
Invention content
It is an object of the invention to overcome the shortcomings of the prior art, provide a kind of for low temperature solder neck
The novel SnBiZn-X leadless welding alloys in domain, the alloy be novel SnBiZn ternary eutectics or nearly eutectic solder alloy system,
The alloy structure is eutectic or near-eutectic alloy, and crystal grain is tiny, excellent combination property, and it is crisp can fundamentally to solve SnBi solders
The problem of property is low, poor reliability.The SnBiZn-X solder alloys of the present invention can also reduce SnBi58 solders conjunction in the prior art
Bi contents in gold, thus the mechanical performance of solder is improved, and reduce because Bi is that the Future that rare element is brought is insufficient
The commercial introduction application risk of appearance.SnBiZn-X solder alloys can solve in welding process because of caused by temperature height simultaneously
The welded part warpages of the appearance such as micro chip and BGA, CSP, deformation, pillow and a series of problems of welded quality brought.
The present invention is achieved through the following technical solutions：
A kind of SnBiZn series low-temperature leadless solder belongs to low temperature solder field leadless welding alloy, the lead-free solder
Alloy includes Bi, Zn and Sn, and weight percent group becomes：Bi 45.5-56.2%, Zn 1.7-2.4%, remaining is for Sn and less
Inevitable impurity is measured, and the weight percent of Bi and Zn meets relational expression b=0.0123a in the solder alloy2-1.27a+
34.652+c, wherein a values are the weight percent of Bi, and b values are the weight percent of Zn, the value range of c be -0.2≤c≤
0.2。
In the leadless welding alloy, c value preferred scopes are -0.2≤c≤- 0.001 or 0.001≤c≤0.2 or -0.2≤c
≤ -0.005 or 0.005≤c≤0.2 or -0.2≤c≤- 0.01 or 0.01≤c≤0.2, more preferably -0.12≤c≤-
0.001 or 0.001≤c≤0.12 or -0.12≤c≤- 0.005 or 0.005≤c≤0.12 or -0.1≤c≤- 0.01 or 0.01
≤c≤0.1。
The leadless welding alloy further includes the metallic element of one or more of Ce, Al, Ti, Sb and Mg.
The weight percent of the Ce is 0.003-3.0%, preferably 0.003-2.5%, more preferably 0.008-
2.5%, most preferably 0.03-1.5%.
The weight percent of the Al is 0.03-0.5%, preferably 0.03-0.3%, more preferably 0.03-0.15%.
The weight percent of the Ti is 0.25-2.5%, preferably 0.25-2.0%, more preferably 0.5-1.6%.
The weight percent of the Sb be 0.05-0.8%, preferably 0.05-0.6%, more preferably 0.05-0.5%, most
Preferably 0.08-0.5%.
The weight percent of the Mg be 0-2.8%, preferably 0.001-2.8%, more preferably 0.1-2.0%, it is optimal
It is selected as 0.5-1.8%.
A kind of preparation method of low temperature solder field SnBiZn series low-temperature leadless solder alloys, this method include following
Step：
1) Sn-Zn intermediate alloys are prepared, or prepare Sn-Zn intermediate alloys and Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb and
One or more of Sn-Mg intermediate alloys；
It 2) will be in Manufactured Sn-Zn intermediate alloys, metal Sn and Bi Sn-Zn intermediate alloy, Sn, Bi and Sn-Ce
Between alloy, Sn-Al intermediate alloys, Sn-Ti intermediate alloys, Sn-Sb intermediate alloys and one kind or several in Sn-Mg intermediate alloys
Kind, it is melted in smelting furnace by alloy proportion；Anti-oxidation solvent is covered in the alloy surface, alloy is heated to 200~450
DEG C, 10~20min is kept the temperature, Surface Oxygen slugging is removed, is cast in mold and SnBiZn series lead-free solder alloy ingot blanks are made；It is described
The weight percent of Bi and Zn need to meet relational expression b=0.0123a in SnBiZn series lead-free solder alloys2-1.27a+34.652+
C, wherein a values are the weight percent of Bi, and b values are the weight percent of Zn, and the value range of c is -0.2≤c≤0.2.
It includes such as that Sn-Zn, Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb, Sn-Mg intermediate alloy is wherein prepared in step 1)
Lower step：Respectively by Sn and Zn, Sn and Ce, Sn and Al, Sn and Ti, Sn and Sb, Sn and Mg that purity is 99.99wt.%, by one
Fixed alloy proportion is added in vacuum melting furnace, vacuumize process to 1 × 10-2-1×10-1Pa after being filled with nitrogen, respectively will
Alloy is heated to 400-1650 DEG C of fusing, while being subject to electromagnetic agitation, so that alloying component is uniform, is then quickly cooled down, vacuum
Casting, prepares Sn-Zn, Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb, Sn-Mg intermediate alloy.
It is rosin or KCl-LiCl fused salts that wherein surface described in step 2), which covers anti-oxidation solvent,.
SnBiZn series low-temperature leadless solder using the present invention is formed by solder joint or weld seam, and the solder joint or weld seam are adopted
With general solder paste reflow, wave soldering, or heat fusing is welded, heat fusing welding include preform weld tabs,
In welding, soldered ball and welding wire etc., the solder joint or weld seam alloy in addition to the ingredient comprising solder, further include but be not limited to Cu, Ag,
The substrates alloying element such as Ni, Au.The weight percent group of the solder joint or weld seam alloy becomes：Bi 45.5-56.2%, Zn
1.7-2.4%, Cu 0.01-1%, Ni 0.01-1%, Ag 0.01-1%, Ce 0-3.0%, Al 0-0.5%, Ti 0-
2.5%, Sb 0-0.8%, Mg 0-2.8%, remaining is Sn and a small amount of inevitably substrate alloying element.
Advantages of the present invention：
The present invention SnBiZn ternary eutectics or nearly eutectic solder alloy, crystal grain is tiny, fusing point at 132-150 DEG C, than
SnAgCu systems solder alloy fusing point reduces nearly 80 DEG C.In the welding process, Zn diffuses to interface to SnBiZn alloys prior to Sn
It is reacted with substrate Cu, generates Cu-Zn intermetallic compounds.The appearance for thus avoiding rich Bi bands, fundamentally improves solder joint
Bond strength and reliability.
The oxidation of metal is oxidation initial stage first, and oxygen occurs chemical reaction with metal and generates one layer of unimolecule oxidation film,
It is the growth for the film realized with electrochemical reaction afterwards.After forming closely knit continuous oxidation film, oxidation process continues to take
Certainly in interfacial reaction speed and participate in diffusion velocity of the reactive material by oxidation film.The present invention adds in SnBiZn solder alloys
Enter a certain amount of Ce, Al, Ti alloying element, by the comprehensive function of element, forms fine and close oxidation film on solder surface, can be compared to
It forms on one layer " barrier layer " so that the oxide of Bi is distributed in subsurface stratum, prevents the oxidation of solder, improves the antioxygen of alloy
The property changed, has been inherently eliminated the black problem of weldering of SnBi solders.And Ce, Sb are solid-solution in matrix in certain proportion, can be shown
Writing improves alloy strength and toughness.Pass through the comprehensive function of Ce, Mg, Al element simultaneously so that the wetability of SnBiZn alloys is aobvious
It writes and improves.
The weight percent of Bi and Zn meets relational expression b=0.0123a2- 1.27a+34.652+c, wherein a values are Bi's
Weight percent, b values are the weight percent of Zn, and the value range of c is -0.2≤c≤0.2, meets the SnBiZn of the relational expression
Be solder alloy be eutectic or nearly eutectic structure, fusing point is low, and melting range is small, excellent in mechanical performance.
Each element of solder alloy fusing point in its selected composition range is below 150 DEG C in the present invention；Use this
The solder joint that solder alloy is formed has preferable inoxidizability and reliability, and solder joint light solderless is black.And Bi contains in the present invention
Amount be 45.5-56.2%, reduce the Bi contents in SnBi58 solder alloys, improve the brittleness of solder, and reduce because
Bi is the commercial introduction application risk that the Future deficiency that rare element is brought occurs.
Below by the drawings and specific embodiments, the present invention will be further described, but is not meant to protect the present invention
Protect the limitation of range.
Description of the drawings
Fig. 1 is the pattern SEM photograph of solder alloy prepared by the embodiment of the present invention 1.
Specific implementation mode
Leadless welding alloy of the present invention includes Bi, Zn and Sn, and weight percent group becomes：Bi45.5-56.2%,
Zn 1.7-2.4%, remaining is Sn, and the weight percent of Bi and Zn meets relational expression b=0.0123a in the solder alloy2-
1.27a+34.652+c, wherein a values are the weight percent of Bi, and b values are the weight percent of Zn, and the value range of c is -0.2
≤c≤0.2.Wherein c values preferred scope be -0.2≤c≤- 0.001 or 0.001≤c≤0.2 or -0.2≤c≤- 0.005 or
0.005≤c≤0.2 or -0.2≤c≤- 0.01 or 0.01≤c≤0.2, more preferable -0.12≤c≤- 0.001 or 0.001≤c
≤ 0.12 or -0.12≤c≤- 0.005 or 0.005≤c≤0.12 or -0.1≤c≤- 0.01 or 0.01≤c≤0.1.
The preparation method of the alloy includes the following steps：The first step prepares Sn-Zn, Sn-Ce, Sn-Al, Sn-Ti, Sn-
Sb, Sn-Mg intermediate alloy, the raw material centainly matched is added separately in vacuum melting furnace, and vacuumize process is then charged with nitrogen
Gas, holding melting chamber pressure are 0.5MPa；It is heated to 400-1650 DEG C of fusing, while being subject to electromagnetic agitation, so that alloying component
Uniformly, it is then quickly cooled down, vacuum casting prepares intermediate alloy.Second step, by the intermediate alloy prepared and Sn, Bi by
Certain alloy proportion melts in smelting furnace, and alloy surface covers anti-oxidation solvent, is heated to 200~450 DEG C, and heat preservation 10~
20min, removes Surface Oxygen slugging, and SnBiZn series lead-free solder alloy ingot blanks are made in cast.
Embodiment 1
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 49%, Zn 2.0%, remaining is Sn, which is ternary eutectic tissue, alloy melting point 133.8-
137.5.The method for preparing the leadless welding alloy includes the following steps：
1) it by metal Sn, Zn that purity is 99.99wt.%, is added in vacuum melting furnace, takes out by certain alloy proportion
It is vacuum-treated to 1 × 10-1Pa, after being filled with nitrogen；Alloy is heated to 500-550 DEG C of fusing, while being subject to electromagnetic agitation, so that
Alloying component is uniform, then vacuum casting, prepares SnZn9 intermediate alloys；
2) it by Manufactured Sn-Zn intermediate alloys and Sn, Bi, is melted in smelting furnace by alloy proportion.In alloy surface
Anti-oxidation solvent (rosin or KCl-LiCl fused salts) is covered, alloy is heated to 200 DEG C, 10min is kept the temperature, removes surface oxidation
Slag is cast in mold and SnBi49Zn2 leadless welding alloy ingot blanks is made.
As shown in Figure 1, for the pattern SEM photograph of solder alloy manufactured in the present embodiment.
Embodiment 2
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 56.2%, Zn 2.1%, remaining is Sn, which is 134.5-142.3 DEG C.Not except alloy proportion
With other than, the method for the leadless welding alloy is prepared with embodiment 1.
Embodiment 3
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 49%, Zn 2.0%, Ce 0.003%, Al 0.03%, remaining is Sn, which is nearly eutectic structure,
Fusing point is 132.8-136.0 DEG C.The method for preparing the leadless welding alloy includes the following steps：
1) by metal Sn and Zn, Sn and Ce, Sn and Al that purity is 99.99wt.%, add respectively by certain alloy proportion
Enter into vacuum melting furnace, vacuumize process to 1 × 10-2Pa, after being filled with nitrogen；Respectively by alloy be heated to 500-550 DEG C,
690-780 DEG C, 400-500 DEG C of fusing, while being subject to electromagnetic agitation, so that alloying component is uniform, then vacuum casting, makes respectively
It is standby go out SnZn9, SnCe10, SnAl5 intermediate alloy；
2) by Manufactured Sn-Zn, Sn-Ce, Sn-Al intermediate alloy and metal Sn, Bi, by alloy proportion in smelting furnace
Fusing.Anti-oxidation solvent (rosin or KCl-LiCl fused salts) is covered in alloy surface, alloy is heated to 300 DEG C, heat preservation
15min removes Surface Oxygen slugging, is cast in mold and SnBi49Zn2Ce0.003Al0.03 leadless welding alloy ingot blanks are made.
Embodiment 4
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 49%, Zn 2.0%, Ce 0.05%, Al 0.05%, Ti 0.25%, remaining is Sn, which is close
Eutectic structure, alloy melting point are 134.2-136.8 DEG C.The method for preparing the leadless welding alloy includes the following steps：
1) by metal Sn and Zn, Sn and Ce, Sn and Al, Sn and Ti that purity is 99.99wt.%, certain conjunction is pressed respectively
Gold proportioning is added in vacuum melting furnace, vacuumize process to 1 × 10-2Pa, after being filled with nitrogen；Alloy is heated to 500- respectively
550 DEG C, 690-780 DEG C, 400-500 DEG C, 1550-1650 DEG C of fusing, while being subject to electromagnetic agitation, so that alloying component is uniform,
Then vacuum casting prepares SnZn9, SnCe10, SnAl5, SnTi20 intermediate alloy respectively；
2) by Manufactured Sn-Zn, Sn-Ce, Sn-Al, Sn-Ti intermediate alloy and Sn, Bi, by alloy proportion in smelting furnace
Middle fusing.Anti-oxidation solvent (rosin or KCl-LiCl fused salts) is covered in alloy surface, alloy is heated to 450 DEG C, heat preservation
15min removes Surface Oxygen slugging, is cast in mold and SnBi49Zn2Ce0.05Al0.05Ti0.25 leadless welding alloys are made
Ingot blank；
Embodiment 5
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 55%, Zn 1.9%, Ce 0.1%, Al 0.1%, Ti 0.5%, remaining is Sn, which is close total
Crystalline substance tissue, alloy melting point are 136.8-141.5 DEG C.In addition to alloy proportion difference, the method for preparing the leadless welding alloy is same
Embodiment 4.
Embodiment 6
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 45.8%, Zn 2.4%, Ce 0.5%, Al 0.2%, Ti 1.0%, Sb 0.05%, remaining is Sn, the Pb-free coating
Material alloy is nearly eutectic structure, and alloy melting point is 137.1-142 DEG C.The method for preparing the leadless welding alloy includes following step
Suddenly：
1) by metal Sn and Zn, Sn and Ce, Sn and Al, Sn and Ti, Sn and Sb that purity is 99.99wt.%, one is pressed respectively
Fixed alloy proportion is added in vacuum melting furnace, vacuumize process to 1 × 10-2Pa, after being filled with nitrogen；Alloy is heated respectively
To 500-550 DEG C, 690-780 DEG C, 400-500 DEG C, 1550-1650 DEG C, 700-800 DEG C of fusing, while being subject to electromagnetic agitation, with
Keep alloying component uniform, then vacuum casting, prepares closed among SnZn9, SnCe10, SnAl5, SnTi20, SnSb20 respectively
Gold；
2) by Manufactured Sn-Zn, Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb intermediate alloy and metal Sn, Bi, match by alloy
Than being melted in smelting furnace.Anti-oxidation solvent (rosin or KCl-LiCl fused salts) is covered in alloy surface, alloy is heated to 450
DEG C, 20min is kept the temperature, Surface Oxygen slugging is removed, is cast in mold and is made
SnBi45.8Zn2.4Ce0.5Al0.2Ti1.0Sb0.05 leadless welding alloy ingot blanks.
Embodiment 7
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 45.5%, Zn 2.3%, Ce1.0%, Al 0.3%, Ti 1.5%, Sb 0.1%, remaining is Sn, the lead-free solder
Alloy is nearly eutectic structure, and alloy melting point is 136.6-145.9 DEG C.In addition to alloy proportion difference, preparation method is the same as implementation
Example 6.
Embodiment 8
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 56.2%, Zn 2.1%, Ce 1.5%, Al 0.3%, Ti 1.5%, Sb 0.3%, Mg 0.5%, remaining is Sn,
The leadless welding alloy is nearly eutectic structure, and alloy melting point is 138.5-145.7 DEG C.Prepare the method packet of the leadless welding alloy
Include following steps：
1) by metal Sn and Zn, Sn and Ce, Sn and Al, Sn and Ti, Sn and Sb, Sn-Mg that purity is 99.99wt.%, divide
It is not added in vacuum melting furnace by certain alloy proportion, vacuumize process to 1 × 10-2Pa, after being filled with nitrogen；It will close respectively
Gold is heated to 500-550 DEG C, 690-780 DEG C, 400-500 DEG C, 1550-1650 DEG C, 700-800 DEG C, 560-670 DEG C of fusing, together
When be subject to electromagnetic agitation so that alloying component is uniform, then vacuum casting, prepare respectively SnZn9, SnCe10, SnAl5,
SnTi20, SnSb20, SnMg5 intermediate alloy；
2) it by Manufactured Sn-Zn, Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb, Sn-Mg intermediate alloy and metal Sn, Bi, presses
Alloy proportion melts in smelting furnace.Cover anti-oxidation solvent (rosin or KCl-LiCl fused salts) in alloy surface, by alloy plus
Heat keeps the temperature 20min, removes Surface Oxygen slugging, be cast in mold and be made to 450 DEG C
SnBi56.2Zn2.1Ce1.5Al0.3Ti1.5Sb0.3Mg0.5 leadless welding alloy ingot blanks.
Embodiment 9
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 51.3%, Zn 1.7%, Ce 2.0%, Al 0.5%, Ti 2.0%, Sb 0.5%, Mg 1.5%, remaining is Sn,
The leadless welding alloy is nearly eutectic structure, alloy melting point 140.7-148.9.In addition to alloy proportion difference, preparation side
Method is the same as embodiment 8.
Embodiment 10
A kind of low temperature solder field leadless welding alloy, by weight percentage, the lead-free solder alloy powder packet
Contain：Bi 55.8%, Zn 2.2%, Ce 2.5%, Al 0.5%, Ti 2.5%, Sb 0.6%, Mg 2.8%, remaining is Sn,
The leadless welding alloy is nearly eutectic structure, alloy melting point 141.9-150.In addition to alloy proportion difference, preparation method
With embodiment 8.
Comparative example 1
A kind of low temperature leadless welding alloy, by weight percentage, which includes：Bi 58%, Sn
42%, which is 138 DEG C.
Comparative example 2
A kind of low temperature leadless welding alloy, by weight percentage, which includes：Bi 57%,
Ag1.0%, remaining is Sn, which is 138-140 DEG C.
Test experiments
1, fusing point measures：
Fusing point test utilizes STA409PC differential scan calorimeters (TA under the conditions of heating rate is 10 DEG C/min
Instrument it) tests, sample quality 30mg, numerical value processing is calculated automatically for software, and with DSC curve peak temperature
It is denoted as solder alloy melting point values.
2, wetability test condition is：
The alloy for weighing 0.6g mixes no-oxygen copper plate (the copper coin table for being placed in 30 × 30 × 0.3mm of size with a certain amount of solder flux
Face deoxygenation decontamination), then copper coin is placed on flattening oven and is heated to 180 DEG C, it is static after solder fusing is sprawled to be cooled to room temperature
Solder joint is formed, the spreading area of solder joint is measured using CAD software.
3, sample prepares：
Stretching sample is prepared with reference to Japanese Industrial Standards JIS Z 3198 and brazing connects sample testing.
4, mechanical performance data tests aircraft measurements according to the method for GB/T228-2002 in AG-50KNE type universal materials,
Tensile speed 5mm/min, each data point are tested three samples and are averaged.
5, reliability estimation method：Vibration experiment, counterweight weight 2kg, record copper sheet welding are carried out to copper sheet welded specimen
Vibration number when sample solder joint is broken, each data point are tested 10 samples and are averaged.
1 solder alloy fusing point of table and wettability compare
2 solder alloy mechanical property of table compares
SnBiZn series low-temperature leadless solder using the present invention can pass through general solder paste reflow, wave soldering, Huo Zhere
Fusion welding forms solder joint or weld seam, and heat fusing welding includes preform weld tabs, welding, soldered ball and welding wire etc., solder joint or weld seam
In alloy in addition to the ingredient comprising solder, the substrates alloying element such as further include but be not limited to Cu, Ag, Ni, Au.Obtained solder joint or
Weld seam weight alloy percentage group becomes：Bi 45.5-56.2%, Zn 1.7-2.4%, Cu 0.01-1%, Ni 0.01-1%,
Ag 0.01-1%, Ce 0-3.0%, Al 0-0.5%, Ti 0-2.5%, Sb 0-0.8%, Mg 0-2.8%, remaining for Sn and
A small amount of inevitably substrate alloying element.
The solder alloy of the present invention is eutectic or nearly eutectic structure, and fusing point is low, and has excellent mechanical property and solder joint
Reliability is suitable for low temperature soft solder field.
Claims (9)
1. a kind of SnBiZn series low-temperature leadless solder, it is characterised in that：The weight percent group of the lead-free solder becomes：Bi
45.5-56.2%, Zn 1.7-2.4%, remaining is Sn, and the weight percent of Bi and Zn meets relational expression b=0.0123a2-
1.27a+34.652+c, wherein a are the weight percent of Bi, and b is the weight percent of Zn, and the value range of c is -0.2≤c
≤ -0.001,0.001≤c≤0.2, -0.2≤c≤- 0.005,0.005≤c≤0.2, -0.2≤c≤- 0.01 or 0.01≤c
≤0.2。
2. SnBiZn series low-temperature leadless solder according to claim 1, it is characterised in that：In the lead-free solder, c's
Value range be -0.12≤c≤- 0.001,0.001≤c≤0.12, -0.12≤c≤- 0.005,0.005≤c≤0.12, -
0.1≤c≤- 0.01 or 0.01≤c≤0.1.
3. SnBiZn series low-temperature leadless solder according to claim 1, it is characterised in that：The leadless welding alloy is also
Element including one or more of Ce, Al, Ti, Sb and Mg.
4. SnBiZn series low-temperature leadless solder according to claim 3, it is characterised in that：The weight percent of the Ce is
The weight percent of 0.003-3.0%, the Al are 0.03-0.5%, and the weight percent of the Ti is 0.25-2.5%, institute
The weight percent for stating Sb is 0.05-0.8%, and the weight percent of the Mg is 0-2.8%.
5. the preparation method of the SnBiZn series low-temperature leadless solders described in any one of claim 1-4, includes the following steps：
1) Sn-Zn intermediate alloys are prepared, or prepare Sn-Zn intermediate alloys and Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb and Sn-Mg
One or more of intermediate alloy；
2) by Manufactured Sn-Zn intermediate alloys, Sn and Bi Sn-Zn intermediate alloys, Sn, Bi and Sn-Ce intermediate alloy,
One or more of Sn-Al intermediate alloys, Sn-Ti intermediate alloys, Sn-Sb intermediate alloys and Sn-Mg intermediate alloys, by alloy
Proportioning melts in smelting furnace；Anti-oxidation solvent is covered in the alloy surface, alloy is heated to 200~450 DEG C, heat preservation 10
~20min removes Surface Oxygen slugging, is cast in mold and SnBiZn series lead-free solder alloy ingot blanks are made.
6. the preparation method of SnBiZn series low-temperature leadless solder according to claim 5, it is characterised in that：The Sn-Zn,
The preparation method of Sn-Ce, Sn-Al, Sn-Ti, Sn-Sb or Sn-Mg intermediate alloy includes the following steps：It is by purity respectively
The Sn and Zn of 99.99wt.%, Sn and Ce, Sn and Al, Sn and Ti, Sn and Sb, Sn and Mg, are added to by certain alloy proportion
In vacuum melting furnace, vacuumize process to 1 × 10-2-1×10-1Alloy after being filled with nitrogen, is heated to 400-1650 by Pa respectively
DEG C fusing, while being subject to electromagnetic agitation, so that alloying component is uniform, then vacuum casting, is prepared Sn-Zn, Sn-Ce, Sn-
Al, Sn-Ti, Sn-Sb or Sn-Mg intermediate alloy.
7. the preparation method of SnBiZn series low-temperature leadless solder according to claim 5, it is characterised in that：The oxygen
It is rosin or KCl-LiCl fused salts to change solvent.
8. being formed by solder joint or weld seam using the SnBiZn series low-temperature leadless solders described in any one of claim 1-4.
9. SnBiZn series low-temperature leadless solder according to claim 8 is formed by solder joint or weld seam, it is characterised in that：Institute
The solder joint or weld seam stated are welded using solder paste reflow, wave soldering or heat fusing, and heat fusing welding includes pre-
The weight percent group of forming weld tabs, welding, soldered ball and welding wire, the solder joint or weld seam alloy becomes：Bi 45.5-56.2%,
Zn 1.7-2.4%, Cu 0.01-1%, Ni 0.01-1%, Ag 0.01-1%, Ce 0-3.0%, Al 0-0.5%, Ti 0-
2.5%, Sb 0-0.8%, Mg 0-2.8%, remaining is Sn and a small amount of inevitably substrate alloying element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610657055.9A CN106181108B (en) | 2016-08-11 | 2016-08-11 | A kind of SnBiZn series low-temperature leadless solder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610657055.9A CN106181108B (en) | 2016-08-11 | 2016-08-11 | A kind of SnBiZn series low-temperature leadless solder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106181108A CN106181108A (en) | 2016-12-07 |
| CN106181108B true CN106181108B (en) | 2018-08-24 |
Family
ID=57514292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610657055.9A Active CN106181108B (en) | 2016-08-11 | 2016-08-11 | A kind of SnBiZn series low-temperature leadless solder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106181108B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106695161A (en) * | 2016-12-29 | 2017-05-24 | 安徽华众焊业有限公司 | Pb-free Sn-Bi alloy solder and preparation method thereof |
| CN106825979B (en) * | 2017-01-04 | 2019-11-12 | 南京信息工程大学 | A kind of low melting point Sn-Zn-Bi-Mg series lead-free solder and preparation method thereof |
| CN109518019B (en) * | 2018-10-12 | 2020-06-19 | 北京康普锡威科技有限公司 | Method for modifying SnBi series hypoeutectic alloy and alloy obtained by method |
| CN112342417B (en) * | 2020-11-17 | 2022-03-15 | 昆明理工大学 | Tin-based solder and preparation method thereof |
| CN115041864A (en) * | 2022-07-08 | 2022-09-13 | 深圳市博士达焊锡制品有限公司 | High-reliability low-temperature lead-free solder and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001239392A (en) * | 2000-02-29 | 2001-09-04 | Mitsubishi Electric Corp | Lead-free solder, solder junction and it's jointing method using the same |
| US6503338B1 (en) * | 2000-04-28 | 2003-01-07 | Senju Metal Industry Co., Ltd. | Lead-free solder alloys |
| CN101380700B (en) * | 2007-09-05 | 2011-04-20 | 北京康普锡威科技有限公司 | Tin bismuth cuprum series leadless solder and preparation method thereof |
| CN101618484A (en) * | 2008-07-02 | 2010-01-06 | 比亚迪股份有限公司 | Lead-free solder and preparation method thereof |
| CN101733575A (en) * | 2008-11-13 | 2010-06-16 | 北京有色金属研究总院 | Tin-zinc-bismuth-copper leadless solder with low cost and welding spot thereof |
| CN101700605A (en) * | 2009-11-13 | 2010-05-05 | 苏州优诺电子材料科技有限公司 | Low melting point lead-free welding material alloy |
| CN103264237A (en) * | 2013-05-23 | 2013-08-28 | 东莞市焊宏爱法电子科技有限公司 | Novel alloy soldering paste and preparation method thereof |
-
2016
- 2016-08-11 CN CN201610657055.9A patent/CN106181108B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106181108A (en) | 2016-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106216872B (en) | A kind of SnBiSb series low-temperature leadless solder and preparation method thereof | |
| CN106181108B (en) | A kind of SnBiZn series low-temperature leadless solder and preparation method thereof | |
| Feng et al. | Reliability studies of Cu/Al joints brazed with Zn–Al–Ce filler metals | |
| CN104411450B (en) | Alloy | |
| CN103249519B (en) | Pb-free solder alloy having Zn as main component | |
| CN101348875A (en) | Tin, bismuth and copper type low temperature lead-free solder alloy | |
| CN102172805B (en) | Low-cost anti-aging brazing filler material used for electronic packaging and preparation method thereof | |
| CN109434317A (en) | A kind of leadless environment-friendly soldering and its preparation method and application | |
| CN101862921A (en) | Sn-Cu-Ni lead-free solder containing Pr, Sr and Ga | |
| CN106141494A (en) | For the solder of soldering molybdenum rhenium alloys foil and preparation method and soldering processes | |
| CN106392366B (en) | A kind of BiSbAg system high temperature lead-free solder and preparation method thereof | |
| CN110238557A (en) | A kind of ZnSn base high-temperature leadless solder and preparation method thereof | |
| CN114293066A (en) | Lead-free low-temperature solder alloy material containing Ni and preparation method thereof | |
| JP3081230B2 (en) | Copper alloy used as brazing filler metal | |
| CN113677477B (en) | Solder alloy, solder paste, solder preform, solder ball, wire-like solder, cored solder, solder joint, electronic circuit board, and multilayer electronic circuit board | |
| CN105562956A (en) | Brazing filler metal suitable for braze welding of magnesium-aluminum dissimilar alloys and preparation method for brazing filler metal | |
| CN108161271A (en) | A kind of SnPbBiSb systems low temperature enhancing solder and preparation method thereof | |
| CN115430949B (en) | Five-membered eutectic high-toughness low-Wen Xibi-series solder and preparation method thereof | |
| CN106825983A (en) | A kind of SnAgSbNi series lead-free soldering tins alloy and its preparation method and application | |
| CN114227057B (en) | Lead-free solder alloy and preparation method and application thereof | |
| JP6887183B1 (en) | Solder alloys and molded solders | |
| CN110014246B (en) | Welding wire for welding magnesium alloy material and preparation method thereof | |
| CN106825979B (en) | A kind of low melting point Sn-Zn-Bi-Mg series lead-free solder and preparation method thereof | |
| JP2016016453A (en) | Au-Ge-Sn-based solder alloy | |
| CN114193020B (en) | BiCuSnNiP high-temperature lead-free solder and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhang Shaoming Inventor after: Li Cuan Inventor after: He Huijun Inventor after: Liu Xixue Inventor after: Sun Yanbin Inventor after: Wang Zhigang Inventor after: Hu Qiang Inventor after: Zhu Zhihua Inventor after: Xu Lei Inventor after: Li Xiaoqiang Inventor before: He Huijun Inventor before: Liu Xixue Inventor before: Sun Yanbin Inventor before: Wang Zhigang Inventor before: Hu Qiang Inventor before: Zhu Zhihua Inventor before: Xu Lei Inventor before: Li Xiaoqiang Inventor before: Li Cuan |
|
| CB03 | Change of inventor or designer information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |