CN1895838B - Sn-Ag-Cu-Cr-X lead-free soldering material and its preparation - Google Patents
Sn-Ag-Cu-Cr-X lead-free soldering material and its preparation Download PDFInfo
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- CN1895838B CN1895838B CN2005100830111A CN200510083011A CN1895838B CN 1895838 B CN1895838 B CN 1895838B CN 2005100830111 A CN2005100830111 A CN 2005100830111A CN 200510083011 A CN200510083011 A CN 200510083011A CN 1895838 B CN1895838 B CN 1895838B
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- 238000002360 preparation method Methods 0.000 title description 42
- 238000005476 soldering Methods 0.000 title description 6
- 239000000463 material Substances 0.000 title description 4
- 229910000679 solder Inorganic materials 0.000 claims abstract description 29
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims description 26
- 239000010949 copper Substances 0.000 claims description 26
- 238000005275 alloying Methods 0.000 claims description 18
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 239000004411 aluminium Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 153
- 239000000956 alloy Substances 0.000 abstract description 153
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 229910020888 Sn-Cu Inorganic materials 0.000 abstract description 4
- 229910019204 Sn—Cu Inorganic materials 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 3
- 229910020836 Sn-Ag Inorganic materials 0.000 abstract description 2
- 229910020988 Sn—Ag Inorganic materials 0.000 abstract description 2
- 229910018725 Sn—Al Inorganic materials 0.000 abstract description 2
- 229910019192 Sn—Cr Inorganic materials 0.000 abstract description 2
- 229910009038 Sn—P Inorganic materials 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 29
- 238000005266 casting Methods 0.000 description 28
- 238000005303 weighing Methods 0.000 description 16
- 239000002893 slag Substances 0.000 description 14
- 238000010301 surface-oxidation reaction Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 9
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- 238000005516 engineering process Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910017813 Cu—Cr Inorganic materials 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 235000006708 antioxidants Nutrition 0.000 description 4
- 239000013068 control sample Substances 0.000 description 4
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- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910002482 Cu–Ni Inorganic materials 0.000 description 1
- 229910017932 Cu—Sb Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910020882 Sn-Cu-Ni Inorganic materials 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
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Abstract
A lead-free Sn-Ag-Cu-Cr-X solder is proportionally prepared from Cu, Cr, alloy of one or more of Ga, Bi, In, Ni, Ge, La, Ce, Sb, Mn and Zn, Ag, P and/or Al and Sn through smelting in vacuum or protecting atmosphere to preparing intermediate alloys Sn-Cu, Sn-Cr, Sn-Ag, Sn-P and Sn-Al, and proportional smelting.
Description
Technical field
Sn-Ag-Cu-Cr series lead-free solder of a kind of modification and preparation method thereof belongs to the manufacturing technology field of tin-base lead-free solder.
Background technology
As a kind of novel Lead-free Electronics Packaging scolder, should have processing performance good (fusing point is low, melting region is little, good, the anticorrosive antioxygenic property of wetability is good, mechanical property is good, good conductivity), technology yield height (spreading rate is fast, solder yield is high, slagging rate height), welding spot reliability good (solder joint bond strength height, creep-resistant property good), characteristics such as with low cost.Current unleaded wave-soldering has developed into two main alloy systems: Sn-Ag-Cu system and based on Sn-Cu eutectic system, to weigh as value equation according to the user, and all there is intrinsic defective in the two.The Sn-Ag-Cu of argentiferous 3～4% is that scolder can provide good reliability and technology yield, but the antioxidant anticorrosive performance is also unsatisfactory, the high cost that causes of bullion content improves; The cost of Sn-Cu eutectic system and modified alloy Sn-Cu-Ni thereof is low, but there are certain problem in soldering reliability and technology yield.Current large usage quantity, more welcome Sn-Ag-Cu are tied to form the focal point into scientific research personnel and manufacturer, because of it can be applied to the various forms of scolder, wave-soldering, Reflow Soldering and manual welding are all had the better manufacturability energy.Current quaternary scolder by the development of Sn-Ag-Cu system mainly contains: (ITRI recommends scolder to Sn-Ag-Cu-Sb, but price height, fusing point is also high slightly, and the most important thing is that Sb has the toxicity that is only second to Pb) and Sn-Ag-Cu-Bi (USP4879096 and CAP1299471 scolder, being easy to generate solder joint peels off), Sn-Ag-Cu-Ni (USP4758407, non-oxidizability is poor slightly), NCMS recommends the Sn-Ag-Cu-Zn of use, and the Kang Puxiwei of BeiJing, China recommends the Sn-Ag-Cu-Cr scolder (Chinese patent 98101071.7) of use etc., these quaternary scolders have improved Sn-Ag-Cu ternary scolder to a certain extent, but are also all having deficiency (contain other toxic elements or non-oxidizability poor slightly or contain fragility phase solder joint in conjunction with bad etc.) aspect certain.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of anti-oxidant corrosion resistance; Fusing point, wetability are all better; Mechanical performance, electrical property is good, the technology yield is good, service-strong Sn-Ag-Cu-Cr-X lead-free solder and preparation method thereof.
For achieving the above object, the present invention takes following technical scheme:
Sn-Ag-Cu-Cr-X lead-free solder of the present invention, the composition of this scolder and content is the percentage meter by weight, silver: 1.0～8.0%, copper: 0.2～1.5%, chromium: 0.05～0.6%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin, and wherein, trace alloying element is one or more in the alloying elements such as Ga, Bi, In, Ni, Ge, La, Ce, Sb, Mn, Zn.
Described trace alloying element: 0-0.1%, in other words, the content of trace alloying element can be 0, but does not also get rid of in the alloying elements such as containing Ga, Bi, In, Ni, Ge, La, Ce, Sb, Mn, Zn one or more, and microalloy element content total amount should be less than 0.1%.
The present invention has added the Al element on Sn-Ag-Cu-Cr system basis, purpose is to overcome problems of the prior art, and obtaining a kind of performance, intact (anti-oxidant corrosion resistance is good; Fusing point, wetability are all better; Mechanical performance, electrical property are good), good, the service-strong Sn-Ag-Cu-Cr-X lead-free solder of technology yield.
The optimal technical scheme of Sn-Ag-Cu-Cr-X lead-free solder of the present invention is: the composition of this scolder and content is the percentage meter by weight, silver: 1.0～2.5%, copper: 0.5～0.8%, chromium: 0.05～0.25%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin.
The more preferably technical scheme of Sn-Ag-Cu-Cr-X lead-free solder of the present invention is: the composition of this scolder and content is the percentage meter by weight, silver: 2.5～4.0%, copper: 0.2～1.5%, chromium: 0.1～0.4%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin.
The most preferred technique scheme of Sn-Ag-Cu-Cr-X lead-free solder of the present invention is: the composition of this scolder and content is the percentage meter by weight, silver: 4.0～8.0%, copper: 0.2～1.5%, chromium: 0.1～0.6%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin.
The preparation method of Sn-Ag-Cu-Cr-X lead-free solder of the present invention, this method comprises following step:
1. percentage meter weighing by weight earlier, silver: 3.0～48.0%, surplus is a tin; Copper: 0.5～35.0%, surplus is a tin; Chromium: 1.0～25.0%, surplus is a tin; Aluminium: 1.0～20.0%, surplus is a tin.
2. again at protective gas atmosphere or molten protection state, also or under vacuum state, adopt foundry alloy: Sn-(0.5～35.0) Cu in the middle of existing method of smelting and the equipment preparation, Sn-(1.0～25.0) Cr, Sn-(3.0～48.0) Ag, Sn-(1.0～20.0) Al.
3. then, the weight that is converted into Sn-Cu, Sn-Cr, Sn-Ag, Sn-Al intermediate alloy and pure Sn and trace alloying element and intermediate alloy thereof by the composition and the weight proportion of scolder of the present invention on resistance furnace is prepared into Sn-Ag-Cu-Cr-X solder alloy ingot blank.
The preparation method of Sn-Ag-Cu-Cr-X lead-free solder of the present invention, this method also comprises following step:
With the alloy ingot blank that obtains in above-mentioned 3 at 300～400 ℃ of fusing cast sliverings, ingot scolders or squeeze to draw and be rolled into silk, plate scolder, also can atomize and make welding powder and use as the soldering paste base-material.
The content of alloying element aluminium should be controlled at 0.001～0.1 weight % among the present invention.Be higher than the wetability that this scope will improve alloy melting point and fragility or reduce scolder, worsen the comprehensive serviceability of scolder; Be lower than this scope, the high-temperature oxidation resistant corrosivity of alloy is had the deterioration effect.Alloying element helps crystal grain thinning, improves solder joint or weld seam bond strength in this scope; Help the material wetability, improve the welding procedure yield; Help forming the fine and close protective layer of preferential oxidation, improve its antioxidant anticorrosive, reduce the consuming cost of material.In addition, in patent of the present invention, also can add total amount less than among 0.1% microalloy element Ga, Bi, In, Ni, Ge, La, Ce, Sb, Mn, the Zn etc. one or more, in the hope of better improving the welding performance and the serviceability of this lead-free solder.
Be below by embodiment and comparative example and in conjunction with the accompanying drawings 1,2 and table 1, table 2 be elaborated.It should be understood that only to relate to the preferred embodiments of the invention described in the table that under the situation that does not break away from the spirit and scope of the present invention, various changes and modifications all are possible.
Description of drawings
Fig. 1 is the process chart of preparation lead-free solder of the present invention;
Fig. 2 is embodiment 4,5 and thermogravimetric (TGA) analytic curve of control sample under 250 ℃ of air atmosphere conditions.
The specific embodiment
As shown in Figure 1, carrying out raw material by the percetage by weight of intermediate alloy earlier prepares and weighing 1, carry out the intermediate frequency preparation 2 of intermediate alloy ingot blank again, carry out the preparation 3 of prealloy scolder ingot blank then, carry out the preparation 4 of scolder ingot blank at last, perhaps carry out the preparation 5 of band filament plate scolder, perhaps the preparation 6 of scolder powder
The preparation of embodiment 1 Sn-Ag1.0-Cu0.9-Cr0.6-Al0.001:
Proportioning by weight percentage, Ag is 1.0%, Cu is 0.9%, Cr is 0.6%, Al is 0.001%.Its preparation process is: prepare Sn-Ag20 intermediate alloy 5.0kg in resistance furnace by weight ratio; Frequently prepare Sn-Cu10 intermediate alloy 5.0kg, Sn-Cr7.5 intermediate alloy 5.0kg, Sn-Al5.0 intermediate alloy 5.0kg, Sn-P5.0 intermediate alloy 5.0kg in the induction furnace in a vacuum; In the preparation process: 1. the pure Sn that will weigh up earlier is melted to 500 ℃ at resistance furnace, adds the Ag bar that weighs up, and stirs and is melted to 400～500 ℃ of furnace temperature, stirs and is incubated half an hour, pours into square little ingot and is prepared into the Sn-Ag20 intermediate alloy; 2. the pure Sn that will weigh up earlier stove in the vacuum induction melting stove is melted to 650 ℃, adds the pure Cu sheet that weighs up, and stirs and is melted to 500～600 ℃ of furnace temperature, stirs insulation 10 minutes, pours into square little ingot and is prepared into the Sn-Cu10 intermediate alloy; 3. the pure Sn that will weigh up earlier melts in the induction furnace in a vacuum frequently, adds the pure Cr piece that weighs up, and stirs and is melted to 1300～1400 ℃ of furnace temperature, stirs and is incubated half an hour, pours into square little ingot and is prepared into the Sn-Cr7.5 alloy; 4. the pure Sn that will weigh up earlier melts in the induction furnace in a vacuum frequently, adds the pure Al piece that weighs up, and stirs and is melted to 500～600 ℃ of furnace temperature, stirs insulation 10 minutes, pours into square little ingot and is prepared into the Sn-Al5 alloy; 5. the pure Sn that will weigh up earlier is melted to 500～600 ℃ in pressure furnace, is poured in the mould that red P powder is housed, and treats alloy graining final vacuum remelting stirring insulation 10 minutes, pours into square little ingot and is prepared into the Sn-P5 alloy.Take by weighing Sn-Ag20 intermediate alloy 10.0g, Sn-Cu10 intermediate alloy 18.0g, Sn-Cr7.5 intermediate alloy 16.00g, Sn-Al5 intermediate alloy 0.040g, pure Sn155.96g.Again pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-Al5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 2 Sn-Ag2-Cu0.7-Cr0.3-Al0.01:
Proportioning by weight percentage, Ag is 2.0%, Cu is 0.7%, Cr is 0.3%, Al is 0.01%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 20.0g, Sn-Cu10 intermediate alloy 14.0g, Sn-Cr7.5 intermediate alloy 8.00g, Sn-Al5 intermediate alloy 0.40g, pure Sn157.6g.Again pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-Al5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 3 Sn-Ag2-Cu0.7-Cr0.1-P0.05:
Proportioning by weight percentage, Ag is 2.0%, Cu is 0.7%, Cr is 0.1%, P is 0.05%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 20.0g, Sn-Cu10 intermediate alloy 14.0g, Sn-Cr7.5 intermediate alloy 2.70g, Sn-P5 intermediate alloy 2.0g, pure Sn161.3g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 4 Sn-Ag3.0-Cu0.5-Cr0.1-P0.005:
Proportioning by weight percentage, Ag is 3.0%, Cu is 0.5%, Cr is 0.1%, P is 0.005%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 30.0g, Sn-Cu10 intermediate alloy 10.0g, Sn-Cr7.5 intermediate alloy 2.70g, Sn-P5 intermediate alloy 0.2g, pure Sn157.1g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 5 Sn-Ag3.0-Cu0.5-Cr0.1-P0.005-Al0.005:
Proportioning by weight percentage, Ag is 3.0%, Cu is 0.5%, Cr is 0.1%, P is 0.005%, Al is 0.005%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 30.0g, Sn-Cu10 intermediate alloy 10.0g, Sn-Cr7.5 intermediate alloy 2.70g, Sn-P5 intermediate alloy 0.2g, Sn-Al5 intermediate alloy 0.2g, pure Sn156.9g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy, Sn-P5 intermediate alloy and Sn-Al5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 6 Sn-Ag3.4-Cu0.5-Cr0.1-Al0.05:
Proportioning by weight percentage, Ag is 3.4%, Cu is 0.5%, Cr is 0.1%, Al is 0.05%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 34.0g, Sn-Cu10 intermediate alloy 10.0g, Sn-Cr7.5 intermediate alloy 2.70g, Sn-Al5 intermediate alloy 2.0g, pure Sn151.3g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-Al5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 7 Sn-Ag3.4-Cu0.5-Cr0.2-P0.05:
Proportioning by weight percentage, Ag is 3.4%, Cu is 0.5%, Cr is 0.2%, P is 0.05%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 34.0g, Sn-Cu10 intermediate alloy 10.0g, Sn-Cr7.5 intermediate alloy 5.40g, Sn-P5 intermediate alloy 2.0g, pure Sn148.6g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 8 Sn-Ag8.0-Cu0.2-Cr0.05-P0.1:
Proportioning by weight percentage, Ag is 8.0%, Cu is 0.2%, Cr is 0.05%, P is 0.1%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 80.0g, Sn-Cu10 intermediate alloy 4.0g, Sn-Cr7.5 intermediate alloy 1.33g, Sn-P5 intermediate alloy 4.0g, pure Sn110.67g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 9 Sn-Ag4.5-Cu1.5-Cr0.1-P0.001:
Proportioning by weight percentage, Ag is 4.5%, Cu is 1.5%, Cr is 0.1%, P is 0.001%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 45.0g, Sn-Cu10 intermediate alloy 30.0g, Sn-Cr7.5 intermediate alloy 2.7g, Sn-P5 intermediate alloy 0.04g, pure Sn122.26g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 10 Sn-Ag8.0-Cu0.2-Cr0.05-P0.05:
Proportioning by weight percentage, Ag is 8.0%, Cu is 0.2%, Cr is 0.05%, P is 0.05%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 80.0g, Sn-Cu10 intermediate alloy 4.0g, Sn-Cr7.5 intermediate alloy 1.33g, Sn-P5 intermediate alloy 2.0g, pure Sn112.67g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 11 Sn-Ag2.5-Cu0.2-Cr0.05-Al0.1:
Proportioning by weight percentage, Ag is 2.5%, Cu is 0.2%, Cr is 0.05%, Al is 0.1%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 25.0g, Sn-Cu10 intermediate alloy 4.0g, Sn-Cr7.5 intermediate alloy 1.33g, Sn-Al5 intermediate alloy 4.0g, pure Sn165.67g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-Al5 intermediate alloy successively, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 12 Sn-Ag3.0-Cu0.7-Cr0.1-Al0.01-Zn0.005-Ga0.005:
Proportioning by weight percentage, Ag is 3.0%, Cu is 0.7%, Cr is 0.1%, Al is 0.01%, Zn is 0.005%, Ga is 0.005%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 30.0g, Sn-Cu10 intermediate alloy 14.0g, Sn-Cr7.5 intermediate alloy 2.7g, Sn-Al5 intermediate alloy 0.4g, pure Zn0.01g, pure Ga0.01g, pure Sn152.88g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-Al5 intermediate alloy successively, treat to add pure Zn, Ga etc. more successively behind the alloy melting, strong agitation, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat again ingot casting remelting to 300 ℃ to be incubated 10min after ingot casting solidifies fully, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 13 Sn-Ag3.0-Cu0.7-Cr0.1-P0.01-In0.01-Ge0.01-Bi0.01:
Proportioning by weight percentage, Ag is 3.0%, Cu is 0.7%, Cr is 0.1%, P is 0.01%, In is 0.01%, Ge is 0.01%, Bi is 0.01%.The preparation of intermediate alloy is with example 1.Take by weighing Sn-Ag20 intermediate alloy 30.0g, Sn-Cu10 intermediate alloy 14.0g, Sn-Cr7.5 intermediate alloy 2.7g, Sn-P5 intermediate alloy 0.4g, pure In0.02g, pure Ge0.02g, pure Bi0.02g, pure Sn152.84g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add Sn-Ag20 intermediate alloy, Sn-Cu10 intermediate alloy, Sn-Cr7.5 intermediate alloy and Sn-P5 intermediate alloy successively, treat to add pure In, Ge, Bi etc. more successively behind the alloy melting, strong agitation, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat again ingot casting remelting to 300 ℃ to be incubated 10min after ingot casting solidifies fully, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The preparation of embodiment 14 Sn-Ag3.0-Cu0.7-Cr0.1-P0.1-Sb0.01-Ce0.01-Mn0.01-La0.01-Ni 0.01:
Proportioning by weight percentage, Ag is 3.0%, Cu is 0.7%, Cr is 0.1%, P is 0.01%, Sb is 0.01%, Ce is 0.01%, Mn is 0.01%, La is 0.01%, Ni is 0.01%.The preparation of host element intermediate alloy is with example 1, in addition again with vacuum Medium frequency induction melting Sn-Sb5, Sn-Ce5, Sn-La5, intermediate alloys such as Sn-Mn5, Sn-Ni5.Take by weighing Sn-Ag20 intermediate alloy 30.0g, Sn-Cu10 intermediate alloy 14.0g, Sn-Cr7.5 intermediate alloy 2.7g, Sn-P5 intermediate alloy 4.0g, Sn-Sb5 is that 0.4g, Sn-Ce5 are that 0.4g, Sn-La5 are that 0.4g, Sn-Mn5 are that 0.4g, Sn-Ni5 are 0.4g, pure Sn147.3g.Earlier pure Sn is melted in resistance furnace and be heated to 300 ℃, add intermediate alloys such as Sn-Ag20, Sn-Cu10, Sn-Cr7.5, Sn-P5, Sn-Sb5, Sn-Ce5, Sn-La5, Sn-Mn5, Sn-Ni5 successively, strong agitation, be heated to 300 ℃ of insulation 10min, be cast in the cylindrical mold, treat ingot casting solidify fully after again with ingot casting remelting to 300 ℃ insulation 10min, pull out the surface oxidation slag, be cast in that to make the ingot blank scolder in the mould standby.
The component content analysis tabulation of table 1, lead-free solder intermediate alloy
| Lead-free solder and intermediate alloy constituent content analysis | Ag(wt％) | Cu(wt％) | Cr(wt％) | Al(wt％) | P(wt％) |
| Sn-Cu10 | - | 9.84 | - | - | - |
| Sn-Ag20 | 20.03 | - | - | - | - |
| Sn-Cr7.5 | - | - | 7.62 | - | - |
| Sn-Al5 | - | - | - | 4.98 | - |
| Sn-P5 | - | - | - | - | 4.69 |
The performance of table 2, modification lead-free solder and traditional Sn-Ag-Cu, Sn-Ag-Cu-Cr lead-free solder compare:
As can be seen from Table 2: the more original Sn-Ag-Cu scolder of scolder of the present invention has higher strength character, and than Sn-Ag-Cu-Cr scolder better plasticity and spreading property is arranged; Electrical conductivity and fusing point are but influenced not quite.
Y1 is control sample Sn-Ag3.0-Cu0.5-Cr0.2 among Fig. 2; Y2 is control sample Sn-Ag3.0-Cu0.5; Y3 is embodiment 5Sn-Ag3.0-Cu0.5-Cr0.1-P0.005-Al0.005; Y4 is embodiment 4Sn-Ag3.0-Cu0.5-Cr0.1-P0.005.Fig. 2 illustrates that modification lead-free solder of the present invention has better high-temperature oxidation resistance, is better than control sample.
Claims (4)
1. the Sn-Ag-Cu-Cr-X lead-free solder of a modification, it is characterized in that, the composition of this scolder and content is the percentage meter by weight, silver: 1.0～8.0%, and copper: 0.2～1.5%, chromium: 0.05～0.6%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin, wherein, trace alloying element is one or more in Ga, Bi, In, Ni, Ge, La, Ce, Sb, Mn, the Zn alloying element.
2. Sn-Ag-Cu-Cr-X lead-free solder according to claim 1, it is characterized in that, the composition of this scolder and content is the percentage meter by weight, silver: 1.0～2.5%, copper: 0.5～0.8%, chromium: 0.05～0.25%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin.
3. Sn-Ag-Cu-Cr-X lead-free solder according to claim 1 is characterized in that the composition of this scolder and content is the percentage meter by weight, silver: 2.5～4.0%, copper: 0.2～1.5%, chromium: 0.1～0.4%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin.
4. Sn-Ag-Cu-Cr-X lead-free solder according to claim 1 is characterized in that the composition of this scolder and content is the percentage meter by weight, silver: 4.0～8.0%, copper: 0.2～1.5%, chromium: 0.1～0.6%, aluminium: 0.001～0.1%, trace alloying element: 0-0.1%, surplus is a tin.
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| CN100439028C (en) * | 2007-01-24 | 2008-12-03 | 太仓市南仓金属材料有限公司 | Leadless soft tin solder |
| CN101767198B (en) * | 2010-03-18 | 2011-11-30 | 中南大学 | Method for cladding modified lead-free solder alloy powder |
| CN101880792B (en) * | 2010-06-07 | 2012-08-22 | 深圳市亿铖达工业有限公司 | Anti-corrosive anti-oxidation Pb-free solder alloy for aluminum soldering |
| CN102085604A (en) * | 2011-03-04 | 2011-06-08 | 上海交通大学 | Sn-Ag-Cu-Bi-Cr low-silver and lead-free solder |
| CN102560311A (en) * | 2012-03-16 | 2012-07-11 | 鹰潭市众鑫成铜业有限公司 | Alloy used in hot plating process of tinned wire |
| CN103008919B (en) * | 2012-12-13 | 2015-05-27 | 郴州金箭焊料有限公司 | Low-silver halogen-free lead-free solder paste |
| CN103008905A (en) * | 2012-12-13 | 2013-04-03 | 郴州金箭焊料有限公司 | Sn-Ag-Cu-Ce-Bi-Cr lead-free solder |
| CN102990250A (en) * | 2012-12-14 | 2013-03-27 | 郴州金箭焊料有限公司 | Sn-Cu-Ni-Ce-Cr lead-free solder and preparation method thereof |
| CN108406158A (en) * | 2015-12-30 | 2018-08-17 | 弘硕科技（宁波）有限公司 | High temperature resistance timeliness high intensity Pb-free solder |
| CN107999993A (en) * | 2017-12-05 | 2018-05-08 | 广东省焊接技术研究所（广东省中乌研究院） | A kind of lead-free solder for temperature controller bellows iron bottom plate solder and preparation method thereof |
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| CN1075416C (en) * | 1998-04-01 | 2001-11-28 | 北京有色金属研究总院 | Low melting point and low steam pressure soldering alloyed metal powder for welding stainless steel vessel and its prodn. method |
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