CN1482266A - Industrial pure tin with resistance to liquid surface oxidizing and application - Google Patents
Industrial pure tin with resistance to liquid surface oxidizing and application Download PDFInfo
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- CN1482266A CN1482266A CNA03133847XA CN03133847A CN1482266A CN 1482266 A CN1482266 A CN 1482266A CN A03133847X A CNA03133847X A CN A03133847XA CN 03133847 A CN03133847 A CN 03133847A CN 1482266 A CN1482266 A CN 1482266A
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- Prior art keywords
- tin
- oxidation
- industrial pure
- pure tin
- liquid
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 230000001590 oxidative effect Effects 0.000 title 1
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 13
- 235000013619 trace mineral Nutrition 0.000 claims abstract description 13
- 239000011573 trace mineral Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910000679 solder Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 30
- 238000007254 oxidation reaction Methods 0.000 abstract description 30
- 229910045601 alloy Inorganic materials 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 abstract description 11
- 238000005476 soldering Methods 0.000 abstract description 6
- 229910001338 liquidmetal Inorganic materials 0.000 abstract description 5
- 229910052732 germanium Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 description 11
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 238000003466 welding Methods 0.000 description 10
- 238000009413 insulation Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000004927 fusion Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 241000209456 Plumbago Species 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 229910020816 Sn Pb Inorganic materials 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 229910020922 Sn-Pb Inorganic materials 0.000 description 2
- 229910008783 Sn—Pb Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910020888 Sn-Cu Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910019204 Sn—Cu Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- -1 fusing points Chemical compound 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
- Coating With Molten Metal (AREA)
Abstract
The present invention provides one kind of industrial pure tin resisting liquid surface oxidation. One or several of trace elements Sb, Ag, Zn, P and Ge in the amount of 0.01-0.2 wt% is added into tin so as to raise the oxidation resistance of liquid metal surface in atmosphere condition. This kind of industrial pure tin may be used as material for producing various pure tin products or tin-base alloy, and is especially suitable for preparing various tin-base electronic soldering alloy requiring high liquid metal surface oxidation resisting performance.
Description
Technical field:
The present invention relates to a kind of industrial pure tin starting material, a kind of industrial pure tin of anti-liquid surface oxidation specifically is provided, this industrial pure tin can be used as a kind of starting material and is used to prepare various pure Sn goods or tin-based alloy, especially be fit to preparation tinbase electronic solder alloy, to improve the resistance of oxidation of its fluid surface.
Background technology:
Tin is a kind of metal with extensive use, wherein is mainly used in the preparation of scolder and bush material based on the alloy of tin, and owing to the fast development of electronic industry, tin is used for the ratio of electronic solder in rapid rising in recent years.Simultaneously, modern microelectronic packaging technology is through nearly 30 years connecting technique progress, very perfect foundation and developed some new welding technique, to adapt to the production needs that solder joint in enormous quantities welds simultaneously, as Reflow Solder Technology and wave soldering technology etc., these new technologies can be to realizing in the hyundai electronics industry that electronic component is with the printed circuit board (PCB) production in enormous quantities with reliable connection of solder joint provide assurance.Wherein the wave soldering technology has special requirement to the oxidation susceptibility of tin alloy.
The principle of work of wave soldering technology is with welding flux alloy heat fused in weld groove, liquid alloy after the fusing is by means of the effect of electronic tin pump, form continuous and stable projection crest at the solder bath liquid level, on the other hand will be in advance plug-in mounting the printed circuit board (PCB) of electronic devices and components place on the conveyer chain, move continuously with the crest of certain movement speed to welding flux alloy, before arriving the fusion welding crest, spray solder flux at place to be welded earlier, the liquid solder crest of high-temperature fusion is immersed and passes at circuit card place to be welded rapidly then, once finish the leg heating, liquid solder is being welded wetting on the mother metal and is being sprawled, the surface reaction of scolder and mother metal and connection procedure, thereby realizing that large quantities of solder joints once weld finishes, and this technology is called the group's weldering and the welding of flowing again.Owing to can increase substantially productivity, this welding technique has obtained to use widely in electronic industry, is that the hyundai electronics encapsulation is the most ripe, influence is the widest, the modern technique that production efficiency is the highest.The main tin-base soft solder that uses comprises the Sn-Pb eutectic solder, and Sn-Pb-Ag is a scolder, and various lead-free solders such as Sn-Cu are scolder, and Sn-Ag-Cu is a scolder etc.The major industry raw material for preparing these welding materials is a pure tin, and its content is that 60% (Sn-Pb eutectic solder) do not wait to 99.3% (Su-0.7Cu% scolder).
One of key technical problem that exists in the wave soldering technology is how to prevent quick oxidation of liquid level at high temperature of liquid tin-based solder and the scruff problem that is caused by oxidation at present.Common tin-based alloy under welding temperature, the very fast formation layer of oxide layer in surface, and accumulation forms scruff in the molten bath.It is very fast that this technology produces the speed of scruff, one Daepori leads to crest welder every day because the loss that the oxidation scruff produces can reach more than the several kilograms of tin, these surface scums have not only lost a large amount of scolders, and cause the inclusion in scolder molten bath to pollute, must be by manually constantly taking off slag operation, crest welder is run well, otherwise, these scruffs showy or that be deposited in the scolder molten bath are easy to adhere to by on the weldering solder joint, cause rack of fusion, welding flaws such as microbonding, therefore, how reducing the oxidation of molten state solder surface, is one of the key problem in technology that will solve in the wave soldering technology and the major technique approach that reduces production costs.According to existing research at present, in the oxidation products of tin solder, mainly be the oxidation of tin, therefore to address this problem, most critical be to adopt the industrial raw material of the tin of anti-liquid oxidatively as preparation Sn parent metal.
Summary of the invention:
The industrial pure tin that the purpose of this invention is to provide a kind of anti-bath surface oxidation, make it in Sn scolder operating temperature range, can under atmospheric condition, have good anti-surface oxidation ability, this industrial pure tin can use separately, also can be used as to use after a kind of industrial raw material and other element are fused into alloy.
To achieve these goals, the present invention specifically provides a kind of industrial pure tin of anti-liquid level oxidation, and chemical formulation is as follows: (weight percent):
Trace element 0.01%～0.2%
The tin surplus
Wherein trace element is selected from the compound of a kind of among Sb, Ag, Zn, P, the Ge or them, and it adds total amount between 0.01%～0.2%.
Anti-bath surface oxidation industry pure tin provided by the invention, can select a kind of common addition means that alloying element is added in the fused industry pure tin, stir and realize homogenizing, usually after adding these trace elements, except that improving antioxidant property, little to influences such as other physicalies of industrial pure tin such as fusing points, can be used as the general industry pure tin and use, particularly can be used to make tin solder.
By discovering of liquid towards industry pure tin or tin-based alloy surface film oxide, mainly be the oxide compound of tin.The oxide on surface of tin is mainly by SnO
2With SnO and composite oxides Sn
3O
4Etc. several thing phase composites.SnO wherein
2Account for major portion; the high oxide of this Sn forms the back at bath surface the protection melt is prevented the indifferent of further oxidation; therefore to reduce the liquid level oxidation of melt Sn; the major technique approach is the structure that changes oxidation products; make the liquid level oxide film form the zone of oxidation structure of protectiveness; reduce the speed of growth of liquid level oxide film, reach inhibition or reduce the purpose of liquid metal in welding high temperature lower surface oxidation rate.
Based on above-mentioned theory; the know-why of the industrial pure tin of anti-liquid surface oxidation provided by the invention is when tin is in molten state; described trace element is owing to the difference at liquid phase and chemical mobility of the surface; ten minutes is easy to segregation and is enriched in the surface of fusion liquid phase; because these trace elements are in the enrichment on surface; changed the protective value of composition, structure and the liquid towards metal of original liquid tin surface layer oxide film; make it to form one deck densification and successive oxide thin layer film, thereby reached the oxidation resistant purpose of liquid alloy.
In the industrial pure tin of the anti-bath surface oxidation of the present invention, the selection principle of trace element addition is, when trace element very little the time, these trace elements mainly are dissolved in the liquid tin, segregate to liquid metal tin the surface amount very little, be not enough to bring into play its antioxygenation, and addition is when too many, then be easy to form insoluble being mingled with, influence various other physicalies of liquid metal tin, the technological standard of industrial pure tin itself has also proposed to require as proposing tin content 〉=99.8% of tin stanniferous amount 〉=99.9%, No. two tin among the GB728-84 to the upper limit of foreign matter content simultaneously.
Description of drawings:
Fig. 1 is the speed (250 ℃, the crucible of 20 mm dias) of the oxidation sludge loss of industrial pure tin under atmosphere.
Embodiment:
Embodiment 1
With No. 1 tin of industry is raw material, adds micro-0.05%Ge (weight percent, down together), is prepared into a kind of anti-liquid surface oxidation tin.Get the 100g sample plumbago crucible heat fused that to place a diameter be 20mm, and be warmed up to 250 ℃ of insulations, scrape off a surperficial skim gently with scraper after, the blue or green condition of the oxidation on observation of liquid state metal melt surface.After just having scraped off surface film, metal bath surface is very bright.Can estimate its anti-oxidant degree from the degree of metal bath surface light easily, in case because oxide film forms, the liquid level of this light can rapidly disappear.By observing tin long-time heating and the insulation under atmosphere that to find to add above-mentioned trace element, the molten tin surface still can keep light, is incubated 5 hours down at 250 ℃, and the liquid level center is light still, the longest once the observation 5 days, metal bath surface still keep light.The color no change of a small amount of oxide thin layer film of liquid level illustrates the existing further oxidation of imitating the prevention liquid level of established oxide film.Therefore, this sample resistance of oxidation is good.
Embodiment 2
The sample composition of preparation is 0.03%P, and all the other are industrial pure tin, and test method and program are identical with embodiment 1.250 ℃ of down insulations, the fusion liquid level keeps light in long-time, and oxidation is after 5 hours, and the liquid level center is still bright, and edge surface has the very thin oxide film of one deck, and does not have color and further change, so this sample resistance of oxidation is good.
Embodiment 3
The sample composition of preparation is 0.05%Sb, and 0.02%Ge, and all the other are industrial pure tin, and test method and program are identical with embodiment 1.250 ℃ of down insulations, the fusion liquid level keeps light in long-time, and oxidation is after 5 hours, and the liquid level center is still bright, and edge surface has the very thin oxide film of one deck, and does not have color and further change, so this sample resistance of oxidation is good.
Embodiment 4
The sample composition of preparation is 0.02Zn%, 0.02Ag% and 0.01%P, and all the other are industrial pure tin, test method and program are identical with embodiment 1.250 ℃ of down insulations, oxidation is after 5 hours under the atmosphere, and the liquid level center is light still, and edge surface has the very thin oxide film of one deck, and does not have color and further change, so this sample resistance of oxidation is good.
Comparative Examples 1
With No. 1 tin of industry is raw material, gets the 100g sample plumbago crucible heat fused that to place a diameter be 20mm, and is warmed up to 250 ℃ of insulations, scrape off a surperficial skim gently with scraper after, the blue or green condition of the oxidation on observation of liquid state metal melt surface.By finding with the contrast of the foregoing description, under similarity condition, the industrial pure tin that does not add trace element is 250 ℃ of insulations down, as long as 5min has promptly formed the complete oxide film of one deck, after scraping off a surperficial skim gently with scraper, generate the new oxide film of one deck again rapidly on the surface after the oxidation between weak point advances, carry out so repeatedly, the oxidation sludge weight and the time relation of acquisition are seen Fig. 1.If do not scrape off this layer liquid level oxide film, it will be grown gradually and thicken, about 20 minutes, the oxide film color gradually change by bright as silver become pale yellow, continue the insulation oxidation, liquid level oxide film color further becomes avy blue again until blue grey at last by the pale yellow golden yellow that becomes, illustrate that the liquid level oxide film is thickening always, established oxide film can not stop the further oxidation of liquid level.The result of this result and the invention described above relatively, advantage of the present invention is conspicuous, because anti-oxidant tin of the present invention can keep the liquid level light for a long time, takes off the quantity of slag so can significantly reduce in production and use, improve the quality of products, reduce production costs.
Comparative example 2
The sample composition of preparation is 0.5Zn%, and all the other are industrial pure tin, gets the 100g sample plumbago crucible heat fused that to place a diameter be 20mm, and is warmed up to 250 ℃ of insulations, compares with other embodiment and has formed thicker oxide film.
Claims (2)
1, a kind of industrial pure tin of anti-liquid surface oxidation is characterized in that chemical formulation is as follows, weight percent:
Trace element 0.01%～0.2%;
The tin surplus;
Wherein trace element is selected from a kind of among Sb, Ag, Zn, P, the Ge or theirs is compound.
2, the industrial pure tin of the described anti-liquid surface oxidation of claim 1 is used to make tin solder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133847 CN1230567C (en) | 2003-07-02 | 2003-07-02 | Industrial pure tin with resistance to liquid surface oxidizing and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03133847 CN1230567C (en) | 2003-07-02 | 2003-07-02 | Industrial pure tin with resistance to liquid surface oxidizing and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1482266A true CN1482266A (en) | 2004-03-17 |
| CN1230567C CN1230567C (en) | 2005-12-07 |
Family
ID=34154358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03133847 Expired - Fee Related CN1230567C (en) | 2003-07-02 | 2003-07-02 | Industrial pure tin with resistance to liquid surface oxidizing and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1230567C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1905985B (en) * | 2004-07-29 | 2010-12-08 | 千住金属工业株式会社 | Lead-free solder alloy |
| CN101988165A (en) * | 2009-07-31 | 2011-03-23 | 中国科学院金属研究所 | High-temperature oxidation resistant lead-free tin-coated alloy |
| CN102337422A (en) * | 2010-07-21 | 2012-02-01 | 中国科学院金属研究所 | Low-ablation lead-free tin plating alloy under high temperature |
| CN101905388B (en) * | 2005-05-20 | 2012-05-30 | 富士电机株式会社 | Method for manufacturing semiconductor device |
| CN102477501A (en) * | 2010-11-22 | 2012-05-30 | 中国科学院金属研究所 | Atmospheric corrosion resisting industrial pure Sn and application thereof |
| CN102560194A (en) * | 2012-03-13 | 2012-07-11 | 南京理工大学 | Non-lead metal material and application of non-lead metal material to cord type initiating explosive devices |
-
2003
- 2003-07-02 CN CN 03133847 patent/CN1230567C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1905985B (en) * | 2004-07-29 | 2010-12-08 | 千住金属工业株式会社 | Lead-free solder alloy |
| CN101905388B (en) * | 2005-05-20 | 2012-05-30 | 富士电机株式会社 | Method for manufacturing semiconductor device |
| CN101988165A (en) * | 2009-07-31 | 2011-03-23 | 中国科学院金属研究所 | High-temperature oxidation resistant lead-free tin-coated alloy |
| CN101988165B (en) * | 2009-07-31 | 2014-06-18 | 中国科学院金属研究所 | High-temperature oxidation resistant lead-free tin-coated alloy |
| CN102337422A (en) * | 2010-07-21 | 2012-02-01 | 中国科学院金属研究所 | Low-ablation lead-free tin plating alloy under high temperature |
| CN102337422B (en) * | 2010-07-21 | 2015-12-09 | 中国科学院金属研究所 | A kind of high temperature bends down the unleaded application warding off tin alloy of corrode |
| CN102477501A (en) * | 2010-11-22 | 2012-05-30 | 中国科学院金属研究所 | Atmospheric corrosion resisting industrial pure Sn and application thereof |
| CN102477501B (en) * | 2010-11-22 | 2014-06-25 | 中国科学院金属研究所 | Atmospheric corrosion resisting industrial pure Sn and application thereof |
| CN102560194A (en) * | 2012-03-13 | 2012-07-11 | 南京理工大学 | Non-lead metal material and application of non-lead metal material to cord type initiating explosive devices |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1230567C (en) | 2005-12-07 |
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Granted publication date: 20051207 |