CN100364712C - Rare earth Er contained SnZn based leadless solder and its preparation method - Google Patents
Rare earth Er contained SnZn based leadless solder and its preparation method Download PDFInfo
- Publication number
- CN100364712C CN100364712C CNB2004101012483A CN200410101248A CN100364712C CN 100364712 C CN100364712 C CN 100364712C CN B2004101012483 A CNB2004101012483 A CN B2004101012483A CN 200410101248 A CN200410101248 A CN 200410101248A CN 100364712 C CN100364712 C CN 100364712C
- Authority
- CN
- China
- Prior art keywords
- rare earth
- solder
- snzn
- alloy
- contained
- 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.)
- Expired - Fee Related
Links
Images
Abstract
The present invention relates to rare earth Er contained SnZn-base lead-free solder and a preparation method thereof which belong to the technical field of manufacturing lead-free solder for electronic packaging in microelectron industry. The solder has the components, in weight percentages, 5 to 9% of Zn, 0 to 1.5 % of Ag, 0.05 to 1.0 % of commercial rare earth Er or simultaneous 3 to 5% of Bi, and Sn in balancing amount. The rare earth Er contained SnZn-base lead-free solder has the preparation method that a salt mixture with the weight ratio of potassium chloride to lithium chloride of (1 to 1.6): (0.8 to 1.2) is melted and poured on Sn; after the Sn is melted, weighed Zn or additional Bi and additional Ag are added in a Sn solution to make the Zn melted; then, the commercial rare earth Er is pressed into the salt mixture and the SnZn-base alloy by a bell jar of which the wall is provided with holes; and the bell jar is rotated, temperature is preserved for 1 to 2 hours after complete melt, and the surface salt mixture is removed after agitation, stationary placement and solidification. The solder of has the advantages of microscopic structure refinement and uniformity, purity increase, convenient smelting, low cost and no pollution, and the wetting technological property and the metallurgy quality are obvious improved.
Description
Technical field
A kind of rare earth Er contained SnZn base leadless solder belongs to the assembling of microelectronic industry electronics and uses lead-free brazing manufacturing technology field.
Background technology
Over past ten years, researched and developed out multiple lead-free solder alloy both at home and abroad, patent just relates to hundreds of.The lead-free solder alloy of research mainly concentrates on three temperature sections and several alloy series at present.Wherein, most representative is the middle-temperature section lead-free solder alloy, as Sn-Cu, Sn-Ag, Sn-Zn binary system alloy, and ternary alloy such as Sn-Ag-Cu, Sn-Ag-Bi, Sn-Zn-Bi or multicomponent alloy more.
Basic demand to lead-free brazing should comprise: fusion temperature should be near the SnPb eutectic temperature, and fusion temperature is suitable little at interval; Wetability or soldering processes performance are preferably arranged, and good wetability can reduce weld defect, improve soldering productivity ratio; Good physical and mechanical property as the stability of intensity, creep-resistant property, heating power fatigue resistance, metallography tissue, satisfies the reliability requirement of electronic product; Performances such as good electricity is led, thermal conductance should be arranged in addition; Chemical property is also very important, makes soldered fitting that good corrosion resistance be arranged; Lead-free brazing should not comprise new toxic component; The solder cost is low, in order to applying etc.
From the domestic and international research present situation, most widely used middle-temperature section can realize aborning in a short time unleaded alternative will be Sn-Cu, Sn-Ag binary alloy system and Sn-Ag-Cu ternary alloy system or more multicomponent alloy solder based on this.The Sn-Cu solder will be mainly used in wave-soldering, and the Sn-Ag-Cu brazing filler metal will be mainly used in reflow welding.
At present, the selection of brazing filler metal alloy in fact still is in the stage of fumbling, and main relevant with product or application, major influence factors remains welding temperature and price.When welding temperature was the key issue that must consider, Japan just adopted SnZn base solder alloy to be used for the household appliances manufacturing, 191 ℃-195 ℃ of fusion temperatures, and also cost is low.In the Sn8Zn3Bi alloy,, can improve the decay resistance of Zn in the wet environment with Bi instead of part Zn.Japan generally accepts to contain the solder of Bi.
The SnZn brazing filler metal alloy species that occurs in the world is a lot of at present, representational patent brazing filler metal alloy has: Sn-(6.7-19.2) Zn-(2.7-19.4) In[U.S. Pat P 5242658], Sn-(16-30) Zn-(2-11) Ag[U.S. Pat P 5698160], Sn-(7-11) Zn-(1-5) Bi[U.S. Pat P 6391123] and Sn-(4-10) Zn-(0.05-1) RE[Chinese patent ZL 01131275.0] etc.
The advantage of SnZn eutectic alloy is that fusion temperature is low, and near the SnPb eutectic solder.On the basis of SnZn alloy, add In, Bi, can improve the wettability of solder, reduce the solder fusion temperature, substitute part Zn, can also improve the corrosive nature of SnZn solder alloy with Bi.But too much Bi can increase crystallization range, may cause solder joint to form fire check, or reduces solder joint plasticity.In addition, In is a rare metal, and the abundance in the earth's crust is very low, and costs an arm and a leg, and is not suitable for extensive use.The interpolation of RE has the effect that improves metallurgical microstructure and property, also may improve the soldering processes performance of sprawling.Mainly be to add Ce, La mixed rear earth at present.
Summary of the invention
Effect of the present invention and advantage be, on the basis of low eutectic of fusion temperature or nearly eutectic SnZn alloy, adds a small amount of rare earth Er, or add Ag or Bi simultaneously.Because the metamorphism of rare earth Er, can make solder microstructure thinning, evenly, degree of purity increases, and it is convenient, cheap to smelt, and improves the effect such as processing performance of sprawling of solder.
Rare earth Er contained SnZn base leadless solder involved in the present invention is characterized in that: contain percentage by weight and be 5～9% Zn, and 0～1.5% Ag, 0.05～1% commercially available rare earth Er when the content of Ag is 0%, contains 3～5% Bi, and all the other are Sn.
The invention provides a kind of preparation method of rare earth Er contained SnZn base leadless solder, it is characterized in that:
(1) by weight with potassium chloride: lithium chloride=(1～1.6): the salt-mixture of (0.8～1.2) is watering on the tin that is weighing up after the fusing down at 450 ℃～550 ℃;
(2) temperature is risen to 600 ℃～800 ℃, treat tin fusing after, with the Zn that weighs up or also have Bi or Ag to join in the middle of the tin liquor of fusion, stir, form alloy;
(3) treat its fusing evenly after, commercially available rare earth Er is pressed into rapidly in the alloy of above-mentioned fusion with stainless steel bell jar with holes on the wall, rotate bell jar;
(4) treat that rare earth melts fully after, be incubated 1～2 hour, stir, make the alloy homogenising, leave standstill and come out of the stove, solidify the salt-mixture that the surface is removed in the back.
Performance after improving with the rare earth Er contained lead-free brazing of formal specification the present invention of chart below by the test data of some examples, and compare with the traditional SnZn solder that obtains under the same conditions.
Table 1 is 8 kinds of rare earth Er contained SnZn base leadless solders and traditional SnZn solder component list, forms in the table all to be weight percentage, and Er represents rare earth erbium, gives the liquidus temperature and the solidus temperature of each solder simultaneously.The liquidus curve of solder and solidus temperature record by slow cooling curve.As can be seen from Table 1, example 1～8 of the present invention has the fusion temperature scope close with the SnZn lead-free brazing, is fit to present unleaded soldering processes condition.
Table 2 is comparisons of example 1～8 of the present invention and traditional SnZn lead-free brazing shear strength and spreading area.As can be seen from the table, the shear strength of example 1～8 of the present invention and spreading area and traditional SnZn solder quite or make moderate progress are applicable to the microelectronic industry surface-assembled.
Fig. 1 and Fig. 2 are respectively the rare earth Er contained tin base leadless soldering-flux of the present invention and the comparison of traditional SnZn solder microscopic structure.As can be seen, the solder microscopic structure of adding rare earth Er is tiny, and the crystalline structure that does not add rare earth Er is thick, high directivity, fragility are big.This has also disclosed the reason that rare earth Er contained lead-free brazing can improve the solder metallurgical quality from microcosmic angle.
In addition, because the density of Er is slightly larger than Sn, during alloy smelting, rare earth can not swim in the surface of Sn base alloy, makes that smelting process is more convenient to carry out.
Description of drawings:
Fig. 1: the microscopic structure of the rare earth Er contained unleaded brazing metal of SnZn base.
Fig. 2: the microscopic structure of the unleaded brazing metal of traditional SnZn.
The specific embodiment
Example 1: the potassium chloride and the 20 grams lithium chloride salt-mixtures of 26 grams are watered on 94 gram tin after the fusing down at 460 ℃.Furnace temperature is risen to 620 ℃, 5 gram Zn are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 1 gram.Be incubated 1 hour, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 360 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 2: the potassium chloride and the 20 grams lithium chloride salt-mixtures of 26 grams are watered on 92.5 gram tin after the fusing down at 460 ℃.Furnace temperature is risen to 780 ℃, 7 gram Zn are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.5 gram.Be incubated 1.5 hours, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 380 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 3: the potassium chloride and the 18 grams lithium chloride salt-mixtures of 23.4 grams are watered on 90.75 gram tin after the fusing down at 490 ℃.Furnace temperature is risen to 680 ℃, 9 gram Zn are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.25 gram.Be incubated 1 hour, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 360 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 4: the potassium chloride and the 20 grams lithium chloride salt-mixtures of 26 grams are watered on 89.95 gram tin after the fusing down at 510 ℃.Furnace temperature is risen to 720 ℃, 10 gram Zn are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.05 gram.Be incubated 2 hours, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 400 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 5: the potassium chloride and the 25 grams lithium chloride salt-mixtures of 32.5 grams are watered on 88.75 gram tin after the fusing down at 500 ℃.Furnace temperature is risen to 720 ℃, 8 gram Zn and 3 gram Bi are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.25 gram.Be incubated 1.5 hours, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 380 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 6: the potassium chloride and the 20 grams lithium chloride salt-mixtures of 26 grams are watered on 86.5 gram tin after the fusing down at 460 ℃.Furnace temperature is risen to 800 ℃, 8 gram Zn and 5 gram Bi are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.5 gram.Be incubated 2 hours, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 400 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 7: the potassium chloride and the 20 grams lithium chloride salt-mixtures of 26 grams are watered on 90.25 gram tin after the fusing down at 550 ℃.Furnace temperature is risen to 800 ℃, 9 gram Zn and 0.5 gram Ag are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.25 gram.Be incubated 2 hours, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 400 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Example 8: the potassium chloride and the 20 grams lithium chloride salt-mixtures of 26 grams are watered on 89 gram tin after the fusing down at 450 ℃.Furnace temperature is risen to 600 ℃, 9 gram Zn and 1.5 gram Bi are joined in the middle of the tin liquor after making the fusing of tin and salt-mixture, constantly stir simultaneously, form alloy; Be pressed into rapidly in the middle of the above-mentioned molten alloy with stainless steel bell jar with holes on the wall rare earth Er, and constantly stir, till rare earth melts fully 0.5 gram.Be incubated 2 hours, constantly stir, make the alloy homogenising.Leave standstill and come out of the stove, treat to remove surperficial salt-mixture behind the alloy graining.Furnace temperature is reduced to 400 ℃ the solder piece reheated fusing, stand-by into strips at the angle bar top-pour then.
Table 1 brazing filler metal alloy composition and fusion temperature
| Example | Sn(wt ％) | Zn(wt％) | Er(wt％) | Bi(wt％) | Ag(wt％) | Liquidus temperature (℃) | Solidus temperature (℃) |
| Comparative Examples | 91 | 9 | 0 | 0 | 0 | 197.9 | 192.3 |
| Embodiment 1 | 94 | 5 | 1 | 0 | 0 | 210.9 | 194.0 |
| Embodiment 2 | 92.5 | 7 | 0.5 | 0 | 0 | 200.5 | 194.0 |
| Embodiment 3 | 90.75 | 9 | 0.25 | 0 | 0 | 197.9 | 192.7 |
| Embodiment 4 | 89.95 | 10 | 0.05 | 0 | 0 | 198.4 | 194.0 |
| Embodiment 5 | 88.75 | 8 | 0.25 | 3 | 0 | 194.3 | 186.3 |
| Embodiment 6 | 86.5 | 8 | 0.5 | 5 | 0 | 193.2 | 183.7 |
| Embodiment 7 | 90.25 | 9 | 0.25 | 0 | 0.5 | 195.5 | 191.0 |
| Embodiment 8 | 89 | 9 | 0.5 | 0 | 1.5 | 205.3 | 194.9 |
Table 2 shear strength and spreading area
| Example | Shear strength (MPa) | Spreading area (mm2) |
| Comparative Examples | 58.7 | 41.4 |
| Embodiment 1 | 36.6 | 34.4 |
| Embodiment 2 | 45.1 | 38.3 |
| Embodiment 3 | 69.1 | 43.7 |
| Embodiment 4 | 64.6 | 40.4 |
| Embodiment 5 | 53.6 | 37.6 |
| Embodiment 6 | 45.1 | 42.9 |
| Embodiment 7 | 52.7 | 39.9 |
| Embodiment 8 | 46.8 | 35.1 |
Claims (1)
1. rare earth Er contained SnZn base leadless solder is characterized in that: contain percentage by weight and be 5～9% Zn, and 0～1.5% Ag, 0.05～1% commercially available rare earth Er contains 3～5% Bi when the content of Ag is 0%, and all the other are Sn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101012483A CN100364712C (en) | 2004-12-17 | 2004-12-17 | Rare earth Er contained SnZn based leadless solder and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101012483A CN100364712C (en) | 2004-12-17 | 2004-12-17 | Rare earth Er contained SnZn based leadless solder and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1621195A CN1621195A (en) | 2005-06-01 |
| CN100364712C true CN100364712C (en) | 2008-01-30 |
Family
ID=34766754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101012483A Expired - Fee Related CN100364712C (en) | 2004-12-17 | 2004-12-17 | Rare earth Er contained SnZn based leadless solder and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100364712C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100462183C (en) * | 2006-04-30 | 2009-02-18 | 东莞市中实焊锡有限公司 | Lead-free anti-oxidation rare-earth-contg. type SnZn alloy welding flux, and its prepn. method |
| CN103042315B (en) | 2013-01-22 | 2015-05-27 | 马莒生 | Heat-resistant and moisture-resistant low-melting-point lead-free solder alloy |
| CN104002058B (en) * | 2013-02-25 | 2017-04-05 | 北京有色金属与稀土应用研究所 | A kind of Sn Zn Ag Ni alloy lead-free solders and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW504428B (en) * | 2001-12-21 | 2002-10-01 | Chuan-Sheng Liu | Vibration-resistant lead-free solder composition |
| CN1152768C (en) * | 2002-07-02 | 2004-06-09 | 北京工业大学 | High creep resistance rareearth contained tin base leadless soldering-flux and preparation method thereof |
| CN1161205C (en) * | 2001-09-05 | 2004-08-11 | 北京工业大学 | Rare earth-containing tin-base lead-less brazing alloy and its prepn |
| CN1175956C (en) * | 2002-05-10 | 2004-11-17 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
-
2004
- 2004-12-17 CN CNB2004101012483A patent/CN100364712C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1161205C (en) * | 2001-09-05 | 2004-08-11 | 北京工业大学 | Rare earth-containing tin-base lead-less brazing alloy and its prepn |
| TW504428B (en) * | 2001-12-21 | 2002-10-01 | Chuan-Sheng Liu | Vibration-resistant lead-free solder composition |
| CN1175956C (en) * | 2002-05-10 | 2004-11-17 | 大连理工大学 | Leadfree SnZn-base alloy solder containing rare-earth elements |
| CN1152768C (en) * | 2002-07-02 | 2004-06-09 | 北京工业大学 | High creep resistance rareearth contained tin base leadless soldering-flux and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1621195A (en) | 2005-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100462183C (en) | Lead-free anti-oxidation rare-earth-contg. type SnZn alloy welding flux, and its prepn. method | |
| CN101348875A (en) | Tin, bismuth and copper type low temperature lead-free solder alloy | |
| CN101491866B (en) | Low-temperature leadless cored solder alloy and produced solder paste | |
| CN101780607B (en) | Lead-free solder for electronic packaging, assembling and soldering and preparation method thereof | |
| CN101380700A (en) | Tin bismuth cuprum series leadless solder and preparation method thereof | |
| CN109352208B (en) | Sn-Bi low-silver lead-free solder alloy and preparation method thereof | |
| CN102699563A (en) | Low-silver lead-free soft solder | |
| CN103406686A (en) | Co-included Sn-Bi-based high-strength lead-free low-temperature welding flux | |
| CN101356293A (en) | Lead-free solder with low copper dissolution | |
| CN101862921A (en) | Sn-Cu-Ni lead-free solder containing Pr, Sr and Ga | |
| CN101157162A (en) | SnAgCu leadless brazing filler metal with antioxygenic performance | |
| CN101585119A (en) | Oxidation resistant lead-free solder alloy in low silver | |
| CN100352596C (en) | Lead-free soft brazing alloy containing mixed rare earth and production thereof | |
| CN103028863A (en) | High-anti-oxidation lead-free solder | |
| CN100467192C (en) | Pb-free solder alloy compositions comprising essentially tin, silver, copper and phosphorus | |
| CN102476249A (en) | Sn-Ag-Cu welding flux capable of resisting atmospheric corrosion | |
| CN106271187B (en) | Lead-free high-temperature oxidation-resistant solder and preparation method thereof | |
| CN102642099A (en) | Sn-Zn-based lead-free solder alloy for aluminum bronze soldering and method for preparing same | |
| CN100364712C (en) | Rare earth Er contained SnZn based leadless solder and its preparation method | |
| CN102500946A (en) | Sn-Ag-Cu-Bi-Er low-silver and lead-free welding flux and preparation method for same | |
| CN1203960C (en) | Oxidation-inhibited lead-free welding materials | |
| CN101733575A (en) | Tin-zinc-bismuth-copper leadless solder with low cost and welding spot thereof | |
| CN101224526A (en) | Lead-free compound solder by Ni particle strengthening tin and silver group and preparing method thereof | |
| CN1285443C (en) | Rare earth contained SnAgCuEr tin based leadless solder and its preparation method | |
| CN101088698A (en) | No-lead soft brazing alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080130 Termination date: 20101217 |