CN102337422A - Low-ablation lead-free tin plating alloy under high temperature - Google Patents
Low-ablation lead-free tin plating alloy under high temperature Download PDFInfo
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- CN102337422A CN102337422A CN201010232451XA CN201010232451A CN102337422A CN 102337422 A CN102337422 A CN 102337422A CN 201010232451X A CN201010232451X A CN 201010232451XA CN 201010232451 A CN201010232451 A CN 201010232451A CN 102337422 A CN102337422 A CN 102337422A
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Abstract
The invention belongs to the field of electronic and electric appliance manufacturing, and relates to tin-based alloy used in high-temperature tin thermal-plating (tin plating) on surfaces of electronic and electric element weld joints. Specifically, the invention provides a Sn-Ni based low-ablation lead-free tin plating alloy under a high temperature. The alloy comprises chemical components of, by weight: 0.1 to 1.5% of Ni, 0.001 to 0.1% of third group components (wherein the third group components indicate one or a composition of components selected from Ag, Cu, Si, P, Ge, Al, Ga, and Ti), and balance of Sn and inevitable impurities. Compared to common tin alloys, the alloy provided by the invention is advantaged in that: a heavy metal lead is not contained in the alloy; and under a relatively high tin plating temperature (300 to 400 DEG C), the ablation speed of the alloy upon a copper substrate is slow. Therefore, the alloy can be widely applied in lead-free surface tin plating technologies of various elements under a high temperature, wherein the elements are manufactured from Cu, Fe, Al, or alloys thereof. The alloy is especially suitable for high-temperature lead-free tin plating technologies on surfaces of small-sized Cu or Cu alloys.
Description
Technical field
The invention belongs to electronics and electrical equipment and make the field, relate to the employed tin-based alloy of electronics and electric elements leg surface elevated temperature heat zinc-plated (warding off tin), the unleaded tin alloy of warding off of low corrode under specifically a kind of Sn-Ni base high temperature.
Background technology
In electronics and electrical equipment process industry field, carrying out soldering with tin-based solder is one of the most frequently used interconnection technique, is mainly used in electricity and mechanical connection between metal and the metal.In the modern industry, copper is present best conducting metal, so soldering mainly is used to the connection of copper and copper alloy.Because place under field conditions (factors), there are the natural sull of one deck in copper or copper alloy surface, when actual welding, the fused tin solder is difficult for sprawling with wetting at the copper substrate surface that sull is arranged.In order to overcome this shortcoming; Modern industry generally adds one leg electroplating surfaces with tin technology in electronic device fabrication processes solves; After copper or copper alloy surface were zinc-plated, the fused tinsolder greatly improved in zinc-plated wetting of surfaces property, had guaranteed that thus follow-up mother metal has good weldability.
At present, the electroplating surfaces with tin technology of copper or copper alloy mainly contains electroplates or two kinds of hot dip processs, also claims to ward off tin in latter's industry.Generally speaking, electroplating technology is relatively complicated, and it not only requires part to be plated to have surface of good to prepare, the plating condition of accurately controlling, but also certain plating aftertreatment will be arranged; In addition, the discharging of electroplating effluent also relates to the cost for wastewater treatment of great number, and particularly each major industrial country of the world has improved emission standard in succession at present, so the production cost of eleetrotinplate has the trend that significantly rises.As a comparison, it is relatively simple to ward off process of tin, and it is that copper matrix (copper wire, copper sheet etc.) is directly immersed the tin or the tin alloy of high-temperature fusion; React through solid/liquid interfaces; After treating that one deck tin is stained with on the surface, the tin from high-temperature fusion takes out rapidly, solidifies the back and forms the surface heat tin coating.This technology does not generally need follow-up surface treatment, does not have the problem of electroplating wastewater discharging yet, is a kind of energy-saving and emission-reducing technique therefore.Along with the attention gradually of national environmental pollution problem, can predict, in the future in this area, high temperature is warded off process of tin will have very strong technological competitiveness.
It mainly is eutectic tin-lead alloy (Sn63%-Pb37%) that traditional heat is warded off tin alloy, and its fusing point is 183 ℃, because this alloy materials cost is low and the good fluidity of eutectic alloy itself, thereby once is widely used by industry member.In recent years, owing to countries in the world government causes the attention of problem of environmental pollution to using heavy metal lead in electronics and the electrical equipment industry, countries in the world are in succession to using heavy metal lead to carry out restriction or forbidding in electronics and the electrical equipment industry.Through a large amount of scientific researches, industry member has been developed some lead-free alloys and has been substituted original eutectic tin-lead alloy at present.For example; For on the Cu matrix, warding off tin, be representative mainly with the Sn-Cu alloy, lead-free alloy commonly used at present is eutectic or hypereutectic gun-metal; Copper content is 0.7wt%-4wt%; Wherein the main effect of alloy element copper is the dissolution rate that when high temperature is warded off tin, reduces in the liquid tin of copper matrix, and the principles of science of its foundation is a kind of solid metal in the melt near self saturation solubility, dissolves because the dissolution equilibrium of solid/liquid interfaces is difficult for quilt again.
A subject matter that adopts eutectic or hypereutectic tin copper lead-free alloy to carry out running into when heat is warded off the tin operation is to warding off the restriction of Xi Wendu, and according to copper-Xi binary phase diagram, the Sn-Cu eutectic point is 227 ℃ (containing Cu0.7wt%); When temperature raises, the saturation solubility of copper in tin will sharply raise, when warding off Xi Wendu and reach 300 ℃; The saturation solubility of copper in tin is near 4%; And temperature is when reaching 400 ℃, and the saturation solubility of copper in liquid tin will be near 8%, because a large amount of copper dissolutions is in liquid tin; Increase the melt viscosity of hypereutectic alloy; The latter sharply reduces the liquid fluidity of alloy itself again, causes very big difficulty to warding off the tin operation thus, so copper content is unsuitable too high.And the Sn-4%Cu alloy higher as far as copper content, warding off Xi Wendu should not surpass 300 ℃, otherwise the dissolution rate of copper matrix in liquid tin will sharply rise.
Yet; Often need ward off the tin operation in electronics and the electrical equipment industry above under 300 ℃ the high temperature; Particularly tin is warded off on the thin copper wire surface that has an enameled wire, some surfaces; Require thin copper wire under the situation of not removing surperficial paint film, directly to carry out the surface in the production and ward off tin,, save production cost to reduce relevant process procedure.Production practice show; The paint film general requirement on enameled wire surface immerses in the 350-400 ℃ of hot tin of pyritous and could remove rapidly; Therefore relevant industrial requires the Xi Wendu that wards off of alloy to bring up to this TR, directly carries out the technical requirements that tin is warded off on the surface to satisfy to produce, and improves the production high-level efficiency.Yet as preceding said, when warding off the Xi Wendu rising, because the saturation solubility of copper in tin also will sharply raise, at 350-400 ℃ of high temperature range, the Sn-4%Cu alloy is far below its saturation solubility, and at this moment the dissolution rate of copper will increase sharply.With this understanding, the copper wire thinner as far as some diameters warded off in the tin process; The control of immersion time must be very strict, and the time is too short, and surperficial paint film does not remove as yet; The not sticking as yet tin in copper wire surface, and the time is long slightly, because the dissolving of the high speed of copper; Copper wire dissolving fully in molten tin, both all cause and ward off the tin failure.Therefore, how to reduce effectively that the solubleness of copper in molten tin alloy is that present high temperature is warded off one of key problem in technology that urgently will solve in the process of tin under the high temperature.
Summary of the invention
Ward off copper rapidly-soluble problem in liquid tin in the tin process in order to overcome high temperature, the present invention provides a kind of new supplied high temperature to ward off the low corrode leadless tin-base alloy of tin.
Main technical schemes of the present invention is:
The unleaded tin alloy of warding off of low corrode under a kind of high temperature; Through in industrial pure tin, adding a spot of nickel, form Sn-Ni base alloy, owing to contain a spot of nickel in the alloy; It effectively reduces copper dissolution rate in tin under the high temperature, thereby is easy to realize the industrial technical need that elevated temperature heat is warded off tin that goes up.
The unleaded tin alloy of warding off of low corrode is an essentially consist with the Sn-Ni alloy under the described high temperature, and adding a small amount of the 3rd constituent element is antioxidant addn, and the weight percent of its alloy consists of:
Ni 0.1-1.5% (preferable range 0.3-1%);
The 3rd constituent element 0.001-0.1% (preferable range 0.005-0.05%);
Sn and unavoidable impurities surplus.
Among the present invention, described the 3rd constituent element refers to Ag, Cu, and Si, P, Ge, Ga, Al, the combination of one or more among the Ti, under the situation of several kinds the 3rd constituent element combinations, its total amount is no more than the concentration range of its composition regulation.
High temperature provided by the invention is warded off tin alloy and can be selected a kind of common smelting technique to smelt, and after alloy fully melts and stirs, can cool off by ingot casting, obtains alloy product.
Know-why of the present invention is following:
The present invention is through discovering the dissolution kinetics of copper in high-temperature fusion tin; The dissolving of copper in liquid tin can be divided into two primary processes; When copper immerses in the high-temperature liquid state tin, at first form layer of copper-Sn intermetallic compound and (be lower than under 415 ℃ of situation, at first forming Cu at the interface
6Sn
5, and form Cu on the solid-liquid interface when being higher than 415 ℃
3Sn).Then, this layer intermetallic compound further is dissolved in the liquid tin again.Two processes hocket and all dissolve until copper.According to the understanding to this dissolution kinetics process, the present invention adds a spot of nickel in liquid tin, and when copper immersed the fused solution tin alloy, dissolved nickel at first segregated to liquid/liquid/solid interface in the liquid state, and forms one deck nickel-Sn intermetallic compound (Ni
3Sn
4), the intermetallic compound that this layer is new has been isolated copper-Sn intermetallic compound, make it can not with the contacting of liquid tin, and actual what contact with liquid tin is the nickel Sn intermetallic compound.Because the nickel Sn intermetallic compound is more stable than copper Sn intermetallic compound, and be difficult for being dissolved by liquid tin.Therefore, copper or the copper alloy dissolution rate in this Sn-Ni alloy just has been suppressed effectively.According to this principle, when the addition of nickel is not enough, its can not segregation in solid/liquid interfaces; Form the successive resist, thereby can not suppress the quick dissolving of copper in liquid tin under the high temperature effectively, and when the addition of nickel is too much; Can in liquid tin, form solid-state nickel tin compound particle; Influence the viscosity and the flowability of liquid alloy, as previously mentioned, the liquid alloy flowability of difference will have a strong impact on the use characteristics of warding off tin.
Technological merit of the present invention is:
1, the present invention does not contain heavy metal lead, is a kind of lead-free alloy of environment-friendly type;
2, alloy of the present invention can use down at the higher Xi Wendu (350-400 ℃) that wards off, and in this TR, enameled wire top layer paint film is easy to oxidized removal; Because alloying element has effectively suppressed copper dissolution rate in high-temperature liquid state tin, the copper wire that therefore can be implemented in the band enameled wire in the industry directly carries out the purpose that high temperature is warded off tin without surface paint removal, and the latter might reduce the production cost of warding off process of tin significantly.
3, compare with common tin alloy, the present invention is slow to the corrosion speed of copper matrix, can be widely used in the unleaded process of tin of warding off of various piece surfaces under the hot conditions; Comprise Cu; Fe, Al and their alloy, the high-temp leadless that is specially adapted to undersized Cu or Cu alloy surface is warded off process of tin.
Embodiment
Embodiment 1:
By weight percentage, preparation Ni 0.5%, Ag 0.01%; Ga 0.01%, and Si 0.005%, and all the other are the Sn-Ni alloy of Sn; Select a kind of common smelting technique that technical pure Sn is melted; Add the various alloying elements weigh up by weight percentage then, treat that it fully is dissolved in the LIQUID Sn after, stir and ingot casting subsequent use.
Get this alloy and place an open pot, use the retort furnace heat fused, and be warming up to 400 ℃ of insulations 30 minutes, make LIQUID Sn alloy temperature homogenizing.Get the thin copper wire (Φ 0.6mm) of one section band enameled wire, an end is immersed in the preprepared brazing flux, take out and remove unnecessary brazing flux; Immerse then in the off-the-shelf LIQUID Sn base alloy; Last layer Sn has been warded off on the copper wire surface after 2 minutes, and it was soaked in LIQUID Sn 5 minutes, and taking out the diameter of measuring copper wire is 0.5mm; It is thus clear that copper wire is relatively low in this Sn base alloy dissolution rate, directly wards off tin and has obtained good effect.
Embodiment 2:
By weight percentage, preparation Ni 1.0%, Cu 0.03%, and Ge 0.02%, and all the other be the Sn-Ni alloy of Sn, and the experimental technique that employing is identical with embodiment 1 is directly warded off tin at 400 ℃, has obtained good effect.
Embodiment 3:
By weight percentage, preparation Ni 0.3%, P 0.02%, and all the other be the Sn-Ni alloy of Sn, and the experimental technique that employing is identical with embodiment 1 is directly warded off tin at 350 ℃, has obtained good effect.
Embodiment 4:
By weight percentage, preparation Ni 0.5%, Al 0.005%, and all the other be the Sn-Ni alloy of Sn, and the experimental technique that employing is identical with embodiment 1 is directly warded off tin at 360 ℃, has obtained good effect.
Embodiment 5:
By weight percentage, preparation Ni 0.4%, Ag 0.03%, and Ti 0.003%, and all the other be the Sn-Ni alloy of Sn, and the experimental technique that employing is identical with embodiment 1 is directly warded off tin at 370 ℃, has obtained good effect.
Embodiment 6:
By weight percentage, preparation Ni 0.6%, Si 0.005%, and P 0.01%, and all the other be the Sn-Ni alloy of Sn, and the experimental technique that employing is identical with embodiment 1 is directly warded off tin at 380 ℃, has obtained good effect.
Claims (4)
1. the unleaded tin alloy of warding off of low corrode under the high temperature is characterized in that: in industrial pure tin, add the Ni of 0.1-1.5wt%, and anti-oxidant micro-the 3rd constituent element, the content of anti-oxidant micro-the 3rd constituent element is 0.001-0.1wt%.
2. by the unleaded tin alloy of warding off described in the claim 1, it is characterized in that: anti-oxidant micro-the 3rd constituent element refers to Ag, Cu, and Si, P, Ge, Al, Ga, one or more among the Ti are compound.
3. by the described unleaded tin alloy of warding off of claim 1, it is characterized in that: Ni content preferable range is 0.3-1wt%.
4. by the described unleaded tin alloy of warding off of claim 1, it is characterized in that: the preferable range of anti-oxidant micro-the 3rd constituent element content is 0.005-0.05wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010232451.XA CN102337422B (en) | 2010-07-21 | 2010-07-21 | A kind of high temperature bends down the unleaded application warding off tin alloy of corrode |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010232451.XA CN102337422B (en) | 2010-07-21 | 2010-07-21 | A kind of high temperature bends down the unleaded application warding off tin alloy of corrode |
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| Publication Number | Publication Date |
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| CN102337422A true CN102337422A (en) | 2012-02-01 |
| CN102337422B CN102337422B (en) | 2015-12-09 |
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| CN201010232451.XA Expired - Fee Related CN102337422B (en) | 2010-07-21 | 2010-07-21 | A kind of high temperature bends down the unleaded application warding off tin alloy of corrode |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390176A (en) * | 2015-12-15 | 2016-03-09 | 北京有色金属与稀土应用研究所 | Tin-lead plating flat copper wire and preparation method thereof |
| CN107475563A (en) * | 2017-10-24 | 2017-12-15 | 河南科技大学 | One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof |
| CN112736366A (en) * | 2020-12-29 | 2021-04-30 | 上海应用技术大学 | Method for cast welding light metal negative grid lead storage battery busbar |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482266A (en) * | 2003-07-02 | 2004-03-17 | 中国科学院金属研究所 | Industrial pure tin with resistance to liquid surface oxidizing and application |
| CN1803379A (en) * | 2006-01-24 | 2006-07-19 | 昆山成利焊锡制造有限公司 | Leadless soft soldering material |
| CN101223002A (en) * | 2005-07-19 | 2008-07-16 | 斯比瑞尔社股份有限公司 | Solder free from lead for additional supply and method of regulating Cu concentration and Ni concentration in solder bath |
-
2010
- 2010-07-21 CN CN201010232451.XA patent/CN102337422B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1482266A (en) * | 2003-07-02 | 2004-03-17 | 中国科学院金属研究所 | Industrial pure tin with resistance to liquid surface oxidizing and application |
| CN101223002A (en) * | 2005-07-19 | 2008-07-16 | 斯比瑞尔社股份有限公司 | Solder free from lead for additional supply and method of regulating Cu concentration and Ni concentration in solder bath |
| CN1803379A (en) * | 2006-01-24 | 2006-07-19 | 昆山成利焊锡制造有限公司 | Leadless soft soldering material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390176A (en) * | 2015-12-15 | 2016-03-09 | 北京有色金属与稀土应用研究所 | Tin-lead plating flat copper wire and preparation method thereof |
| CN107475563A (en) * | 2017-10-24 | 2017-12-15 | 河南科技大学 | One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof |
| CN107475563B (en) * | 2017-10-24 | 2019-04-12 | 河南科技大学 | One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof |
| CN112736366A (en) * | 2020-12-29 | 2021-04-30 | 上海应用技术大学 | Method for cast welding light metal negative grid lead storage battery busbar |
| CN112736366B (en) * | 2020-12-29 | 2023-06-27 | 上海应用技术大学 | Method for cast-welding light metal negative grid lead storage battery busbar |
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| CN102337422B (en) | 2015-12-09 |
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Granted publication date: 20151209 Termination date: 20160721 |