CN100513640C - Metal spraying material without lead - Google Patents
Metal spraying material without lead Download PDFInfo
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- CN100513640C CN100513640C CNB2007100685579A CN200710068557A CN100513640C CN 100513640 C CN100513640 C CN 100513640C CN B2007100685579 A CNB2007100685579 A CN B2007100685579A CN 200710068557 A CN200710068557 A CN 200710068557A CN 100513640 C CN100513640 C CN 100513640C
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Abstract
This invention discloses a leadless sputtering material for end sputtering of metalized thin film capacitor. The leadless sputtering material comprises: Sn 40-79 wt.%, Sb 0.5-2 wt.%, Cu 0.01-0.5 wt.%, Al 1-15 wt.%, impurities less than or equal to 0.1 wt.%, and Zn as balance. Besides, mixed rare earth metals such as La and Ce 0.01-0.2 wt.%, preferential 0.1-0.15 wt.%, can also be added. The leadless sputtering material can be directly used for end sputtering of metalized thin film capacitor without the need for spraying a base layer first, which can largely simplify the spraying operation. The leadless sputtering material has high compatibility with present spraying apparatus and process.
Description
Technical field
The present invention relates to a kind of no-lead gold spraying material, belong to the preparing technical field of metallic film capacitor end face spraying with metallic substance.
Background technology
The metallized film container end face metal spraying material (abbreviation gold spraying material) that has been widely used, typical in five yuan of gold spraying materials of lead base, because of it contains lead about 55%, in the unleaded global tide of electronic devices and components, basically be eliminated at present, there is quite a large amount of producers to use the zinc silk, Zn-Al alloy wire and tin zinc series alloy silk etc. replace five yuan of gold spraying materials of lead base, because tin zinc series alloy has and same good end face sticking power of five yuan of gold spraying materials of lead base and superior welding property, its fusing point is also low than zinc silk and aluminium zinc, therefore, tin zinc series alloy becomes the metal spraying material of electrical condenser manufacturer first-selection, but in order to guarantee good contact of gilding layer and film metal evaporation layer, often to spray the pure zinc bottom of one deck earlier, spray again and contain the red brass surface layer, can reduce cost, can meet the requirement of capacitor performance again, and this has just increased operation, make complex technical processization, Chinese patent ZL02111554.0 provides a kind of no-lead gold spraying material of tin zinc series, the problems referred to above have been efficiently solved, but as no-lead gold spraying material, at fusing point, price, aspects such as performance can't satisfy the requirement of vast electrical condenser manufacturers.
Summary of the invention
The purpose of this invention is to provide the no-lead gold spraying material that an a kind of metal spraying can meet the capacitor performance requirement and have the more approaching leaded gold spraying material of good cost performance, performance.
The present invention is a kind of no-lead gold spraying material, comprises tin, zinc, antimony, copper etc. is characterized in that also comprising simultaneously aluminium, and the composition of each component is respectively by weight percentage: tin (Sn) 40～79%, antimony (Sb) 0.5～2%, copper (Cu) 0.01～0.5%, aluminium (Al) 1～15%, total amount is not more than 0.1% impurity, all the other are zinc (Zn), and the weight percent summation of each component is 100%.
The content of described tin (Sn) preferably can be 45～70%.The content of described antimony (Sb) preferably can be 0.6～1.5%.The content of described copper (Cu) preferably can be 0.03～0.3%.The content of described aluminium (Al) preferably can be 5～11%.
Another technical scheme of the present invention is the norium (Re) that further adds based on lanthanum (La), cerium lightweight rare earth elements such as (Ce), and its add-on is 0.01～0.2% by weight percentage, preferentially can be 0.1～0.15%.
The composition of each component can be respectively by weight percentage in the described impurity: plumbous (Pb)≤0.03%, cadmium (Cd)≤0.002%, iron (Fe)≤0.01%, silicon (Si)≤0.01%, bismuth (Bi)≤0.05%.
Tin is the matrix of alloy ingredient, make alloy keep a lower fusing point level, tin-based alloy keeps one and metal spraying matrix good binding state simultaneously, has weldability good when welding again with electrode, but because the tin high price is expensive, too high levels influences cost, and content is crossed the low fusing point that then can make and raise, and solderability descends.Take all factors into consideration the factor of Cost And Performance, the present invention determines that tin content is 40～79%, and preferred content is 45～70%.
Zinc is the main component of alloy, the adding of zinc, alloy strength is increased substantially, simultaneously the zinc price relatively, the adding of zinc makes alloy have certain price advantage, but zinc is a kind of active element, very easily oxidation, too much zinc can make gilding layer surface easy oxidation discoloration, and weldability descends, thereby makes the processing condition of capacitor fabrication become harsh.
The adding of copper: studies show that an amount of oxidation activity that copper helps to reduce zinc, reduction surface tension, the wettability of raising alloy on copper material of adding in red brass.In addition, in the capacitor lead wire welding process, tin in the gold spraying material and zinc element will react with the copper in the lead-in wire, cause lead-in wire copper melt, in gold spraying material, add a little copper can suppress to go between copper melt, improve the physical strength of solder joint.Simultaneously, between gilding layer and copper lead-in wire, form a good concentration gradient, reduce the potential difference between gilding layer and the lead-in wire, delay the generation of galvanic corrosion, improve the reliability of solder joint.
But copper forms many intermetallic compounds again in red brass, as Cu
6Sn
5, Cu
5Zn
8Deng, influence the alloy processing characteristics, when particularly zinc content was higher, the processing characteristics of red brass itself descended.In addition, the price of copper is than zinc height, and heavy addition can influence the material cost of gold spraying material, therefore, takes all factors into consideration the present invention and determines that copper content is 0.01～0.5%, and preferred content is 0.03～0.3%.
The adding of antimony element: result of study confirms, adds the tensile strength that a small amount of antimony can improve the welding flux alloy solder joint in tin-base lead-free solder, delays the generation of intermetallic compound, and crystal grain thinning improves welding property.Find after deliberation, add a small amount of antimony after, antimony and tin formation compound S bSn (β mutually and β ' phase), this has NaCl (B mutually
1) cube structure of type, it be in the alloy hard mutually and strengthening phase.In the metal spraying process, the particulate of ejection is before arriving capacitor end surface, the SbSn alloy of this hard phase and strengthening phase is frozen into small hard solid prior to other element, break up the metallic film surface zone of oxidation when arriving capacitor end surface, other low melting point part resolidification then, and on the interface, form multiple intermetallic compound, as Cu-Zn (galvanized metal film), Al-Sb (metallic membrane of aluminizing) or the like, can improve the electrical contact performance of gilding layer and metal-plated rete greatly, reduce electrical loss, help reducing condenser loss angle (DF).
Add antimony in addition and form the higher melt compound, when alloyage, at first solidify and separate out, this effect of separating out is to make grain refining; The 2nd, suppress segregation, the result makes alloy structure more even.
But similar with copper, the adding of antimony descends the alloy processing characteristics greatly, improves the gold spraying material cost simultaneously.Therefore, the present invention determines that antimony content is 0.5～2%, and preferred content is 0.6～1.5%.
So the adding of aluminium element is the key element that the present invention can set up, compared with prior art, the adding of aluminium also has following outstanding advantage and effect except antioxidant property improves:
1. make on the film of metallic film capacitor, be that to adopt the way of vacuum evaporation to plate a layer thickness only be following aluminium or aluminium zinc layer of 1 μ m, according to similar bonded principle, add after the aluminium in the gold spraying material, can make sprayed coating strengthen greatly with film on the evaporation layer in conjunction with fastness (also being sticking power), improve electrical contact performance, improve electrical condenser 100kHz high-frequency test qualification rate.
2. the adding that studies show that aluminium obviously reduces alloy liquid phase line temperature, thereby alloy solidus curve and liquidus temperature are more close, through repeatedly measuring, preferred component of the present invention, its solidus temperature is 198.3～202.4 ℃, liquidus temperature is for being no more than 334 ℃, Gu, the temperature difference of liquidus line is obviously dwindled than the tin zinc antimony copper quaternary no-lead gold spraying material that uses at present, with tin content 50% is example, add aluminium after, the no-lead gold spraying material of the comparable prior art of its liquidus line descends more than 40 ℃, the molten state scope that means gilding layer is little, the structure of gilding layer is more reliable, has reduced the possibility of the plastics film of burning, and the electrical condenser yield rate is further improved.
3. aluminium is the good metal of conductivity, improves aluminium content the conductivity of alloy is made moderate progress, and resistivity reduces; Less (the 2.7g/cm of the density of aluminium
3), can obviously reduce the density of quinary alloy, reduce cost; Bauxite resource is abundant than tin and zinc, and price is lower relatively, is very beneficial for reducing cost and Sustainable development.
Though the adding of aluminium brings a series of excellent properties, add very fewly, DeGrain adds too much, can cause short texture in the air-breathing increase of smelt stage, and processing difficulties is 1～15% so the present invention determines aluminium content, and preferred content is 5～11%.
Another technical scheme of the present invention is the norium (Re) that further adds based on lanthanum (La), cerium lightweight rare earth elements such as (Ce), the adding of norium, except bring advantages such as degasification slagging-off, removal of impurities, crystal grain thinning, increase resistance of oxidation to alloy, also have following outstanding advantage and positively effect:
1, rare earth element is a kind of active element, the liquid rare earth that accumulates in the surface down makes the surface energy of alloy significantly reduce, thereby reduce alloy and, improved the seam condition, so the combination of gilding layer and base metal surface is good by the interfacial tension between the metal spraying metal material surface.
Studies show that 2, mishmetal is the same with aluminium, have the effect that reduces liquidus temperature in the present invention, when it used separately, effect was not very obvious, but added fashionablely simultaneously with aluminium, and it reduces playing a role clearly of fusing point.
3, gas content reduces in the alloy because the adding of rare earth element makes, and compact structure makes FeAL simultaneously
3Hard crisp reduce mutually and tissue attenuates, thereby effectively improved conductivity.
Mixed rare-earth elements is a kind of trace alloying element, but the add-on of rare earth element less than 0.01%, this moment, rare earth element mainly was present in the brilliant and eutectic of birth with the solid solution form, the rare earth phase does not appear, thereby effect is not remarkable, has only ree content to increase, and makes REAL
4Have when growing up condition preferably, could form the rare earth phase, play the effect of capturing detrimental impurity, but content of rare earth is excessive, except making the cost rising, also form the viscid rare earth oxide easily and be mingled with and scum silica frost, the fusion-casting process difficulty is strengthened, so it is 0.01～0.2% that the present invention determines the add-on of rare earth element, preferred content is 0.1～0.15%.
The present invention stipulates that lead (Pb) content must not be greater than 0.03%, cadmium (Cd) content must not be greater than 0.002%, this is unleaded requirement, though the existence of the two does not influence processing characteristics and other electric, mechanical integrated performance of alloy, but no-lead gold spraying material is as the substitute of lead base gold spraying material, and the principle of environmental protection must be adhered to.Stipulate also among the present invention that iron (Fe) content must not be greater than 0.01%, this is because iron meeting and zinc form FeZn
7Frangible compounds becomes fragile alloy, and conduction and solidity to corrosion descend, and the mobile variation during molten state so iron is a kind of detrimental impurity composition that must strictly control, must be controlled at below 0.01%, could keep every performance of alloy.Other impurity composition regulation is as follows: silicon (Si)≤0.01%, and bismuth (Bi)≤0.05%, above-mentioned total impurities is not more than 0.1%.
The present invention is directed to the performance requriements of metallic film capacitor end face metal spraying material, compare through optimization design and test of many times, by in no-lead gold spraying material, adding aluminium and mixed rare-earth elements, through practical probation, prove that no-lead gold spraying material of the present invention is used for the spraying of metallic film capacitor end face, once success needn't spray bottom earlier, simplified the metal spraying operating procedure greatly, the present invention simultaneously also has more good consistency with existing metal spraying equipment and technology.
Embodiment
Below the composition of 17 embodiment of the present invention and 4 Comparative Examples each components of existing conventional products tin zinc Venus regulus and the contrast of every performance index are listed as follows, to further specify excellent properties of the present invention.
The present invention is not limited to following embodiment, when practical application, can require and use occasion according to different performance, selects the different proportionings among the following embodiment, or the different proportionings except that following each embodiment, but does not all limit the scope of the invention in any form.
Claims (8)
1, a kind of no-lead gold spraying material comprises tin, zinc, antimony, copper is characterized in that also comprising simultaneously aluminium, and the composition of each component is respectively by weight percentage: tin 40～79%, antimony 0.5～2%, copper 0.01～0.5%, aluminium 2～15%, total amount is not more than 0.1% impurity, all the other are zinc, and the weight percent summation of each component is 100%.
2, by the described a kind of no-lead gold spraying material of claim 1, the content that it is characterized in that described tin is 45～70%.
3, by the described a kind of no-lead gold spraying material of claim 1, the content that it is characterized in that described antimony is 0.6～1.5%.
4, by the described a kind of no-lead gold spraying material of claim 1, the content that it is characterized in that described copper is 0.03～0.3%.
5, by the described a kind of no-lead gold spraying material of claim 1, the content that it is characterized in that described aluminium is 5～11%.
6, by the described a kind of no-lead gold spraying material of claim 1, it is characterized in that also adding the norium based on lanthanum, cerium lightweight rare earth element, its add-on is 0.01～0.2% by weight percentage.
7,, it is characterized in that the add-on based on the norium of lanthanum, cerium lightweight rare earth element is 0.1～0.15% by the described a kind of no-lead gold spraying material of claim 6.
8, by the described a kind of no-lead gold spraying material of claim 1, it is characterized in that the composition of each component in the described impurity is respectively by weight percentage: plumbous≤0.03%, cadmium≤0.002%, iron≤0.01%, silicon≤0.01%, bismuth≤0.05%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100685579A CN100513640C (en) | 2007-05-17 | 2007-05-17 | Metal spraying material without lead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100685579A CN100513640C (en) | 2007-05-17 | 2007-05-17 | Metal spraying material without lead |
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| Publication Number | Publication Date |
|---|---|
| CN101050528A CN101050528A (en) | 2007-10-10 |
| CN100513640C true CN100513640C (en) | 2009-07-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100685579A Expired - Fee Related CN100513640C (en) | 2007-05-17 | 2007-05-17 | Metal spraying material without lead |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014203425A1 (en) * | 2013-06-20 | 2014-12-24 | 三菱電機株式会社 | Zn-based lead-free solder and semiconductor power module |
| CN104625465A (en) * | 2014-12-23 | 2015-05-20 | 苏州龙腾万里化工科技有限公司 | Manufacturing method of low-temperature tin wire |
| JP6119909B1 (en) * | 2016-07-27 | 2017-04-26 | 千住金属工業株式会社 | Thermal spray alloys, thermal spray alloy wires, film capacitors, and solder alloys |
| CN106884108A (en) * | 2017-02-17 | 2017-06-23 | 佛山市三水顺达永丰锡材有限公司 | A kind of novel capacitor no-lead gold spraying material |
| CN110164691A (en) * | 2019-05-06 | 2019-08-23 | 艾华新动力电容(苏州)有限公司 | A kind of high moisture-proof metalizing polypropylene thin film capacitor and its processing method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609246A (en) * | 2004-09-11 | 2005-04-27 | 戴国水 | Zinc-aluminium alloy silk containing rare earth and producing process thereof |
| CN1749423A (en) * | 2005-10-06 | 2006-03-22 | 戴国水 | No-lead gold spraying material |
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- 2007-05-17 CN CNB2007100685579A patent/CN100513640C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1609246A (en) * | 2004-09-11 | 2005-04-27 | 戴国水 | Zinc-aluminium alloy silk containing rare earth and producing process thereof |
| CN1749423A (en) * | 2005-10-06 | 2006-03-22 | 戴国水 | No-lead gold spraying material |
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| CN101050528A (en) | 2007-10-10 |
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Granted publication date: 20090715 Termination date: 20130517 |