CN101197230B - Low-melting point alloy wire and temperature fuse adopting the same - Google Patents
Low-melting point alloy wire and temperature fuse adopting the same Download PDFInfo
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- CN101197230B CN101197230B CN2006101574244A CN200610157424A CN101197230B CN 101197230 B CN101197230 B CN 101197230B CN 2006101574244 A CN2006101574244 A CN 2006101574244A CN 200610157424 A CN200610157424 A CN 200610157424A CN 101197230 B CN101197230 B CN 101197230B
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Abstract
The present invention relates to a low molten point alloy wire and a temperature fuse using the alloy wire, wherein the temperature fuse comprises two electrode sheets (1), an insulation bottom film (21) and an insulation upper film (22), a flux (3) and a low motel point allow wire (4). Two electrode sheets (1) are positioned on the insulation bottom film (21). Two ends of the low motel point alloy wire (4) are respectively connected with two electrode sheets (1). The molten flux (3) is coated on the low motel point alloy wire (4) and is coated with the insulation upper film (22). The mass percentages of the low motel point alloy wire (4) include: 50 percent to 56 percent In, 30 percent to 38 percent Sn, 6 percent to 15 percent Bi and a small quantity of Ag, Cu, and Zn. The flux (3) is constituted by rosin, stearine acid, liquid alcohol and small molecule acid. The temperature fuse of the present invention can work for longer time on 8A current, thereby improving the blow-out temperature accuracy of the temperature fuse at the same time.
Description
Technical field
The invention belongs to the circuit protection technical field, in particular for the laminar Thermal Cutoffs of the alloy-type of cells in notebook computer.
Technical background
Various electronics and electric equipment products in use regular meeting because overcurrent, overheated etc. former thereby cause damage of circuit, thereby influence the normal use of product.Electronic products such as existing mobile phone, digital camera use lithium ion battery more, in order to guarantee the safe in utilization of lithium battery, mostly are provided with Thermal Cutoffs on the lithium battery.When above-mentioned situation takes place, thus Thermal Cutoffs fusing protective circuit and product.The general insurance silk is the low-melting alloy silk that is enclosed with flux.
If when the electric device abnormal heating of this fuse was housed, the heat that is discharged can make the fusion of low-melting alloy silk.When a certain amount of alloy silk changes liquid phase into, because the liquid metal that exists of flux is shunk to two ends, finally be separated into two spherical drop under capillary effect, realize that circuit turn-offs action.The thin temperature fuse of in invention CN2433729Y, reporting that is used for cellular li-ion battery, adopt fusible metal to connect two electrode slices, and sealed by the folded confined space that forms of two coverlays, owing to only rely on metal-coverlay interfacial surface tension as separation force, its fusing-off temperature wider distribution, can reach 100 ± 10 ℃, precision is relatively poor.Reported a kind of Thermal Cutoffs among the CN1442868A, wherein the alloy silk composition of fuse comprises In 37-43%, Sn 10-18%, all the other are for Bi 32.99-45.5%, and metallic addition Ag, Cu, the Ni of 0.01-3.5%.But above-mentioned fuse Bi content is greater than 30%, and resistivity is relatively still bigger, and alloy silk processing characteristics is undesirable.
Over the past two years, because the notebook computer explosion accident constantly takes place, with the safety in utilization of lithium ion battery higher requirement had been arranged for notebook.And Notebook Battery requires higher rated current, owing to generating heat from body that the very difficult effective Control current of the higher existing fuse of resistance causes, causes the fusing-off temperature error to become big, fail safe decline under this electric current.
In addition, alloy is in the temperature uphill process, because existing liquid phase generates in the solid-liquid coexistence, so in theory below liquid phase limit temperature (being made as T), melting process remains unfulfilled, and when alloy has abundant flowability and surface tension when enough big, fuse has possessed the fusing condition.If the liquid phase limit is Δ T (temperature range that promptly belongs to the solid-liquid coexistence) with the temperature range that satisfies the fusing condition down to liquid phase limit place, for satisfying fuse working temperature precision, require Δ T as far as possible little, it is as far as possible little promptly to make the required metal solid-liquid coexistence of low-melting alloy silk.Simultaneously, between tour, any phase change--comprises solid transformation, crystal transfer etc.--all might influence the relevant physical property of alloy at alloy solid-liquid.When selecting the low-temperature alloy of preparation low-melting alloy silk, should evade this type of transformation as far as possible.not only satisfy Δ T as far as possible little but also avoid the phase change of alloy in, often the resistivity of existing alloy silk is higher.P=I
2R, i.e. fuse spontaneous heating power equals the product of current squaring and resistance, but the resistance of alloy silk reduces geometric ratio reduction heating power in theory, effectively suppresses spontaneous heating.
Summary of the invention
The object of the present invention is to provide a kind of at low-melting alloy silk and the Thermal Cutoffs that adopts this low-melting alloy silk, adopt In-Sn-Bi system in the alloying component of this low-melting alloy silk, fusing-off temperature is in 95 ± 2 ℃ of scopes, rated current 8A, can suppress spontaneous heating preferably, and further reduce resistance, improve the alloy-type temperature fuse of fusing-off temperature precision.
A kind of quality percentage composition of low-melting alloy silk comprises: In 50-56%, Sn 30-38%, Bi 6-15%.
Adopt the Thermal Cutoffs of this low-melting alloy silk, Thermal Cutoffs comprises two electrode slices (1), insulating counterdie (21) and insulation upward film (22), flux (3) and low-melting alloy silk (4), wherein two electrode slices (1) are positioned on the insulating counterdie (21), low-melting alloy silk (4) two ends are connected with two electrode slices (1) respectively, be covered with flux (3) on the low-melting alloy silk (4), be covered with insulation on the flux (3) and go up film (22), the quality percentage composition of this low-melting alloy silk (4) comprising: In 50-56%, Sn 30-38%, Bi 6-15%; Be preferably: In 50-52%, Sn 33-35%, Bi 12-15%.Adopt the low-melting alloy silk (4) of above-mentioned prescription of the present invention can reduce the resistance of alloy silk further, effectively suppress the fuse spontaneous heating, improve the fusing precision.
Thermal Cutoffs of the present invention is the Thermal Cutoffs that uses on the notebook computer, and therefore, the fusing-off temperature of Thermal Cutoffs of the present invention is 92 ℃-97 ℃.Working temperature is meant the temperature when fuse is worked under the normally state in circuit, the working temperature of Thermal Cutoffs of the present invention is 57 ℃-63 ℃, and operating current is 8A.
Wherein, low-melting alloy silk (4) also comprises one or several the combination among additive metal Ag, Cu, the Zn, and the quality percentage composition of additive metal accounts for the 2%-4% of alloy silk total amount.
Utilize Ag, Cu, Zn to suppress alloy solid transformation at low temperatures, reduced the bad reaction under thermal cycle.The melting range of low-melting alloy silk (4) is 60～100 ℃.
In above-mentioned, allowing to contain unavoidable impurities in the manufacturing of each raw material briquet and in the fusion of these raw materials stirring.
Wherein, flux (3) is mixed as following weight percent by rosin, stearic acid, liquid alcohols and micromolecule acid: rosin 50～70, stearic acid 5～20, liquid alcohols 10～40, micromolecule acid 0.5～16.Liquid alcohols is one or several the mixing in ethanol, n-butanol, the isobutanol.Micromolecule acid is the acid of 40-100 for molecular weight, as one or several the mixing in formic acid, glacial acetic acid, the phenylacetic acid.Rosin is one or several the mixing in Foral, disproportionation rosin, newtrex, the common rosin, and the weight percentage of rosin accounts for 50～70% of flux total amount.
Flux (3) mixes under the fusion situation, the insulation dehydration.By holding temperature and temperature retention time control n-butanol volatilization degree, by stearic acid and acetate trim end product, and then control its surface tension, to realize the fusing controlled function of its involutory spun gold.
In the alloy-type fuse of the present invention, coating film uses biaxial tension PETG (PET) up and down, and electrode slice is that the punching press of half-hard state nickel strap is made.
Prepare insulating counterdie (21) and insulate upward film (22) by ambroin.
The cylindrical first alloy silk is carried out mold pressing form low-melting alloy silk (4) in mould, wherein, it is 1.0～1.3mm that the present invention adopts cylindrical first diameter of alloy wire, and the sectional area of the low-melting alloy silk (4) that is molded into is 0.79mm
2-1.33mm
2Existing cylindrical first diameter of alloy wire that is used to prepare the Thermal Cutoffs of lithium ion battery is 0.3～0.5mm, and the sectional area of the low-melting alloy silk that is molded into is 0.071mm
2-0.196mm
2Cylindrical first diameter of alloy wire of employing of the present invention is about the twice of the cylindrical first alloy filament diameter of the existing Thermal Cutoffs that is used to prepare lithium ion battery.The sectional area of the low-melting alloy silk (4) that mold pressing obtains is about 4 times of existing low-melting alloy silk sectional area.
According to the resistance calculations formula, for the cylindrical resistance of ideal
When the fuse diameter d increased 2 times, its resistance R can be reduced to original 1/4.In actual applications, sectional area increases can obviously reduce resistance, but effect is lower than theoretical cylindrical boundary calculated value.
Therefore the present invention adopts low-melting alloy silk sectional area to be about four times of existing low-melting alloy silk sectional area, thereby reduction resistance, simultaneously, the present invention selects low resistance alloy silk prescription for use, and the low-melting alloy silk (4) that adopts shape as shown in Figure 3 is with further reduction fuse resistance, thereby effectively control makes it still can effectively work under the high current work environment of notebook computer from the body heating.
In addition, draft capillary flux (3) fusing-off temperature is delayed to more than the liquidus curve near 1 ℃, change mutually in the solid-liquid coexistence and, further improve the fusing-off temperature precision by the fusing-off temperature uncertainty that Δ T scope causes to eliminate by selecting for use.
Description of drawings
Fig. 1 is the alloy-type temperature fuse outside drawing
Fig. 2 is the electrode slice outline drawing
Fig. 3 is a low-melting alloy silk outline drawing
Fig. 4 is alloy-type temperature fuse STRUCTURE DECOMPOSITION figure
Film, 3-flux, 4-low-melting alloy silk in 1-electrode slice, 21-insulating counterdie, the 22-insulation
Embodiment
A kind of Thermal Cutoffs of the present invention, comprise two electrode slices (1), insulating counterdie (21) and insulation upward film (22), flux (3) and low-melting alloy silk (4), wherein two electrode slices (1) are positioned on the insulating counterdie (21), low-melting alloy silk (4) two ends are connected with two electrode slices (1) respectively, be covered with flux (3) on the low-melting alloy silk (4), be covered with insulation on the flux (3) and go up film (22), as Fig. 1.Two electrode slices (1) are arranged in a linear, the middle determining deviation that keeps; Low-melting alloy silk (4) is connected in the relative end place of two electrode slices; Low-melting alloy silk (4) is all wrapped up by flux (3); Outermost layer is combined closely into closed state by film (22) in the insulation that plays the insulation protection effect with insulating counterdie (21), as Fig. 1.The end place of two electrode slices adopts local tin plating to improve welding performance, and the grid regions among Fig. 2 is zinc-plated part.The low-melting alloy silk of fuse is connected with electrode slice.
On concrete, the cooperation by In-Sn-Bi realizes this purpose, and the content that has reduced Bi as far as possible is to reduce resistance alloys and to improve processing characteristics; In content surpasses 50%, has improved the processing characteristics of alloy on the one hand, and trace alloying element that cooperation is simultaneously added improves the heat-resistant stability of alloy.
The applied amount of flux (3) should guarantee to fill the space except that low-melting alloy silk (4) between coating film up and down, to suppress the appearance of bubble.
Film in the insulation (22) links to each other with insulating counterdie (21) with hot pressing, hyperacoustic mode, constitute a complete insulation confined space low-melting alloy silk (4) and flux (3) are isolated from the outside, film (22) is gone up in this insulation should have good heat-conductive characteristic to reduce the film internal-external temperature difference.
Be described further below in conjunction with specific embodiment:
Sectional area through the low-melting alloy silk (4) after the mold pressing of the present invention is 1.13mm
2, raw-material diameter is 1.2mm, main component is In 52%, Sn 31%, Bi 13%, Ag 1%, Cu 1%, Zn 2%.
Flux of the present invention makes by following technology: take by weighing the 6g stearic acid and join in the 10g n-butanol, the insulating box of putting into 120 ℃ dissolves up to it, add 20g Foral, 10g disproportionation rosin then, mix, putting into heating furnace is heated to till the boiling, take out the back and add the 1g glacial acetic acid till its cool to room temperature, with above-mentioned flux with point gum machine point on coverlay, the ultrasonic bonding moulding.
Embodiment 2
Sectional area through the low-melting alloy silk (4) after the mold pressing of the present invention is 1.33mm
2, raw-material diameter is 1.3mm, main component is In 54%, Sn 35%, Bi 8%, Ag 1%, Cu 2%.Means of testing is with embodiment 1.
Taking by weighing the 6.5g stearic acid joins in the 10g n-butanol, the insulating box of putting into 120 ℃ dissolves up to it, add 15g disproportionation rosin, 15g newtrex then, mix, putting into heating furnace is heated to till the boiling, take out the back and add the 1g glacial acetic acid till its cool to room temperature, other preparation technologies are with embodiment 1.
The sectional area through the low-melting alloy silk (4) after the mold pressing of invention is 1.33mm
2, raw-material diameter is 1.3mm, main component is In 50%, Sn 33%, Bi 15%, Cu 1%, Zn1%.Means of testing is with embodiment 1.
Take by weighing the 6g stearic acid and join in the 10g n-butanol, the insulating box of putting into 120 ℃ dissolves up to it, adds the 25g common rosin then, mix, put into heating furnace and be heated to till the boiling, take out the back and add 1g hydrochloric acid till its cool to room temperature, other preparation technologies are with embodiment 1.
Comparative Examples 1
This Comparative Examples is used for illustrating that the present invention's Thermal Cutoffs is the acting in conjunction of flux and alloy silk, with respect to the performance of the alloy silk among the CN1442868A.Raw-material diameter 0.3mm among the prior art CN1442868A, main component In 40%, Sn 14%, Bi 46%; The sectional area 0.07mm of this alloy silk
2, fusing-off temperature is 72 ± 4 ℃.
Being prepared as of flux: common rosin 3.5g, methyl-silicone oil 2g, aerosil 0.06g, solvent are right amount alcohol, heating for dissolving, stirring, cooling.
Comparative Examples 2
This Comparative Examples is used for illustrating the performance of the present invention's flux.
The alloy silk is alloy silk of the present invention with embodiment 1.
The content of flux is: common rosin 3.5g, and vaseline 2g, diethylamine hydrochloride 0.06g, solvent are right amount alcohol, heating for dissolving, stirring, cooling.
Comparative Examples 3
This Comparative Examples is used for illustrating the progress of the present invention's alloy silk with respect to the CN1442868A prior art.
The low-melting alloy silk is the alloy silk among the CN1442868A with Comparative Examples 1.The content of flux is flux of the present invention with embodiment 1.
Comparative Examples 4
This Comparative Examples is used to illustrate the performance of the alloy silk of CN1442868A with respect to the anti-big electric current of Thermal Cutoffs of the present invention.
Preparation Comparative Examples Thermal Cutoffs, wherein, alloy silk size is with the size of the alloy silk of embodiment 1, and the sectional area of the alloy silk after the process mold pressing is 1.13mm
2, raw-material diameter is 1.2mm; The main component of alloy silk is with the main component of the alloy silk among the CN1442868A: In40%, Sn 14%, Bi 46%; The content of flux is with the flux of Comparative Examples 1.
Test condition is as follows:
Adopt the liquid phase limit temperature of DSC (differential scanning calorimetry) test low-melting alloy silk.Temperature when solid changes liquid into fully is a metering temperature, and this temperature is exactly a liquid phase limit temperature.The alloy silk could fuse after changing liquid phase fully in theory, and liquid phase limit temperature is exactly the theoretical fusing-off temperature of fuse.Fusing-off temperature adopts water-bath or oil bath, product is sandwiched in the universal instrument ohms range, places heating fluid (water or silicone oil), with the speed heating of 0.5-1 ℃/min, until blown fuse, body lotion (water or the silicone oil) temperature of noting this moment is the Thermal Cutoffs fusing-off temperature.
It is w that the Thermal Cutoffs fusing-off temperature deducts alloy silk liquid phase limit temperature.General Thermal Cutoffs has fused less than alloy silk liquid phase limit temperature the time.So w of the prior art is a negative value ,-3～-5 ℃.
The Wheatstone bridge method is adopted in the internal resistance test.
Test result specifically is shown in Table 1:
Table 1
| |
Embodiment 2 | |
Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Thermal Cutoffs fusing-off temperature precision (℃) | ±1.5 | ±2 | ±2 | ±4 | ±5 | ±2 |
| Alloy silk liquid phase limit temperature (℃) | 94 | 94 | 93 | 75 | 96 | 68 |
| The Thermal Cutoffs fusing-off temperature (℃) | 95 | 95 | 94 | 70 | 93 | 70 |
| W(℃) | 1 | 1 | 1 | -5 | -3 | 2 |
| Thermal Cutoffs fusing time (s) | 3s | 2s | 2s | 4s | 3s | 4s |
| The internal resistance of Thermal Cutoffs (m Ω) | 3 | 2 | 2 | 5 | 3 | 5 |
The fusing-off temperature scope of the Thermal Cutoffs of embodiment is little than the value of Comparative Examples as can be seen from Table 1, the precision that Thermal Cutoffs fusing-off temperature of the present invention is described is higher, the Thermal Cutoffs fusing time will be lacked than Comparative Examples, has shortened the Thermal Cutoffs fusing time.Learn that from the Comparative Examples 2 and the data of Comparative Examples 1, Comparative Examples 3 flux of the present invention improves Thermal Cutoffs fusing-off temperature precision.From the W value of Comparative Examples 3 and Comparative Examples 1, Comparative Examples 2 more as can be known, flux of the present invention make the w value by negative value become on the occasion of, help improving the fusing-off temperature precision.Learn that from the data of embodiment and Comparative Examples 1, Comparative Examples 3 alloy silk of the present invention helps reducing the internal resistance of Thermal Cutoffs, improved alloy silk liquid phase limit temperature simultaneously.Learn from the data of embodiment and Comparative Examples that the internal resistance of alloy silk reduces further, reduced the spontaneous heating of fuse when work, will drop to minimumly, help its steady operation under big electric current environment the harmful effect of fusing precision.
Under the big current condition of 8A,, can obtain table 2 with the big current work performance of Thermal Cutoffs in the loop of test implementation example 1 with Comparative Examples 4:
Table 2
| |
Comparative Examples 4 | |
| Electric current (A) | 8 | 8 |
| Internal resistance (m Ω) | 3 | 5 |
| Thermal Cutoffs surface temperature after 30 seconds (℃) | 38 | 54 |
| Retention time (hour) | Not 48 (not disconnected) | 8 (fusing) |
As can be seen from Table 2, under the big current condition of 8A, Thermal Cutoffs of the present invention over time, the temperature and the room temperature on Thermal Cutoffs surface are more or less the same, the variations in temperature that explanation is caused by the spontaneous heating of Thermal Cutoffs own is fully in controlled range, and the internal resistance of the internal resistance Thermal Cutoffs of the present invention relatively of the Thermal Cutoffs in the Comparative Examples 4 itself is bigger, and the variations in temperature that causes self-heating to cause is bigger with respect to embodiment 1.Comparative Examples 4 fuses and Thermal Cutoffs of the present invention can tolerate the big current work of long period soon under 8A.
In sum, Thermal Cutoffs fusing time of the present invention has shortened, the fusing-off temperature of Thermal Cutoffs is more accurate, the internal resistance of alloy silk reduces further, reduced the spontaneous heating of fuse when work, to drop to minimumly to the harmful effect of fusing precision, help its steady operation for a long time under the big electric current environment of 8A.
Claims (10)
1. alloy silk, its quality percentage composition comprises: In 50-56%, Sn 30-38% and Bi6-15%; Also comprise additive metal Ag, Cu and Zn, the quality percentage composition of additive metal accounts for the 2%-4% of alloy silk total amount.
2. Thermal Cutoffs, comprise two electrode slices (1), insulating counterdie (21) and insulation upward film (22), flux (3) and alloy silk (4), wherein two electrode slices (1) are positioned on the insulating counterdie (21), alloy silk (4) two ends are connected with two electrode slices (1) respectively, be covered with flux (3) on the alloy silk (4), be covered with insulation on the flux (3) and go up film (22), it is characterized in that: the quality percentage composition of this alloy silk (4) comprising: In 50-56%, Sn 30-38% and Bi 6-15%; Also comprise additive metal Ag, Cu and Zn, the quality percentage composition of additive metal accounts for the 2%-4% of alloy silk total amount.
3. Thermal Cutoffs according to claim 2 is characterized in that: the sectional area of described alloy silk (4) is 0.79mm
2-1.33mm
2
4. according to claim 2 or 3 described Thermal Cutoffs, it is characterized in that: the fusing-off temperature of described Thermal Cutoffs is 92 ℃-97 ℃.
5. according to claim 2 or 3 described Thermal Cutoffs, it is characterized in that: the working temperature of described Thermal Cutoffs is 57 ℃-63 ℃, and operating current is 8A.
6. a kind of Thermal Cutoffs according to claim 2 is characterized in that: described flux (3) is that the micromolecule acid of 40-100 mixes as following weight percent by rosin, stearic acid, liquid alcohols and molecular weight:
7. Thermal Cutoffs according to claim 6, wherein, described liquid alcohols is one or several the mixing in ethanol, n-butanol, the isobutanol.
8. according to any described Thermal Cutoffs among the claim 6-7, wherein, described rosin is one or several the mixing in Foral, disproportionation rosin, newtrex, the common rosin.
9. according to claim 2 or 3 described Thermal Cutoffs, it is characterized in that: the melting range of alloy silk (4) is 60～100 ℃.
10. according to claim 2 or 3 described Thermal Cutoffs, it is characterized in that: prepare insulating counterdie (21) and insulate by ambroin and go up film (22).
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| CN2006101574244A CN101197230B (en) | 2006-12-05 | 2006-12-05 | Low-melting point alloy wire and temperature fuse adopting the same |
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| CN2006101574244A CN101197230B (en) | 2006-12-05 | 2006-12-05 | Low-melting point alloy wire and temperature fuse adopting the same |
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| CN101197230B true CN101197230B (en) | 2011-11-16 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8531263B2 (en) * | 2009-11-24 | 2013-09-10 | Littelfuse, Inc. | Circuit protection device |
| CN102117720A (en) * | 2009-12-31 | 2011-07-06 | 比亚迪股份有限公司 | Temperature protection device |
| CN101763983B (en) * | 2009-12-31 | 2014-06-25 | 上海长园维安电子线路保护有限公司 | Thin temperature fuse of profile protective structure and preparing method thereof |
| CN103203568A (en) * | 2013-03-03 | 2013-07-17 | 石盛华 | Rapidly shrinking fusing auxiliary |
| CN103146976A (en) * | 2013-03-22 | 2013-06-12 | 天津百瑞杰焊接材料有限公司 | Lead-free low-temperature alloy having melting point of 100+/-2 DEG C and preparation method for same |
| US20140368309A1 (en) * | 2013-06-18 | 2014-12-18 | Littelfuse, Inc. | Circuit protection device |
| CN106119667B (en) * | 2016-06-29 | 2018-05-25 | 北京态金科技有限公司 | The low-melting-point metal that fusing point is 60 DEG C is bonded cream and its preparation method and application |
| JP6957246B2 (en) * | 2016-11-29 | 2021-11-02 | デクセリアルズ株式会社 | Protective element |
| CN106756381B (en) * | 2016-12-05 | 2018-08-31 | 佛山新瑞科创金属材料有限公司 | A kind of liquid metal that there is anti-molten characteristic to be used for 80-90 DEG C of heat dissipation |
| CN106756382B (en) * | 2016-12-05 | 2018-08-31 | 佛山新瑞科创金属材料有限公司 | A kind of liquid metal that there is anti-molten characteristic to be used for 54-61 DEG C of heat dissipation |
| CN107087316A (en) * | 2017-04-28 | 2017-08-22 | 宁波柔碳电子科技有限公司 | A kind of method for excessive heating protection of graphene Electric radiant Heating Film and graphene Electric radiant Heating Film with overtemperature protection system |
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| CN1455428A (en) * | 2002-05-02 | 2003-11-12 | 内桥艾斯泰克股份有限公司 | Alloy type temp.-fuse and fuse wire element |
| GB2419137A (en) * | 2004-10-15 | 2006-04-19 | Alpha Fry Ltd | Solder alloy |
| CN1709638A (en) * | 2005-08-12 | 2005-12-21 | 北京工业大学 | Rosin halogen-free scaling powder for lead-free soldering paste |
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