CN106835214A - A kind of electro-deposition method of Sn Bi systems lead-free low-temperature solder - Google Patents
A kind of electro-deposition method of Sn Bi systems lead-free low-temperature solder Download PDFInfo
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- CN106835214A CN106835214A CN201611226143.XA CN201611226143A CN106835214A CN 106835214 A CN106835214 A CN 106835214A CN 201611226143 A CN201611226143 A CN 201611226143A CN 106835214 A CN106835214 A CN 106835214A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C12/00—Alloys based on antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
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- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The present invention relates to a kind of electro-deposition method of Sn Bi systems lead-free low-temperature solder, comprising preparation electroplate liquid, it is matrix used to electro-deposition to process, carry out the step of electro-deposition three, the present invention is on the basis of sulfate is for the alloy electroplating bath of medium, using sodium citrate as complexing agent, Sn Bi systems lead-free low-temperature solder is prepared for using the method for electro-deposition, the present invention can increase cathodic polarization, the deposition potential of ion is set to become negative, the insulation barrier of addition middle with hole can change the electric force lines distribution of negative electrode, reduce edge effect to a certain extent, the uniformity that the coating of deposition is distributed on substrate has obtained larger improvement.Additionally, by adjusting dutycycle and pulse frequency, the trend that increase crystal grain is grown up so that the particle of Sn Bi systems solder is thicker.
Description
Technical field
The present invention relates to electrochemical field, it is related to a kind of electro-deposition method of Sn-Bi systems lead-free low-temperature solder.
Background technology
Traditional Sn-Pb solders, are widely used in Electronic Packaging the features such as due to its excellent performance and cheap cost
Industry.But lead is toxic metals, its harmfulness has received the extensive concern in the whole world, as the development and environmental protection of society are anticipated
The enhancing of knowledge, people increasingly pay attention to controlling the pollution of lead, and the research and development of lead-free brazing have turned into electron trade and have been badly in need of asking for solution
Topic.Because Sn-Bi systems lead-free low-temperature solder has the advantages that the electronics that low melting point, excellent wettability energy make it in heat resistance difference
Component package field has larger application prospect, so, in the urgent need to a kind of generation side of Sn-Bi systems lead-free low-temperature solder
Method.
The content of the invention
In view of this, the present invention provides a kind of Sn-Bi systems lead-free low-temperature solder for solving or partly solving the above problems
Electro-deposition method.
To reach the effect of above-mentioned technical proposal, the technical scheme is that：A kind of Sn-Bi systems lead-free low-temperature solder
Electro-deposition method, comprises the steps of：
1) electroplate liquid is prepared；
The process for preparation of electroplate liquid is as follows：
1st, after the distilled water for adding 60% or so volume in coating bath, 8 to 25g sodium citrate is added, is stirred with magnetic force
Mix device to stir 5 to 10 minutes, it is dissolved in distilled water, add the bismuth sulfate of 0.8g to 4.5g, it is heated, promote
Sodium citrate and bismuth sulfate is set fully to dissolve；
2nd, a small amount of distilled water is first added in a beaker and to its appropriate heating after, add 3.88g to 11.24g's
Sulfuric acid, is stirred 1 minute at full tilt with glass bar, after it is fully cooled to 25 DEG C, adds the stannous sulfate of 0.4g to 9g
And the ascorbic acid of 0.2g, it is stirred with magnetic stirring apparatus, it is fully dissolved；
3rd, two kinds of solution for generating 1,2 steps mix, and are diluted with water to liquor capacity for 350ml；
4th, 0.4g phenolsulfonic acid, the ethoxylated α naphthol sulfonic acid of 0.6g is dissolved in an other beaker respectively
In, add the 3rd step generation solution in；
5th, supplement distilled water reaches 800ml, after adjustment pH value, then is filtered, and stirs and analysis and regulation PH is to 7, carries out
Energization is processed, and is used again after examination plating is qualified；
The process for preparation of electroplate liquid is all controlled between 25 DEG C to 50 DEG C；
2) matrix used to electro-deposition to process, matrix includes a piece of platinized platinum and a piece of copper sheet, and it is removed
Rust treatment, and ensure the smooth of surface and dry；
3) carry out electro-deposition, after the completion of cold water treatment is carried out to it, while carry out alcoholic solution dehydration with dry, obtain
To the Sn-Bi series lead-free solders for meeting requirement；
The process of electro-deposition is as follows：
1st, electroplate liquid in coating bath is stirred, and adds the matrix that 2) step is handled well, i.e., a piece of platinized platinum and a piece of
Copper sheet adds an insulation barrier for middle with hole, in the middle of insulation barrier respectively as positive level and negative electrode between positive level and negative electrode
20 holes are uniformly distributed, and electroplate liquid is electrically heated, the temperature of heating is 28 DEG C, using pulse current, pulse current
Dutycycle is that 60%, pulse frequency is 600HZ, and the metal ion of electroplate liquid reaches cloudy by forms such as electromigration, convection current, diffusions
Pole near surface；
2nd, the metal ion of electroplate liquid before reduction near negative electrode or surface occur chemical conversion, the water of hydrated ion
Change number decline, the part of complex ion to convert；
3rd, the metal ion of electroplate liquid obtains electronics and is reduced into metallic atom from cathode surface, is attached to cathode surface
On；
4th, metallic atom is diffused into up to growing point along cathode surface and enters lattice growth, meets to form crystalline substance with other particles
Core, final great achievement crystal long, after crystal cooling, it is content distribution by mass percentage to obtain Sn-Bi series lead-free solders, comprising
50% to 58% Bi, 0.01% to 3.0% Ag, 0.01% to 3.0% Sb, 0.01% to 2.0% ln, 0.005%
Co, 0.001% to 0.002% Cu to 0.1%, 0.002% to 0.004% Zn, and balance of Sn, fusing point is 138
DEG C to 149 DEG C.
Useful achievement of the invention is：The present invention is made on the basis of sulfate is for the alloy electroplating bath of medium with sodium citrate
It is complexing agent, Sn-Bi systems lead-free low-temperature solder is prepared for using the method for electro-deposition, the present invention can increases cathodic polarization, make
The deposition potential of ion becomes negative, and the insulation barrier of addition middle with hole can change the electric force lines distribution of negative electrode, to a certain degree
Upper reduction edge effect, the uniformity that the coating of deposition is distributed on substrate has obtained larger improvement.Additionally, being accounted for by adjustment
Sky ratio and pulse frequency, the trend that increase crystal grain is grown up so that solder particle is thicker.
Specific embodiment
In order that the technical problems to be solved by the invention, technical scheme and beneficial effect become more apparent, below tie
Embodiment is closed, the present invention will be described in detail.It should be noted that specific embodiment described herein is only used to explain
The present invention, is not intended to limit the present invention, and can realize that the product of said function belongs to equivalent and improvement, is all contained in this hair
Within bright protection domain.Specific method is as follows：
Embodiment 1：Following material is used in electroplate liquid, specific composition and function are as follows：
Main salt in stannous sulfate solution, there is provided Sn2+.
Main salt in bismuth sulfate solution, there is provided Bi3+.
Sulfuric acid regulation solution pH value, increases electric conductivity.
Sodium citrate is complexed with Sn2+, Bi3+, adjusts deposition potential.
Ascorbic acid prevents Sn2+ from aoxidizing, maintains bath stability.
Plating production is the important step of plating cleaner production, by the control to plating production, can reduce resource and disappear
Consumption, reduction pollution, increase benefit.
Among these, it is necessary to extend the service life of electroplating solution, the specific method for using is as follows：
(1) amount of bringing into of impurity is reduced.Will using deionized water prepare electroplating solution, into coating bath before want cleaning workpiece,
Reduce the impurity in electroplating solution；And take certain measure to reduce industrial chemicals, anode, frock hanger etc. and bring impurity into
Amount.
(2) impurity in electroplating solution is removed.Mainly take filtration method, electrochemical process and other method.Filtration method is divided into
Continuous filtration method and periodic filtering method.The former is mainly mechanical admixture, organic impurities in removing electroplating solution, moreover it is possible to play stirring
Effect.The method that the latter is mainly precipitation and separation and its adsorbate after periodically treatment electroplating solution.This method may cause solution
Loss, will as far as possible reduce the access times of this method.The metal that electrochemical process for treating is typically used to remove in electroplating solution is miscellaneous
Matter.Other processing methods ooze method and membrane separation process because of its production cost and film then comprising ion-exchange, freezing using more
Quality problems, using not extensive.
(3) maintenance and adjustment of electroplating solution.This maintenance can adjust the purpose that can realize extending bath life, and this is to reduce
Consume, economize on resources, reducing the effective measures of pollution.The adjustment of electroplating solution in time, stably, reliably must make electroplating solution
Composition stabilization in rational scope, to ensure quality of coating.
In the process for preparation of electroplate liquid, it is desirable to reduce the drag-out of electroplating solution.The viscosity of electroplating solution and use temperature
Degree, the shape and surface state of workpiece and hanger and go out residence time of groove and have large effect to the drag-out of electroplating solution,
Controlling these factors can be greatly decreased the drag-out of electroplating solution in plating production process.
(1) selection of the concentration of electroplating solution and temperature in use.The control of electroplating solution concentration can in the lower limit of process conditions
To reduce the drag-out of electroplating solution；The temperature in use of electroplating solution is improved, the viscosity of electroplating solution can be reduced, can also reduced
Take out of；By the surface tension for adding surfactant to reduce electroplating solution, the drag-out of electroplating solution can be also reduced.
(2) design of hanger and selection.Hanger is divided into Special hanger and universal hanger.To determine by actual production demand
Usage type, accomplishes both to meet production needs, can also realize energy-conservation, subtract dirt.Meanwhile, the surface of hanger is as smooth as possible, nothing
The defects such as burr, tangerine peel.
(3) control of groove residence time is gone out.The skyborne residence time can effectively be reduced after proper extension workpiece goes out groove
The drag-out of electroplating solution.
, it is necessary to the workpiece that will wherein use is cleaned after preparation., cleaning water high using cleaning efficiency is few and can
Recycle the cleaning method of workpiece drag-out.The design of electroplating technology should use low concentration electroplating solution, and take effectively
Measure reduces the drag-out of electroplating solution.The electroplating solution drag-out of workpiece unit area will be determined by testing.Accumulator tank or
The rinse water of first order rinse bath will be using the water quality or deionized water for meeting electroplating technology requirement.Recovered liquid reaches back in groove
Coating bath reuse should be filled into during with desired concentration, when recovered liquid produces influence to electroplating solution quality, be using filtering, ion
Reuse again after the method purification such as exchange or diaphragm electrochemical treatment.Finally, metal ion main in rinse bath waste water allows dense
Degree will be determined by electroplating technology technical requirements etc..Data below is used in cleaning：Intermediate deposit cleaning is 5-10mg/L, finally
Coating cleaning is 20-50mg/L.
When electroplating solution evaporation capacity is with water for cleaning amount phase equilibrium in electroplating bath, natural enclosing circulation technology stream is used
Journey；When evaporation capacity is not more than cleaning water consumption, be using pressure closed circulation process flow.
When electroplating technology uses transfer matic production, workpiece cleaning will wash ablution using regurgitating；Using manual operations
When should use intermittence backwash cleaning method or recovery and rinsing method.The cleaning of workpiece pretreatment will be using series connection cleaning process flow, its
Pickling water reusable is in alkali cleaning rinse water.When plating is produced as transfer matic, rinse bath series should use 3-5 grades, by hand
Can be more than 3 grades during operation.The various cleaning methods of workpiece will be by Combination of Methods such as concrete condition and ion exchange, electrochemical treatments
Use.
, it is necessary to metal recovery to using at this after electro-deposition.This reduces resource loss and curbs environmental pollution
Effective measures.Now, ion-exchange, electrochemical process, chemical Treatment sewage and recovery metal process are effectively combined, in treatment
The purpose of metal can be realized reclaiming while the electroplating wastewater of the heavy metals such as stanniferous, lead, copper, zinc, nickel, chromium.
The generation of new macroporous ion exchange resin and ion-exchange fibre, ion-exchange is reclaiming metal, is improving
The technical requirements such as the reclamation rate of water aspect is much better than other method.Generally cleaned from nickel plating using ion-exchange and membrane separation process
Nickel is reclaimed in water.Ion-exchange low cost, the nickel value of recovery can compensate for the investment of reclaimer soon.
The recovery of silver is reclaimed using chemical recovering method and electrochemical cathode treatment.And the process of chemical recovering method silver is complicated also
New pollution is necessarily brought, so, multiplex electrochemical treatment reclaims silver at present.Negative electrode in the electrochemical treatments recovery system of silver
Area is bigger than anode, can be easily peeled off the silver for being deposited on negative electrode using stainless steel making and come, and its purity can be up to 99.99%.
The recovery of gold will be reclaimed using electrochemical cathode treatment, ion-exchange is reclaimed, and also be adapted for using chemical recovering method.At electrochemistry
Reason is reclaimed to be reclaimed with ion exchange and is used in combination, and can ensure that the recovery for cleaning underwater gold is more thorough, to prevent the stream of noble metal
Lose.
Embodiment 2：Electro-deposition refers to the mistake for depositing a thin layer metal or alloy on matrix surface by electrochemical method
Journey.Electric current is set to sequentially pass through anode, electroplate liquid, negative electrode by additional power source, and electronics then flows to negative electrode by power cathode, plating solution
In metal ion then assemble toward cathode direction in the presence of electric field, final metal ion obtains electronics and is reduced into negative electrode
Metallic atom.
As science and technology is developed rapidly with industrial, new requirement, the opposing party are constantly proposed to various material surfaces
Face, alloy layer often has than the single coat of metal more excellent properties, so that the research being co-deposited is subject to more and more wider
General concern.
In order to realize metal co-deposition, it is necessary to meet following two conditions：
1st, a kind of at least metal of two kinds of metals in alloy can individually from its aqueous solution deposition out.Though some metals
From aqueous solution electrodeposition out, but can not so realize being co-deposited from the aqueous solution simultaneously with another metal.
2nd, the primary condition of metal co-deposition is that two kinds of evolution or deposition potentials of metal will be sufficiently close to or equal, makes two kinds of gold
Category ion is realized being co-deposited on negative electrode, and their deposition potential must be equal.
It is intended to promote two kinds of co-depositions of different metal, can typically uses following two measures：
1st, the concentration of metal ion is changed.Concentration is relevant in the plating solution with metal ion for the deposition potential of metal, reduces electricity
The concentration of position calibration metal ion can make its current potential become negative, or improve the concentration that current potential relatively bears metal ion, then make its electricity
Position becomes just, so that equilibrium potential of two metal ion species in the plating solution is close.But, made by changing metal ion activity
The close effect of two metal ion species equilibrium potentials is not notable, and in general, the activity of metal ion often increases or decreases 10
Times, its equilibrium potential is shuffled or negative shifting 29MV respectively.The equilibrium potential difference of most metal ions is larger, golden only with changing
It is clearly impossible to realize co-deposition to belong to the measure of ion concentration.Therefore, this measure is only in two kinds of depositions of metal
Current potential relatively in the case of as a kind of ancillary method.
2nd, appropriate complexing agent is added.Appropriate complexing agent is added in the plating solution, makes the deposition potential of metal ion mutual
Approach and realize being co-deposited, be very effective method.The addition of complexing agent can not only make the equilibrium potential of metal to negative direction
It is mobile, moreover it is possible to increase cathodic polarization.Because metal ion is in the plating solution containing complexing agent, the coordination ion for being formed exists
More stable in plating solution, degree of ionization is smaller, can reduce the valid density of ion, and its activation energy separated out on negative electrode is carried in addition
Height, being so accomplished by energy higher could be in cathodic reduction, so cathodic polarization effect increased.In this way, two kinds of gold can be made
The deposition potential for belonging to ion is approached, and reaches the purpose of co-deposition.
By to electroplating solution electrification in the case of electrodeposition cladding uniformity and different main salt components and complexing agent concentration
The research that scholarship and moral conduct is, draws to draw a conclusion：
(1) during electro-deposition Sn-Bi systems lead-free low-temperature solder, power line in the cathode between be distributed than sparse, due to
Two electrodes of negative and positive fail to completely cut through electroplate liquid so that there is the power line than comparatively dense at the edge and tip of negative electrode.At edge
Under the influence of effect, the Sn-Bi coating of deposition is presented intermediate thin, the thick trend in two ends on copper base.
(2) in testing, one piece of insulation barrier of middle with hole is placed between negative and positive the two poles of the earth, the electric power of negative electrode can be changed
Line is distributed, and edge effect is reduced to a certain extent.Result of the test shows, plus after baffle plate, Sn-Bi coating is equal on substrate
Even property has obtained larger improvement.
(3) polarization curve from different main salt components can be seen that in the presence of complexing agent sodium citrate, relative to mark
There is negative shifting in the deposition potential of collimator electrode current potential, Sn and Bi.Due to being influenceed by Sn2+ ions in plating solution, Sn-Bi is co-deposited
The deposition potential when deposition potential of middle Bi is than independent deposited metal Bi is more negative, and by contrast, the deposition potential change of Sn is smaller.
(4) sodium citrate can form metel complex ion with the metal ion in solution (Sn2+, Bi3+) effect, so that
The deposition potential of ion becomes negative, increases cathodic polarization.Sodium citrate concentration is bigger, and cathodic polarization is stronger so that the analysis of Sn and Bi
Go out current potential to be moved to negative direction.Additionally, the content of sodium citrate is too high, then current efficiency and limiting current density can be caused to subtract
Small, cathode hydrogen evolution seriously waits harmful effect.
The preferred embodiments of the invention is the foregoing is only, claims of the invention are not limited to.
Simultaneously it is described above, for those skilled in the technology concerned it would be appreciated that and implement, therefore other be based on institute of the present invention
The equivalent change that disclosure is completed, should be included in the covering scope of the claims.
Useful achievement of the invention is：The present invention is made on the basis of sulfate is for the alloy electroplating bath of medium with sodium citrate
It is complexing agent, Sn-Bi systems lead-free low-temperature solder is prepared for using the method for electro-deposition, the present invention can increases cathodic polarization, make
The deposition potential of ion becomes negative, and the insulation barrier of addition middle with hole can change the electric force lines distribution of negative electrode, to a certain degree
Upper reduction edge effect, the uniformity that the coating of deposition is distributed on substrate has obtained larger improvement.Additionally, being accounted for by adjustment
Sky ratio and pulse frequency, the trend that increase crystal grain is grown up so that solder particle is thicker.
Claims (1)
1. a kind of electro-deposition method of Sn-Bi systems lead-free low-temperature solder, it is characterised in that the Sn-Bi systems Pb-free coating for obtaining
Material is content distribution by mass percentage, comprising 50% to 58% Bi, 0.01% to 3.0% Ag, 0.01% to 3.0%
Sb, 0.01% to 2.0% ln, 0.005% to 0.1% Co, 0.001% to 0.002% Cu, 0.002% to 0.004%
Zn, and balance of Sn, fusing point is 138 DEG C to 149 DEG C；
The electro-deposition method of the Sn-Bi series lead-free solders is comprised the steps of：
1) electroplate liquid is prepared；
The process for preparation of the electroplate liquid is as follows：
1st, after the distilled water for adding 60% or so volume in coating bath, 8 to 25g sodium citrate is added, uses magnetic stirring apparatus
Stirring 5 to 10 minutes, makes it be dissolved in distilled water, adds the bismuth sulfate of 0.8g to 4.5g, and it is heated, and promotes lemon
Lemon acid sodium and bismuth sulfate fully dissolve；
2nd, a small amount of distilled water is first added in a beaker and to its appropriate heating after, add the sulfuric acid of 3.88g to 11.24g,
Stirred at full tilt with glass bar 1 minute, after it is fully cooled to 25 DEG C, add 0.4g to 9g stannous sulfate and
The ascorbic acid of 0.2g, is stirred with magnetic stirring apparatus, it is fully dissolved；
3rd, two kinds of solution for generating 1,2 steps mix, and are diluted with water to liquor capacity for 350ml；
4th, 0.4g phenolsulfonic acid, the ethoxylated α naphthol sulfonic acid of 0.6g is dissolved in an other beaker respectively,
Add the 3rd step generation solution in；
5th, supplement distilled water reaches 800ml, after adjustment pH value, then is filtered, and stirs and analysis and regulation PH is to 7, is powered
Treatment, is used again after examination plating is qualified；
The process for preparation of the electroplate liquid is all controlled between 25 DEG C to 50 DEG C；
2) matrix used to electro-deposition to process, described matrix includes a piece of platinized platinum and a piece of copper sheet, and it is removed
Rust treatment, and ensure the smooth of surface and dry；
3) carry out electro-deposition, after the completion of cold water treatment is carried out to it, while carry out alcoholic solution dehydration with dry, expired
The Sn-Bi series lead-free solders that foot is required；
The process of electro-deposition is as follows：
1st, electroplate liquid described in coating bath is stirred, and adds the described matrix that 2) step is handled well, i.e., a piece of platinized platinum and
A piece of copper sheet adds an insulation barrier for middle with hole, the insulation respectively as positive level and negative electrode between positive level and negative electrode
20 holes are uniformly distributed in the middle of baffle plate, and the electroplate liquid is electrically heated, the temperature of heating is 28 DEG C, using pulse electricity
Stream, the dutycycle of the pulse current is 60%, pulse frequency is 600HZ, the metal ion of the electroplate liquid by electromigration,
The forms such as convection current, diffusion are reached near cathode surface；
2nd, the metal ion of the electroplate liquid before reduction near negative electrode or surface occur chemical conversion, the water of hydrated ion
Change number decline, the part of complex ion to convert；
3rd, the metal ion of the electroplate liquid obtains electronics and is reduced into metallic atom from cathode surface, is attached to cathode surface
On；
4th, the metallic atom is diffused into up to growing point along cathode surface and enters lattice growth, meets to form crystalline substance with other particles
Core, final great achievement crystal long, after the crystal cooling, it is that content is divided by mass percentage to obtain the Sn-Bi series lead-free solders
Match somebody with somebody, comprising 50% to 58% Bi, 0.01% to 3.0% Ag, 0.01% to 3.0% Sb, 0.01% to 2.0% ln,
0.005% to 0.1% Co, 0.001% to 0.002% Cu, 0.002% to 0.004% Zn, and balance of Sn, melt
Point is 138 DEG C to 149 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611226143.XA CN106835214A (en) | 2016-12-27 | 2016-12-27 | A kind of electro-deposition method of Sn Bi systems lead-free low-temperature solder |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611226143.XA CN106835214A (en) | 2016-12-27 | 2016-12-27 | A kind of electro-deposition method of Sn Bi systems lead-free low-temperature solder |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109837572A (en) * | 2019-04-03 | 2019-06-04 | 浙江亚通焊材有限公司 | A kind of electro-deposition method of Sn-Bi system lead-free low-temperature solder |
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2016
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| CN1379123A (en) * | 2002-01-23 | 2002-11-13 | 武汉大学 | Complexing agent for electroplating Sn-Bi alloy and its preparing process |
| CN101380700A (en) * | 2007-09-05 | 2009-03-11 | 北京康普锡威焊料有限公司 | Tin bismuth cuprum series leadless solder and preparation method thereof |
| CN105431253A (en) * | 2014-06-24 | 2016-03-23 | 播磨化成株式会社 | Solder alloy, solder composition, solder paste and electronic circuit board |
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| CN109837572A (en) * | 2019-04-03 | 2019-06-04 | 浙江亚通焊材有限公司 | A kind of electro-deposition method of Sn-Bi system lead-free low-temperature solder |
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