CN104476006A - Submerged-arc welding high-moisture oxidation-resistant lead-free solder and preparation method thereof - Google Patents

Submerged-arc welding high-moisture oxidation-resistant lead-free solder and preparation method thereof Download PDF

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Publication number
CN104476006A
CN104476006A CN201410653989.6A CN201410653989A CN104476006A CN 104476006 A CN104476006 A CN 104476006A CN 201410653989 A CN201410653989 A CN 201410653989A CN 104476006 A CN104476006 A CN 104476006A
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China
Prior art keywords
lead
free solder
particle
alloying pellet
solder
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CN201410653989.6A
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CN104476006B (en
Inventor
姚正军
姚一波
罗西希
林玉划
周艳军
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/362—Selection of compositions of fluxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40—Making wire or rods for soldering or welding

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Nonmetallic Welding Materials (AREA)

Abstract

The invention relates to a welding material, in particular to a lead-free solder in the field of submerged-arc welding. The lead-free solder comprises, in weight percent, 0.2-0.8% of Cu, 0.075-0.5% of Ni-V alloy particles, 0.1-1.2% of nano ZrO2 particles and the balance Sn. The invention further relates to a preparation method which includes the steps: uniformly mixing components of the lead-free solder according to the mass ratio and then placing the components into an Al2O3 crucible; placing the crucible in a 400-600 DEG C resistance furnace for smelting; keeping the temperature for 100min to 200min after complete smelting; sufficiently stirring the components after keeping the temperature; discharging the components and pouring the components into a solder bar mould; cooling the components to obtain a lead-free solder bar. The lead-free solder has the advantages that wetting property is fine, electromagnetic induction is not generated, the lead-free solder has a fine creep performance and resistant to oxidation and the like.

Description

A kind of height used for submerged arc welding soaks resistance to oxidation lead-free solder and preparation for processing thereof
Technical field
The present invention relates to a kind of welding material, be specifically related to a kind of lead-free solder for submerged arc welding field.
Background technology
Traditional solder is Pb-Sn solder, this kind of solder due to wetability good, the higher and low price of the reliability after welding, is widely used.But, because Pb element has toxicity, great harm can be caused to environment and human body by the product after the manufacture of Pb solder, not meet the requirement of " green industry " and " sustainable development ".Therefore countries in the world all clear stipulaties prohibit the use Pb solder, as European Union in 2003 issue WEEE instruction and ROHS instruction.And China also clear stipulaties prohibit the use containing Pb solder from March, 2007.Therefore the development of lead-free solder is imperative.
The more lead-free solder of current application has following kind: Sn-Cu, Sn-Ag, Sn-Zn, Sn-Ag-Cu.But above-mentioned solder in use all exists some problems, as: Sn-Cu solder low price but wetability is poor; Though Sn-Ag solder wettability is better than Sn-Cu, due to the existence of precious metals ag, therefore cost is too high; Sn-Zn solder has high creep resistance and thermal fatigue property, but due to Zn activity too large, Sn-Zn solder corrosion resistance is very poor.Propose in patent No. CN201410228913 " a kind of lead-free solder " to adopt to add Ni nanoparticle particle to improve the method for the wetability of solder.But because Ni belongs to ferromagnetic material, and its magnetic susceptibility at normal temperatures can reach 10 -3the order of magnitude, for solder alloy, easily produces electromagnetic induction, can make a big impact to the stability in solder use.
Summary of the invention
For the above-mentioned problem mentioned, problem to be solved by this invention is exactly a kind of lead-free solder for submerged arc welding field of exploitation, this lead-free solder possess simultaneously wetability good but do not produce electromagnetic induction, the croop property that had and the advantages such as resistance to oxidation.The object of the invention is to be realized by following technical proposal:
A kind of height used for submerged arc welding soaks resistance to oxidation lead-free solder, it is characterized in that it is made up of the component of following weight percentage:
Cu:0.2-0.8%, Ni-V alloying pellet: 0.075-0.5%, nanometer ZrO 2particle: 0.1-1.2%, surplus is Sn.
Described Ni-V alloying pellet is Ni 3v particle, Ni 2v particle or NiV 3one in particle.
Preferably, described Ni-V alloying pellet is Ni 3v particle, is made up of the component of following weight percentage: Ni:77.3%, V:22.7%.
Preferably, described Ni-V alloying pellet is Ni 2v particle, is made up of the component of following weight percentage: Ni:69.5%, V:30.5%.
Preferably, described Ni-V alloying pellet is NiV 3particle, is made up of the component of following weight percentage: Ni:27.5%, V:72.5%.
Described Ni-V alloying pellet is obtained by following method:
Carry out vacuum arc melting after being mixed with V grain by the Ni powder of above-mentioned mass percent, after complete melting, take out.The annealing furnace then the Ni-V alloy after melting being put into 700 DEG C to 900 DEG C carries out the annealing of 5 to 9 days by a definite date, take out the Ni-V alloy after annealing, nanon ball-mill is utilized to carry out ball milling, arranging rotating speed is 1000 rpm to 2000rpm, Ball-milling Time is 5h to 8h, obtains described Ni-V alloying pellet.
Preferably, the temperature of above-mentioned annealing furnace is 800 DEG C.
Preferably, utilize nanon ball-mill to carry out ball milling, arranging rotating speed is 1500rpm.
Preferably, above-mentioned Ball-milling Time is 6h.
Described Ni-V alloying pellet particle diameter is 3 μm to 40 μm.
Described nanometer ZrO 2grain diameter is 10 nm to 60nm.
As preferably, in above-mentioned leadless welding alloy, described leadless welding alloy contains the percentage by weight of following composition:
Cu:0.3-0.8%, Ni 3v:0.1-0.3%, nanometer ZrO 2: 0.1-1.2%, surplus is Sn.
As preferably, in above-mentioned leadless welding alloy, described leadless welding alloy contains the percentage by weight of following composition:
Cu:0.3-0.8%, Ni 2v:0.15-0.4%, nanometer ZrO 2: 0.1-1.2%, surplus is Sn.
As preferably, in above-mentioned leadless welding alloy, described leadless welding alloy contains the percentage by weight of following composition:
Cu:0.3-0.8%, NiV 3: 0.08-0.2%, nanometer ZrO 2: 0.1-1.2%, surplus is Sn.
Present invention also offers the preparation method of above-mentioned lead-free solder, its technical scheme is as follows:
Height used for submerged arc welding soaks a preparation method for resistance to oxidation lead-free solder, comprises the following steps: by Cu powder, nanometer ZrO 2the Ni-V alloying pellet of particle, preparation, Sn block mix according to above-mentioned mass percent puts into Al 2o 3in crucible, resistance furnace crucible being placed in 400 DEG C to 600 DEG C carries out melting, completely after fusing, carries out 100min to 200min and is incubated, fully stir, come out of the stove after insulation, be cast in welding rod mould, obtains Pb-free coating material strip after cooling.
Preferably, the temperature of carrying out melting in resistance furnace is 500 DEG C.
Preferably, completely after fusing, the time carrying out being incubated is 150min.
Advantage of the present invention is:
the interpolation of Ni-V alloy can serve as surfactant, is adsorbed on fusion welding surface, is beneficial to solder sprawling at substrate surface, reduces its angle of wetting, thus improves the wetability of solder.
the interpolation of Ni-V alloy also can form diffusion barrier Ni with Sn 3sn 4with VSn 2, effectively can suppress the Cu element in solder alloy and form Cu in substrate Cu Elements Diffusion to Sn in encapsulation process 3sn etc. reduce the intermetallic compound of package quality.
v adds the magnetic effectively eliminating Ni, therefore improves the stability of solder alloy greatly.
the nanometer ZrO added 2material is tiny due to grain size, can play the effect of refined crystalline strengthening, effective intensity and the plasticity improving solder alloy, and then improves the croop property of welding point.
nanometer ZrO 2there is good antioxygenic property, therefore can also improve the oxidative resistance of this lead-free solder greatly.
To sum up, lead-free solder wetability of the present invention is good, but does not have magnetic.The obdurability simultaneously had and croop property, and have certain oxidative resistance, be a kind of lead-free solder of high comprehensive performance.
Accompanying drawing explanation
Fig. 1: nanometer ZrO 2interpolation on the impact of solder alloy creep fracture property.
Fig. 2: add nanometer ZrO 2the microscopic structure of the solder alloy before particle.
Fig. 3: add nanometer ZrO 2the microscopic structure of the solder alloy after particle.
Detailed description of the invention
Below in conjunction with embodiment, invention is further described.
embodiment 1
A kind of high wetting resistance to oxidation lead-free solder, is made up of the raw material of following weight percentage:
Cu:0.5%, Ni 3v:0.2%, nanometer ZrO 2particle: 0.6%, surplus is Sn.
According to above-mentioned percentage by weight, by Cu powder, Ni 3v particle, nanometer ZrO 2particle, and Sn block, after mixing, get gross mass 2Kg, be positioned over Al 2o 3in crucible, then sent in the resistance furnace of 500 DEG C and carried out melting.Completely after fusing, insulation 150min, comes out of the stove after fully stirring, is cast in welding rod mould, obtains Pb-free coating material strip after cooling.
embodiment 2
A kind of high wetting resistance to oxidation lead-free solder, is made up of the raw material of following weight percentage:
Cu:0.7%, Ni 2v:0.3%, nanometer ZrO 2particle: 0.5%, surplus is Sn.
In this embodiment, the preparation method of Pb-free coating material strip is consistent with the preparation method of the Pb-free coating material strip in embodiment 1, and the percentage by weight of each component that difference is only in Pb-free coating material strip takes according in the present embodiment.
embodiment 3
A kind of high wetting resistance to oxidation lead-free solder, is made up of the raw material of following weight percentage:
Cu:0.5%, NiV 3: 0.1%, nanometer ZrO 2particle: 0.8%, surplus is Sn.
In this embodiment, the preparation method of Pb-free coating material strip is consistent with the preparation method of the Pb-free coating material strip in embodiment 1, and the percentage by weight of each component that difference is only in Pb-free coating material strip takes according in the present embodiment.
embodiment 4
A kind of high wetting resistance to oxidation lead-free solder, is made up of the raw material of following weight percentage:
Cu:0.5%, Ni 2v:0.2%, nanometer ZrO 2particle: 0.7%, surplus is Sn.
In this embodiment, the preparation method of Pb-free coating material strip is consistent with the preparation method of the Pb-free coating material strip in embodiment 1, and the percentage by weight of each component that difference is only in Pb-free coating material strip takes according in the present embodiment.
embodiment 5
A kind of high wetting resistance to oxidation lead-free solder, is made up of the raw material of following weight percentage:
Cu:0.5%, Ni 2v:0.2%, nanometer ZrO 2particle: 0.9%, surplus is Sn.
In this embodiment, the preparation method of Pb-free coating material strip is consistent with the preparation method of the Pb-free coating material strip in embodiment 1, and the percentage by weight of each component that difference is only in Pb-free coating material strip takes according in the present embodiment.
embodiment 6
A kind of high wetting resistance to oxidation lead-free solder, is made up of the raw material of following weight percentage:
Cu:0.5%, Ni 2v:0.2%, nanometer ZrO 2particle: 1.0%, surplus is Sn.
In this embodiment, the preparation method of Pb-free coating material strip is consistent with the preparation method of the Pb-free coating material strip in embodiment 1, and the percentage by weight of each component that difference is only in Pb-free coating material strip takes according in the present embodiment.
The lead-free solder provided by embodiment 1-6 carries out performance test, and method of testing is as shown in table 1:
Table 1 performance test method therefor and instrument list
The performance test results of embodiment 1-6 is as shown in table 2:
The performance test results of table 2 embodiment 1-6

Claims (10)

1. height used for submerged arc welding soaks a resistance to oxidation lead-free solder, it is characterized in that: it is made up of the component of following weight percentage:
Cu:0.2-0.8%, Ni-V alloying pellet: 0.075-0.5%, nanometer ZrO 2particle: 0.1-1.2%, surplus is Sn.
2. lead-free solder as claimed in claim 1, is characterized in that: described Ni-V alloying pellet is Ni 3v particle, Ni 2v particle or NiV 3one in particle.
3. lead-free solder as claimed in claim 1, is characterized in that: be made up of the component of following weight percentage: Cu:0.3-0.8%, Ni 3v:0.1-0.3%, nanometer ZrO 2: 0.1-1.2%, surplus is Sn.
4. lead-free solder as claimed in claim 1, is characterized in that: be made up of the component of following weight percentage: Cu:0.3-0.8%, Ni 2v:0.15-0.4%, nanometer ZrO 2: 0.1-1.2%, surplus is Sn.
5. lead-free solder as claimed in claim 1, is characterized in that: be made up of the component of following weight percentage: Cu:0.3-0.8%, NiV 3: 0.08-0.2%, nanometer ZrO 2: 0.1-1.2%, surplus is Sn.
6. as claimed in claim 1, it is characterized in that: described nanometer ZrO 2the particle diameter of particle is 10 nm to 60nm.
7. as claimed in claim 2, it is characterized in that: the particle diameter of described Ni-V alloying pellet is 3 μm to 40 μm.
8. lead-free solder as claimed in claim 2, is characterized in that: described Ni-V alloying pellet is made up of the component of following weight percentage:
Ni-V alloying pellet is Ni 3v, wherein Ni:77.3%, V:22.7%; Or Ni-V alloying pellet is Ni 2v, wherein Ni:69.5%, V:30.5%; Or Ni-V alloying pellet is NiV 3, wherein Ni:27.5%, V:72.5%.
9. the lead-free solder as described in any one of claim 2 to 5, is characterized in that: described Ni-V alloying pellet is obtained by following method:
Vacuum arc melting is carried out after being mixed with V grain by Ni powder; after complete melting; take out Ni-V alloy; the annealing furnace putting into 700 DEG C to 900 DEG C carries out the annealing of 5 to 9 days by a definite date; take out the Ni-V alloy after annealing, utilize nanon ball-mill to carry out ball milling, arranging rotating speed is 1000 rpm to 2000rpm; Ball-milling Time is 5h to 8h, obtains described Ni-V alloying pellet.
10. height used for submerged arc welding soaks a preparation method for resistance to oxidation lead-free solder, it is characterized in that: comprise the following steps:
After the component of lead-free solder as claimed in claim 1 being mixed by described quality proportioning, put into Al 2o 3in crucible, resistance furnace crucible being placed in 400 DEG C to 600 DEG C carries out melting, completely after fusing, carries out 100min to 200min and is incubated, fully stir, come out of the stove after insulation, be cast in welding rod mould, obtains Pb-free coating material strip after cooling.
CN201410653989.6A 2014-11-18 2014-11-18 A kind of high wetting resistance to oxidation lead-free solder used for submerged arc welding and preparation for processing thereof Active CN104476006B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923960A (en) * 2015-05-09 2015-09-23 安徽再制造工程设计中心有限公司 Ni-CrC nano welding layer for part welding and preparation method thereof
CN106624433A (en) * 2016-11-30 2017-05-10 安徽华众焊业有限公司 Low-melting-point lead-free solder alloy
CN106624434A (en) * 2016-11-30 2017-05-10 安徽华众焊业有限公司 Tin antimony solder alloy

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1672859A (en) * 2005-05-09 2005-09-28 天津大学 Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process
WO2006038907A2 (en) * 2003-12-23 2006-04-13 Boaz Premakaran T Lead-free solder composition for substrates
US20060147337A1 (en) * 2003-07-03 2006-07-06 Antaya Technologies Corporation Solder composition
CN1907636A (en) * 2006-08-28 2007-02-07 北京航空航天大学 Oxidation resistance tin-based no-lead solder capable of proceeding welding without welding flux in air
CN103978323A (en) * 2014-05-27 2014-08-13 北京理工大学 Lead-free solder

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060147337A1 (en) * 2003-07-03 2006-07-06 Antaya Technologies Corporation Solder composition
WO2006038907A2 (en) * 2003-12-23 2006-04-13 Boaz Premakaran T Lead-free solder composition for substrates
CN1672859A (en) * 2005-05-09 2005-09-28 天津大学 Zirconium oxide nano grain reinforced composite Sn-Ag welding material and its prepn process
CN1907636A (en) * 2006-08-28 2007-02-07 北京航空航天大学 Oxidation resistance tin-based no-lead solder capable of proceeding welding without welding flux in air
CN103978323A (en) * 2014-05-27 2014-08-13 北京理工大学 Lead-free solder

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104923960A (en) * 2015-05-09 2015-09-23 安徽再制造工程设计中心有限公司 Ni-CrC nano welding layer for part welding and preparation method thereof
CN106624433A (en) * 2016-11-30 2017-05-10 安徽华众焊业有限公司 Low-melting-point lead-free solder alloy
CN106624434A (en) * 2016-11-30 2017-05-10 安徽华众焊业有限公司 Tin antimony solder alloy

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