CN101733581A - Cadmium-free silver brazing alloy containing calcium, silicon and erbium - Google Patents
Cadmium-free silver brazing alloy containing calcium, silicon and erbium Download PDFInfo
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- CN101733581A CN101733581A CN200910154506A CN200910154506A CN101733581A CN 101733581 A CN101733581 A CN 101733581A CN 200910154506 A CN200910154506 A CN 200910154506A CN 200910154506 A CN200910154506 A CN 200910154506A CN 101733581 A CN101733581 A CN 101733581A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 67
- 239000000956 alloy Substances 0.000 title claims abstract description 67
- 238000005219 brazing Methods 0.000 title claims abstract description 64
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 56
- 239000004332 silver Substances 0.000 title claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 48
- 229910052691 Erbium Inorganic materials 0.000 title claims abstract description 45
- 239000010703 silicon Substances 0.000 title claims abstract description 45
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 34
- 239000011575 calcium Substances 0.000 title abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 44
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title abstract description 31
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910018956 Sn—In Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 238000005266 casting Methods 0.000 abstract description 13
- 238000003723 Smelting Methods 0.000 abstract description 10
- 238000005096 rolling process Methods 0.000 abstract description 8
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 2
- 238000009749 continuous casting Methods 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 229910000679 solder Inorganic materials 0.000 description 24
- 239000010949 copper Substances 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000005476 soldering Methods 0.000 description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 229910001369 Brass Inorganic materials 0.000 description 9
- 229910000975 Carbon steel Inorganic materials 0.000 description 9
- 239000010951 brass Substances 0.000 description 9
- 239000010962 carbon steel Substances 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 8
- 229910052793 cadmium Inorganic materials 0.000 description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910001316 Ag alloy Inorganic materials 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 241001062472 Stokellia anisodon Species 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 229910004762 CaSiO Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- HAUBPZADNMBYMB-UHFFFAOYSA-N calcium copper Chemical compound [Ca].[Cu] HAUBPZADNMBYMB-UHFFFAOYSA-N 0.000 description 2
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 2
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- ZHNLLLSTOKLTHV-UHFFFAOYSA-N copper erbium Chemical compound [Cu].[Er] ZHNLLLSTOKLTHV-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 230000005619 thermoelectricity Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides cadmium-free silver brazing alloy containing calcium, silicon and erbium and belongs to brazing materials. The cadmium-free silver brazing alloy is characterized by comprising the following components in percentage by mass: 22.0 to 24.0 percent of Cu, 19.0 to 23.0 percent of Zn, 14.0 to 18.0 percent of Sn-In alloy (in mass percentage: 50 percent of Sn and 50 percent of In), 0.1 to 0.2 percent of Ca, 0.07 to 0.14 percent of Si, 0.03 to 0.05 percent of Er, and the balance of Ag. In a mixing ratio of the components, the needed brazing wires are formed by the steps of smelting in an intermediate frequency smelting furnace, casting or horizontal continuous casting, extrusion and drawing. The ingots are extruded into strips, and the strips undergo rough rolling and finish rolling to form the thin strips. The cadmium-free silver brazing alloy of the invention is low in oxygen content (nearly in a range of 0.002 to 0.005 mass percent), relatively low in melting temperature, and has good plasticity and a 20.0 to 40.0 percent higher extensibility than the BAg40CuZnCd brazing materials.
Description
Technical field
The invention belongs to the brazing material class, specifically is the cadmium-free silver brazing alloy of a kind of calcic, silicon and erbium.
Background technology
The silver solder BAg40CuZnCd that standard recommendation is both at home and abroad used, silver content is moderate in its chemical composition, and brazing property is good, and solid-liquid phase line temperature is moderate, therefore is widely used on " large-area brazing " manufacturing process of important structure.Along with the needs that the continuous progress of China's " thermoelectricity " generating equipment manufacture level, particularly " overcritical ", " ultra supercritical " generating equipment are made, soldering tech is had higher requirement.As, the original stock size of width of silver soldering sheet (silver soldering band) is that 60mm～80mm is wide, present width need reach more than the 150mm; Stock size thickness originally is 0.3mm～0.5mm, and present thickness need reach 0.1mm～0.25mm.
For some product, need the thinner brazing wire of diameter, as some product, needing diameter is the silk material of 0.035mm, and the BAg40CuZnCd silver solder among the GB/T 10046-2008 " silver solder " can not satisfy the needs of above-mentioned band preparation, particularly can not satisfy silver soldering sheet (silver soldering band), the diameter of width more than 120mm～150mm is the needs of the silk material preparation of 0.035mm, therefore, must research and solve the difficult problem of BAg40CuZnCd silver solder " plasticity deficiency ", develop novel cadmium-free silver brazing alloy with good plasticity.
Summary of the invention
Purpose of the present invention is at the deficiencies in the prior art, provide that a kind of brazing property is good, solid-liquid phase line temperature is low, silver content is moderate, have the cadmium-free silver brazing alloy of calcic, silicon and the erbium of good plasticity, width reaches the band more than the 150mm to this fibre material and when rolling, weld tabs " do not ftracture ", silk material drawing carefully when diameter is 0.035mm still " not fracture of wire " being processed into.
The cadmium-free silver brazing alloy of calcic of the present invention, silicon and erbium, it is characterized in that, by the mass percent proportioning be: 22.0%～24.0% Cu (copper), 19.0%～23.0% Zn (zinc), (mass percent is Sn50% to 14.0%～18.0% Sn (tin) In (indium) alloy, In50%), 0.1%～0.2% Ca (calcium), 0.07%～0.14% Si (silicon), 0.03%～0.05% Er (erbium), all the other are Ag (silver).
The present invention adopts the smelting of intermediate frequency smelting furnace, casting or horizontal casting, extruding, drawing by composition proportion, promptly obtains required solder wire material.Ingot casting is squeezed into band earlier,, can be prepared into band (strip) again through roughing, finish rolling.Oxygen content low (about 0.002%～0.005% scope, mass percent) has lower fusion temperature, good plasticity in the solder of the present invention, can improve 20.0%～40.0% than BAg40CuZnCd solder percentage elongation.
The invention solves following two key technical problems:
1) discovered that " oxygen content " in the cadmium-free silver brazing alloy is to the rule that influences of cadmium-free silver brazing alloy " plasticity ": promptly in the cadmium-free silver brazing alloy " oxygen content " to oxygen content in the influence of cadmium-free silver brazing alloy " plasticity " and the copper alloy to copper alloy " plasticity " to influence rule similar.If " oxygen content " in the cadmium-free silver brazing alloy can be controlled in the oxygen content scope (promptly≤0.003%) that is equivalent to " oxygen-free copper ", then " plasticity " of cadmium-free silver brazing alloy can improve greatly.A series of result of the test of the present invention has been verified above-mentioned rule.
2) discover that the thinking that traditional " crystal grain thinning " improves plasticity is suitable in the present invention and not exclusively.Because silver solder self " plasticity " is fine, band is rolling process constantly, is accompanied by the process of " grain refinement ".But " grain refinement " back its intensity of material also can improve (being to generally acknowledge " refined crystalline strengthening " in the Metal Material Science), and difficulty of processing also can be increasing.If be rolled again, very easily produce defectives such as " cracking ", " burr "; During fine drawing, then be easy to " fracture of wire ".
The technical scheme that addresses the above problem is:
(1), use commercially available silver, cathode copper, zinc ingot metal, proportioning adopts the intermediate frequency smelting furnace to smelt on demand.After the Ag-Cu-Zn ternary alloy three-partalloy is smelted well, add successively and smelt good (by the definite addition of the composition proportion requirement of design) " tin-indium alloy ", " silicon copper ", " calcium copper alloy ", " erbium copper alloy " in advance.Stir, fully after the dissolving, casting or adopt the horizontal casting mode to obtain casting rod (ingot casting), will cast then rod (ingot casting) by push, drawing, promptly obtain needed solder wire material.Ingot casting is squeezed into band earlier,, can be prepared into band (strip) again through roughing, finish rolling.
(2), by optimizing components test, determined the optimal addn (mass percent) of calcium, silicon and erbium: promptly calcium (Ca) is 0.1%～0.2%, and silicon (Si) is 0.07%～0.14%, and erbium (Er) is 0.03%～0.05%.Special needs to be pointed out is, discover that calcium (Ca) must be controlled at 1: 1 with the mol ratio of silicon (Si), was converted into mass percent and was approximately 1: 0.7.The optimal addn (mass percent) of erbium (Er) then must be controlled at 0.03%～0.05%, in this scope, " oxygen content " in the cadmium-free silver brazing alloy of the present invention is in 0.002%～0.005% scope, BAg40CuZnCd more originally contains oxygen content in the cadmium brazing silver alloy, and (the actual measurement control sample is 0.012%, referring to table 1) reduced approximately 60%, the solder percentage elongation has improved 20.0%～40.0%.Good plasticity has guaranteed solder in the operation of rolling, reaches more than the 155mm, when thickness reaches 0.1mm, still can avoid generation of defects such as " cracking ", " burr " even be rolled down to width; Silk material drawing is when diameter is 0.035mm still " not fracture of wire " carefully.
The cadmium-free silver brazing alloy of calcic of the present invention, silicon and erbium, because the amount of the calcium, silicon and the er element that add is all less, (mass percent is Sn50% to adopt the SnIn alloy, In50%) cadmium element of alternative mass percent equal quantities, therefore contain the cadmium brazing silver alloy contrast with BAg40CuZnCd, solidus temperature and liquidus temperature change little, and suitable with it to wetability, the spreadability of mother metal, the brazed seam mechanical property is all suitable with it.Be solidus temperature 590 ℃～595 ℃ scopes, liquidus temperature is in 630 ℃～635 ℃ scopes (having considered experimental error).
Containing cadmium brazing silver alloy with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, suitable with it to wetability, the spreadability of mother metal, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
The specific embodiment
Creativeness of the present invention is:
1, discovered that " oxygen content " is to containing the rule that influences of cadmium brazing silver alloy " plasticity " in the cadmium-free silver brazing alloy---be that " oxygen content " is low more in the cadmium-free silver brazing alloy, its plasticity is good more, and promptly " solder percentage elongation raising rate " is high more.By " composition optimization ", successfully obtained the cadmium-free silver brazing alloy (referring to table 1) of " low oxygen content ", " high-ductility ".
2, discovered that calcium, silicon, erbium three elements are at the mechanism of action during with oxygen reaction in BAg40CuZnSnIn (according to the model method for expressing of GB/T10046-2008 " silver solder " regulation, the base type of patent of the present invention should the be expressed as BAg40CuZnSnIn) cadmium-free silver brazing alloy:
Be Si+O
2(in the solder melt)=SiO
2(1)
2Ca+O
2(in the solder melt)=2CaO (2)
CaO+SiO
2=CaSiO
3(or CaOSiO
2) (3)
4Er+3O
2(in the solder melt)=2Er
2O
3(or ErO, ErO
2) (4)
BAg40CuZnCd contains the performance comparison (measured value) of cadmium brazing silver alloy in table 1 embodiments of the invention and the prior art
The element that has " deoxidation " when by metallurgical principles as can be known, calcium, silicon, erbium all are metallurgy.But in the smelting of cadmium-free silver brazing alloy, preparation process, Shang Weijian is with its report that uses as " deoxidant element ".And in GB/T 10046-2008 " silver solder ", American National Standard ANSI/AWSA5.8-92 " Specification for Filler Metals for Brazing and Braze Welding ", there is no in cadmium-free silver brazing alloy and to add the report of calcium, more do not add the example or the report of calcium, silicon, erbium three elements simultaneously as alloying element.
2.1, the test in process of the present invention finds, the addition sequence of calcium, silicon, erbium three elements must strictness be controlled to be add earlier silicon, again add calcium, add erbium at last and just can get a desired effect.In addition, the addition of calcium and silicon must be 1: 1 in strict accordance with the mol ratio of calcium (Ca) and silicon (Si), is converted into mass percent and is approximately 1: 0.7 and adds.The optimal addn (mass percent) of erbium (Er) then must be controlled at 0.03%～0.05%, have only in this scope, " oxygen content " in the cadmium-free silver brazing alloy of the present invention just can be controlled in 0.002%～0.005% scope, thereby reaches the purpose that improves cadmium-free silver brazing alloy plasticity.Test shows further that also oxygen content is low more, and the raising amount of cadmium-free silver brazing alloy plasticity (, being expressed as " solder percentage elongation raising rate " among the present invention according to the experimental test result) is high more, does not wait from 20.0%～40.0%.
2.2, the principles of chemistry of above-mentioned statement are:
According to reaction equation (1) and (2) as can be known, smelting the later stage, adding silicon respectively, when calcium carries out deoxidation, respectively the SiO of Sheng Chenging
2With CaO fully " floating upward quickly " enter into " slag ", have only generation CaSiO
3Or CaOSiO
2Back { reaction equation (3) } could " floating upward quickly " enter into " slag ", and this is reflected in " metallurgy of iron and steel ", " weldingmetallurgy " and all touches upon.Therefore, add silicon simultaneously, calcium carries out deoxidation, and " in order ", " in proportion " add, just can obtain the cadmium-free silver brazing alloy of low " oxygen content ".
2.3, for the mol ratio of guaranteeing calcium (Ca) and silicon (Si) be the accurate interpolation of 1: 1 (be converted into mass percent and be approximately 1: 0.7), in process of the present invention, through evidence, can not adopt commercially available " calcium-silicon ", because (discover except that containing ferro element in commercially available " calcium-silicon ", the existence of iron has negative effect to the plasticity and the brazing property of the solder of this invention) outside, can't guarantee that the calcium (Ca) and the mol ratio of silicon (Si) they are 1: 1.Therefore, must with pure calcium, pure silicon and cathode copper in vacuum smelting furnace, smelt into calcium copper alloy, silicon copper in advance, more in order, press the composition required amount and add, just can produce a desired effect.
2.4, according to reaction equation (4) as can be known, erbium belongs to rare earth element, easier and oxygen take place to send out should, and generate Er
2O
3(or ErO, ErO
2).Test finds that the metal erbium is similar to other rare earth element, except having good deoxidation, and metal erbium, Er
2O
3(or ErO, ErO
2) all have the effect of " crystal grain thinning ", therefore, after adding silicon, calcium successively and carrying out deoxidation, add an amount of metal erbium again, have the double action of " further deoxidation " and " crystal grain thinning ".
But test is also found, in alloy system of the present invention, in order to substitute " poisonous and harmful element " cadmium, has added a large amount of low-melting alloys-SnIn alloy.According to the Sn-In binary phase diagraml as can be known, be respectively 50% o'clock at the mass percent of Sn and In, promptly when Sn50%, In50%, the fusing point of SnIn alloy is about 120 ℃.The adding of SnIn alloy, very favourable for the solid, liquid phase line temperature that reduces neoteric cadmium-free silver brazing alloy.But because the existence and the influence of SnIn alloy add other rare earth element, as La, Ce, Pr, Nd and Y element etc., to improving the plasticity of cadmium-free silver brazing alloy of the present invention, effect is all not remarkable, also has " counter productive " sometimes.Through repeated screening, find in BAg40CuZnSnIn quinary alloy silver solder of the present invention, to add after calcium and the silicon, have only the metal of interpolation erbium just can produce a desired effect.
According to the quality recipe ratio of " cadmium-free silver brazing alloy of calcic, silicon and erbium " of the present invention, further narrate embodiments of the invention.
Embodiment 1:
Press the mass percent proportioning, its composition is: 22.0% copper (Cu), 23.0% zinc (Zn), 15.0% SnIn alloy (mass percent, Sn50%, In50%), 0.2% calcium (Ca), 0.14% silicon (Si), 0.05% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 590 ℃, liquidus temperature at 630 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 2
Press the mass percent proportioning, its composition is: 24.0% copper (Cu), 19.0% zinc (Zn), 14.0% SnIn alloy (mass percent, Sn50%, In50%), 0.2% calcium (Ca), 0.14% silicon (Si), 0.05% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 595 ℃, liquidus temperature at 635 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 3:
Press the mass percent proportioning, its composition is: 23.0% copper (Cu), 22.0% zinc (Zn), 16.0% ShIn alloy (mass percent, Sn50%, In50%), 0.2% calcium (Ca), 0.14% silicon (Si), 0.05% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 595 ℃, liquidus temperature at 635 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 4:
Press the mass percent proportioning, its composition is: 21.0% copper (Cu), 23.0% zinc (Zn), 18.0% SnIn alloy (mass percent, Sn50%, In50%), 0.2% calcium (Ca), 0.14% silicon (Si), 0.05% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 590 ℃, liquidus temperature at 635 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 5:
Press the mass percent proportioning, its composition is: 22.5% copper (Cu), 21.5% zinc (Zn), 17.5% SnIn alloy (mass percent, Sn50%, In50%), 0.2% calcium (Ca), 0.14% silicon (Si), 0.05% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 590 ℃, liquidus temperature at 635 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 6:
Press the mass percent proportioning, its composition is: 23.0% copper (Cu), 20.0% zinc (Zn), 17.5% SnIn alloy (mass percent, Sn50%, In50%), 0.1% calcium (Ca), 0.07% silicon (Si), 0.045% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 590 ℃, liquidus temperature at 635 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 7:
Press the mass percent proportioning, its composition is: 22.0% copper (Cu), 23.0% zinc (Zn), 17.0% SnIn alloy (mass percent, Sn50%, In50%), 0.1% calcium (Ca), 0.07% silicon (Si), 0.040% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 590 ℃, liquidus temperature at 630 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
Embodiment 8:
Press the mass percent proportioning, its composition is: 24.0% copper (Cu), 22.5% zinc (Zn), 15.5% SnIn alloy (mass percent, Sn50%, In50%), 0.1% calcium (Ca), 0.07% silicon (Si), 0.03% erbium (Er), all the other are silver (Ag).
" cadmium-free silver brazing alloy of calcic, silicon and the erbium " solidus temperature that obtains according to the mentioned component proportioning at 595 ℃, liquidus temperature at 635 ℃ (having considered experimental error), with BAg40CuZnCd is object of reference, cooperate FB102 (QJ102) brazing flux, during combinations of materials such as soldering red copper-brass, brass-carbon steel, stainless steel-nickel-base alloy, wetability, spreadability to mother metal are suitable with it, the suitable with it (σ of brazed seam mechanical property
b=180～360MPa scope, τ=175～310MPa scope).
The present invention presses the foregoing description composition proportion, adopts the smelting of intermediate frequency smelting furnace, casting or horizontal casting, extruding, drawing, promptly obtains required solder wire material.Ingot casting is squeezed into band earlier,, can be prepared into band (strip) again through roughing, finish rolling.Oxygen content low (about 0.002%～0.005% scope, mass percent) has lower fusion temperature, good plasticity in the solder, can improve 20.0%～40.0% than BAg40CuZnCd solder percentage elongation.
From table 1 and embodiment 1-8 as can be seen, it is still significant to add " further deoxidation " effect of metal erbium.Particularly comparing embodiment 6, embodiment 7 and embodiment 8 are as can be known, adding 0.1% calcium (Ca), behind 0.07% silicon (Si), the addition of erbium (Er) drops to 0.04% and at 0.03% o'clock from 0.045%, oxygen content in the cadmium-free silver brazing alloy rises to 0.005% from 0.004%, and its solder percentage elongation raising rate drops to 21.3% and 20.0% from 24.0%.
Claims (1)
1. the cadmium-free silver brazing alloy of a calcic, silicon and erbium, it is characterized in that: by the mass percent proportioning be 22.0%～24.0% Cu, 19.0%～23.0% Zn, 14.0%～18.0% Sn-In alloy, 0.1%～0.2% Ca, 0.07%～0.14% Si, 0.03%～0.05% Er, all the other are Ag, wherein the mass percent of Sn-In alloy is Sn50%, In50%.
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| CN104942474A (en) * | 2015-07-06 | 2015-09-30 | 江苏科技大学 | Cadmium-free silver brazing solder containing Sn, Si, Zn and Pr and preparation method thereof |
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| US4052531A (en) * | 1975-08-14 | 1977-10-04 | Eutectic Corporation | Indium-containing silver-copper-zinc brazing alloy |
| CN100558499C (en) * | 2007-09-26 | 2009-11-11 | 金李梅 | A kind of manufacture method of cadmium-free silver brazing alloy |
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| CN104942474A (en) * | 2015-07-06 | 2015-09-30 | 江苏科技大学 | Cadmium-free silver brazing solder containing Sn, Si, Zn and Pr and preparation method thereof |
| CN104942474B (en) * | 2015-07-06 | 2017-04-05 | 江苏科技大学 | A kind of cadmium-free silver brazing alloy of stanniferous, silicon, zinc and praseodymium and preparation method thereof |
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