CN106825987A - A kind of silver-based brazing alloy and preparation method thereof - Google Patents
A kind of silver-based brazing alloy and preparation method thereof Download PDFInfo
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- CN106825987A CN106825987A CN201611246004.3A CN201611246004A CN106825987A CN 106825987 A CN106825987 A CN 106825987A CN 201611246004 A CN201611246004 A CN 201611246004A CN 106825987 A CN106825987 A CN 106825987A
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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
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- 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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- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
The present invention provides a kind of silver-based brazing alloy and preparation method thereof, belongs to solder technology field, and the silver-based brazing alloy is made up of following raw material by mass percentage：Ag49~51%, Zn26~28%, Sn0.7~1.3%, Ni0.3~0.65%, Mn6.5~8.5%, In0.8~1.2%, Ga0.1~0.3%, rare earth 0.01~0.05%, Graphene 0.01 0.02%, balance of copper and inevitable impurity.Silver-based brazing alloy high mechanical strength, compactness is good in the present invention, resistivity is low, joint corrosion resistance and creep strength are outstanding, and feedback soldering processes performance is excellent after client's use, soldered fitting steady quality, with good fatigue behaviour, the service life of soldered fitting can be effectively lifted.
Description
Technical field
The present invention relates to a kind of solder technology field, more particularly to a kind of silver based soldering alloy and preparation method thereof.
Background technology
Silver solder is a kind of current most widely used hard solder, and it has excellent processing performance, suitable fusing point, good
Good wetting and the ability in gap is filled up, and the intensity of solder and brazed seam, electric conductivity and excellent corrosion resistance, therefore be widely used in
Soldering mild steel, stainless steel, high temperature alloy, copper and copper alloy and refractory alloy.
Silver solder is the different series solder for adding some other alloying elements to be formed on the basis of yellow gold.Closely
In decades, the research of silver solder is concentrated mainly on 4 aspects：The research of cadmium-free silver brazing alloy, the research of low silver-colored silver-less solder, conjunction
The influence of gold element and the research developed with solder for ceramic soldering of new brazing filler metal alloy system etc..Both at home and abroad to silver solder
Research, be after all the influence for analyzing silver solder alloying element, and based on this, develop various function admirables
Solder meet various requirements in industrial production.
The content of the invention
The present invention provides a kind of silver based soldering alloy and preparation method thereof, and the silver based soldering alloy fusing point is low, intensity is high, can
Copper brazing alloy, steel and stainless steel and the relatively low quenched and tempered steel of pricker temperature.
The technical proposal of the invention is realized in this way：
A kind of silver-based brazing alloy, is made up of following raw material by mass percentage：Ag49~51%, Zn26~28%,
Sn0.7~1.3%, Ni0.3~0.65%, Mn6.5~8.5%, In0.8~1.2%, Ga0.1~0.3%, rare earth 0.01~
0.05%th, Graphene 0.01-0.02%, balance of copper and inevitable impurity.
Wherein it is preferred to, a kind of silver-based brazing alloy is made up of following raw material by mass percentage：Ag50%,
It is Zn27%, Sn0.8~1.2%, Ni0.4~0.55%, Mn6.8~7.2%, In0.9~1.1%, Ga0.15~0.25%, dilute
Soil 0.02~0.04%, Graphene 0.01-0.02%, balance of copper and inevitable impurity.
Preparation method that is of the invention and providing silver-based brazing alloy, comprises the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni,
Cu-P, Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add covering after the completion of charging immediately
Insulation effect is played in agent；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；By in silver-based soldering
Between alloy 100-150 mesh it is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C of degree, grinds 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
With Ag-Cu-Zn as matrix, other each compositions and content determine solder of the invention in the following manner：
The fusing point of indium metal is 156 DEG C, and the fusing point than metallic tin is lower, and addition indium can more significantly reduce solder
Solid, liquid phase line, similar to tin, indium can make the interval reduction of brazing filler metal melts, improve solder fluidity.
Element S n, In maximally effective can drop fusing point and be modified as copper base solder, though it can reduce silver-base solder
Liquidus temperature, but the solidus temperature reduction of solder simultaneously is more, causes that the melting region of solder is bigger, and brazing property enters one
Step is deteriorated.By the brazing property and processing characteristics that add appropriate element S n or/and In to improve solder, make solder existing bright
Aobvious cost declining effect, and with excellent brazing property and processing characteristics.
Ni elements play a part of solution strengthening in being solidly soluted into Cu matrixes, can improve the intensity of solder, so selection
Addition chemical element Ni, increases intensity, the toughness of solder；Ni elements can also play the resistance to corrosion for improving soldered fitting simultaneously
Effect, so as to improve the comprehensive brazing property of solder；But the content of Ni can not be too high, by testing, once the content of Ni
More than 0.55%, can raise the fusion temperature of brazing filler metal alloy, and Ni can increase solder hardness with p-shaped into Ni3P brittlement phases,
Be unfavorable for solder is processed further shaping.
Mn has the effect of secondary deoxidation and improves solder antioxygenic property.Mn, the addition of P element can improve unleaded pricker
The antioxygenic property of material.
Ga-Zn easily forms crystal boundary fragility eutectic, and the processability that Zn contents are conducive to improving brazing filler metal alloy is greatly reduced.
Rare earth：Add trace rare-earth has adjustment effect to solder tissue, can refine the tissue of brazing filler metal alloy, lifting solder
Processing characteristics, while reducing the oxide content in ingot casting, improves the wettability of solder.
Beneficial effects of the present invention：
Silver-based brazing alloy high mechanical strength, compactness is good in the present invention, resistivity is low, and joint corrosion resistance and creep are strong
Degree is outstanding, and feedback soldering processes performance is excellent after client's use, soldered fitting steady quality, with good fatigue behaviour,
The service life of soldered fitting can effectively be lifted；Process performance index requirement, part index number suitable with BCu80AgP copper-phosphorus brazing alloys
Also higher than BCu80AgP copper-phosphorus brazing alloys, can substitute BCu80AgP for the soldering of electromechanics trade.
Specific embodiment
The technical scheme in the embodiment of the present invention is clearly and completely described below, it is clear that described embodiment
Only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
All other embodiment that art personnel are obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
Embodiment 1
The present embodiment provides a kind of silver-based brazing alloy, is made up of following raw material by mass percentage：Ag50%,
Zn27%, Sn1.0%, Ni0.50%, Mn7.0%, In1.0%, Ga0.2%, rare earth 0.03%, Graphene 0.015%, surplus
It is copper and inevitable impurity.
The preparation method of the silver-based brazing alloy of the present embodiment, comprises the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni,
Cu-P, Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add covering after the completion of charging immediately
Insulation effect is played in agent；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；By in silver-based soldering
Between alloy 100-150 mesh it is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C of degree, grinds 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
The silver-based brazing alloy fusion temperature of the present embodiment：650 DEG C of solidus, 670 DEG C of liquidus curve.Wetting power 0.55mN,
Spreading ratio 91.2%, shear strength 140MPa.
Embodiment 2
The present embodiment provides a kind of silver-based brazing alloy, is made up of following raw material by mass percentage：Ag49%,
Zn28%, Sn0.7%, Ni0.65%, Mn6.5%, In1.2%, Ga0.1%, rare earth 0.05%, Graphene 0.01%, surplus
It is copper and inevitable impurity.
The preparation method of the silver-based brazing alloy of the present embodiment, comprises the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni,
Cu-P, Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add covering after the completion of charging immediately
Insulation effect is played in agent；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；By in silver-based soldering
Between alloy 100-150 mesh it is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C of degree, grinds 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
The silver-based brazing alloy fusion temperature of the present embodiment：652 DEG C of solidus, 676 DEG C of liquidus curve.Wetting power 0.58mN,
Spreading ratio 92.1%, shear strength 150MPa.
Embodiment 3
The present embodiment provides a kind of silver-based brazing alloy, is made up of following raw material by mass percentage：Ag51%,
It is Zn26%, Sn1.3%, Ni0.3%, Mn8.5%, In0.8%, Ga0.3%, rare earth 0.01%, Graphene 0.02%, balance of
Copper and inevitable impurity.
The preparation method of the silver-based brazing alloy of the present embodiment, comprises the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni,
Cu-P, Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add covering after the completion of charging immediately
Insulation effect is played in agent；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；By in silver-based soldering
Between alloy 100-150 mesh it is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C of degree, grinds 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
The silver-based brazing alloy fusion temperature of the present embodiment：648 DEG C of solidus, 671 DEG C of liquidus curve.Wetting power 0.56mN,
Spreading ratio 93.2%, shear strength 144MPa.
Embodiment 4
The present embodiment provides a kind of silver-based brazing alloy, is made up of following raw material by mass percentage：Ag50%,
Zn27%, Sn0.8%, Ni0.55%, Mn6.8%, In1.1%, Ga0.15%, rare earth 0.04%, Graphene 0.01%, surplus
It is copper and inevitable impurity.
The preparation method of the silver-based brazing alloy of the present embodiment, comprises the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni,
Cu-P, Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add covering after the completion of charging immediately
Insulation effect is played in agent；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；By in silver-based soldering
Between alloy 100-150 mesh it is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C of degree, grinds 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
The silver-based brazing alloy fusion temperature of the present embodiment：645 DEG C of solidus, 662 DEG C of liquidus curve.Wetting power 0.60mN,
Spreading ratio 93.2%, shear strength 156MPa.
Embodiment 5
The present embodiment provides a kind of silver-based brazing alloy, is made up of following raw material by mass percentage：Ag50%,
Zn27%, Sn1.2%, Ni0.4%, Mn7.2%, In0.9%, Ga0.25%, rare earth 0.02~0.04%, Graphene
0.01%th, balance of copper and inevitable impurity.
The preparation method of the silver-based brazing alloy of the present embodiment, comprises the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni,
Cu-P, Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add covering after the completion of charging immediately
Insulation effect is played in agent；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；By in silver-based soldering
Between alloy 100-150 mesh it is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C of degree, grinds 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
The silver-based brazing alloy fusion temperature of the present embodiment：646 DEG C of solidus, 671 DEG C of liquidus curve.Wetting power 0.59mN,
Spreading ratio 92.3%, shear strength 148MPa.
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Within god and principle, any modification, equivalent substitution and improvements made etc. should be included within the scope of the present invention.
Claims (3)
1. a kind of silver-based brazing alloy, it is characterised in that be made up of following raw material by mass percentage：Ag49~51%,
Zn26~28%, Sn0.7~1.3%, Ni0.3~0.65%, Mn6.5~8.5%, In0.8~1.2%, Ga0.1~0.3%,
Rare earth 0.01~0.05%, Graphene 0.01-0.02%, balance of copper and inevitable impurity.
2. a kind of silver-based brazing alloy according to claim 1, it is characterised in that by mass percentage by following raw material
It is made：Ag50%, Zn27%, Sn0.8~1.2%, Ni0.4~0.55%, Mn6.8~7.2%, In0.9~1.1%,
Ga0.15~0.25%, rare earth 0.02~0.04%, Graphene 0.01-0.02%, balance of copper and inevitable impurity.
3. the preparation method of silver-based brazing alloy according to claim 1 and 2, it is characterised in that comprise the following steps：
(1) Cu of Ni and half quality is carried out into advance melting, is made intermediate alloy Cu-Ni；
(2) Cu of P and half quality is carried out into pre-selection melting, is made intermediate alloy Cu-P；
(3) before melting, to Sn treatment, the Sn of bulk is prepared into filamentous Sn；First added during charging Cu-Ni, Cu-P,
Ag, Zn, Sn, Ni, Mn, In, Ga and rare earth element, add Sn until completely melted, add coverture to rise after the completion of charging immediately
To insulation effect；
(4) after melting, then silver-based soldering intermediate alloy is obtained by continuous casting, crowded company, shaping, cleaning；To be closed in the middle of silver-based soldering
Golden 100-150 mesh is standby；
(5) Graphene is added into alcohol, with ultrasonically treated；
(6) Graphene alcoholic solution and alloyed powder after will be ultrasonically treated add high energy ball mill, 150-200r/min, temperature
150-200 DEG C, grind 10-15min；
(7) Graphene after grinding and alloy powder mixture are dried；
(8) mixture after drying is put into grinding tool, extrusion forming；
(9) by the mixed powder after shaping at 250-300 DEG C, 3-5h is sintered, both obtains silver-based brazing alloy.
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| CN107186331A (en) * | 2017-06-28 | 2017-09-22 | 兰州大学 | A kind of new YBCO coating conductors welding point of graphene-containing and preparation method |
| CN108857149A (en) * | 2018-08-29 | 2018-11-23 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of aluminum welding tin paste |
| CN112059468A (en) * | 2019-07-26 | 2020-12-11 | 昆明贵金属研究所 | Silver-based brazing filler metal alloy, preparation method thereof, and preparation methods of foil strip and wire material |
| CN113369746A (en) * | 2021-06-17 | 2021-09-10 | 云南大学 | High-strength silver-based brazing filler metal and preparation method thereof |
| CN114414333A (en) * | 2022-01-10 | 2022-04-29 | 湘潭大学 | Preparation method and application of rare earth modified graphene oxide composite solder |
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| CN108857149A (en) * | 2018-08-29 | 2018-11-23 | 佛山朝鸿新材料科技有限公司 | A kind of preparation method of aluminum welding tin paste |
| CN112059468A (en) * | 2019-07-26 | 2020-12-11 | 昆明贵金属研究所 | Silver-based brazing filler metal alloy, preparation method thereof, and preparation methods of foil strip and wire material |
| CN112059468B (en) * | 2019-07-26 | 2021-12-24 | 昆明贵金属研究所 | Silver-based brazing filler metal alloy, preparation method thereof, and preparation methods of foil strip and wire material |
| CN113369746A (en) * | 2021-06-17 | 2021-09-10 | 云南大学 | High-strength silver-based brazing filler metal and preparation method thereof |
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Application publication date: 20170613 |