CN107475563B - One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof - Google Patents
One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof Download PDFInfo
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- CN107475563B CN107475563B CN201711000131.XA CN201711000131A CN107475563B CN 107475563 B CN107475563 B CN 107475563B CN 201711000131 A CN201711000131 A CN 201711000131A CN 107475563 B CN107475563 B CN 107475563B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/08—Tin or alloys based thereon
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Abstract
The present invention relates to an Albatra metal hot dip rare earth tin-based alloys, are made of the element of following mass fraction: the RE of the Ag of the Ni of 0.1-2.5%, 0.1-0.5%, 0.05-0.35%, and surplus is Sn and inevitable impurity element.Copper alloy plate strip hot dip of the invention has alloying component relatively easy with rare earth tin-based alloy, at low cost, hot-dip coating IMC thickness is thin and the long main trend of thickness is small, the advantages that being not likely to produce cavity and whisker in use, it can be used for worked copper and copper alloy plate strip, especially CuNiSi series alloy strip, the copper plate/strip product for carrying out hot-dip through alloy of the invention are mainly used for the manufacture of all kinds of electric power connectors in fields such as integrated circuit, electronic apparatus, intelligence equipment, auto industry and electronic connector etc..
Description
Technical field
The present invention relates to metal coating material fields, and in particular to Albatra metal hot dip rare earth tin-based alloy and its a system
Preparation Method.
Background technique
Tin plating copper alloy plate strip is widely used in the high-end fields such as aerospace, military project, automobile, communication and electronics, to the greatest extent
Pipe China copper plate/strip industry continues to develop, but copper alloy plate strip tin plating at present is not still able to satisfy the market demand.At present about
The research of the institutional framework of copper alloy plate strip tin coating, performance and production technology is concentrated mainly on the research of electrotinning, electrotinning
Major advantage is coated metal thickness uniformly and can arbitrarily control, but its complex production process, operation require stringent, electroplating device
Price is high, electroplating bath components are complicated.
Hot-dip is that treated metal works are immersed to a kind of method that the coat of metal is obtained in molten metal, referred to as
Hot dip.Compared with plating, the advantages of hot-dip be weldability is good, plated layer compact securely, production is simple, process is simple, delivery
Phase is short, the simple price of equipment is low etc., the disadvantage is that scruff is more, tin thickness is uneven, tin liquor is oxidizable, resting period is short etc..Mesh
Preceding China is concentrated mainly on the hot dipped tinning of steel surface, i.e., the matrix gold of most of hot dipped tinnings about the research of hot dipped tinning
Belonging to is steel material, and then more rare as the hot dipped tinning of basis material using copper or copper alloy.
Pure tin should not be directly used in or immersion, main reason is that, the room temperature residence time is longer or hot operation holds
So that hot tinning material surface is formed the whisker of electric conductivity, cause electric power connector or integrated circuit board short circuit, thus to copper and
The research of the dedicated kamash alloy of Cu alloy material hot dip is of great significance.
Summary of the invention
The purpose of the present invention is to provide an Albatra metal hot dip rare earth tin-based alloys and preparation method thereof.
In order to solve the above technical problems, the technical scheme adopted by the invention is that: an Albatra metal hot dip rare earth tin-based
Alloy is made of the element of following mass fraction: the RE of the Ag of the Ni of 0.1-2.5%, 0.1-0.5%, 0.05-0.35%, surplus are
Sn and inevitable impurity element.
Further, the RE is La, Ce, Pr and Nd mixture of 45:30:20:5 in mass ratio.
Further, the purity of the RE is calculated as 99.9% or more with the sum of La, Ce, Pr and Nd mass fraction.
Further, the rare earth tin-based alloy is referred to the matter of Ni in the intermediate alloy by pure Sn, intermediate alloy SnNi5(
The mass fraction that amount score be 5%, Sn for 95%), intermediate alloy SnAg3.5(refer to that the mass fraction of Ag in the intermediate alloy is
The mass fraction of 3.5%, Sn by 96.5%) and RE be made.
Further, the purity of the pure Sn is based on mass fraction are as follows: Sn >=99.95%.
Further, the purity of the intermediate alloy SnNi5 is based on mass fraction are as follows: Ni >=4.95%, surplus Sn.
Further, the purity of the intermediate alloy SnAg3.5 is based on mass fraction are as follows: Ag >=3.49%, surplus are
Sn。
Further, the copper alloy is Cu-Ni-Si series alloy strip.
A kind of preparation method of rare earth tin-based alloy, comprising the following steps: by each member in rare earth tin-based alloy described above
The mass fraction of element weighs pure Sn, intermediate alloy SnNi5, intermediate alloy SnAg3.5 and RE, and pure Sn is put into intermediate frequency vacuum melting
Melting is carried out in furnace, being evacuated to pressure in furnace is 0.005-0.010Pa, is then charged with argon gas to 0.2-0.3MPa, is warming up to
600 DEG C, heat preservation to pure Sn is completely melt；Intermediate alloy SnNi5 is added, heat preservation to intermediate alloy SnNi5 is completely melt；In addition
Between alloy SnAg3.5, heat preservation is completely melt to intermediate alloy SnAg3.5；RE is added, heat preservation to RE is completely melt；It is cooled to 400
DEG C casting ingot-forming, obtains rare earth tin-based alloy.
Further, at least one of intermediate alloy SnNi5 and intermediate alloy SnAg3.5 are made with the following method: pressing
Ingredient is weighed according to intermediate alloy each element mass fraction, water cooling copper sleeve vacuum non-consumable smelting furnace is put into, is evacuated to furnace internal pressure
It is by force 0.005-0.010Pa, is then charged with argon gas to 0.2-0.3MPa, electric arc melting to ingredient is completely melt, closing electric arc makes
Melt is cooled to complete solidification, and by melt turn-over after solidification, repeated melting, cooling, turn-over step 2-4 times are obtained corresponding
Intermediate alloy.
In the present invention each alloys producing and the utility model has the advantages that
1, the main function of Ni is to form Ni3Sn、Ni3Sn2、Ni3Sn4Equal intermetallic compounds, inhibit interface C u6Sn5
The growth of intermetallic compound；The wettability of Sn alloy is improved, shortens wetting time, is effectively improved the spreadability of Sn alloy
Energy；Needle-shaped Cu6Sn5Intermetallic compound is changed into spherical or tabular；Improve the mobility of Sn alloy, inhibits interface C u copper
Dissolution；The life quantity of slag of Sn is reduced, antioxygenic property is improved；
2, the wettability of tin alloy can be improved in the effect of Ag, the addition of Trace Ag, refines Sn primary crystal tissue, improves Sn
Alloy plasticity and creep resistance；Interface forms compound layer (Ag between composition metal3Sn+Cu6Sn5), have between hindering interface metal
The effect of compound layer growth；
3, the main function of mischmetal LaCePrNd: there is deoxidization desulfuration, purify the effect of alloy melt；Improve alloy
Mobility reduces alloy molten state viscosity；It prevents alloy surface from further aoxidizing, there is the shape for hindering alloy surface tin content
At；
4, the performance indicator of rare earth tin-based alloy of the invention are as follows: standard electrode potential 0.3178-0.3384V, fusing point
188.2-217.8 DEG C, tensile strength 50.6-90.4MPa, elongation percentage 36.1-61.6%；Copper alloy plate strip hot dip of the invention is used
Rare earth tin-based alloy has alloying component relatively easy, and at low cost, hot-dip coating IMC thickness is thin and the long main trend of thickness is small, uses
In be not likely to produce cavity and the advantages that whisker, can be used for worked copper and copper alloy plate strip, especially Cu-Ni-Si series alloy plate
Band, wetability and adhesion are good, are not likely to produce dross phenomenon, and the copper plate/strip product for carrying out hot-dip through alloy of the invention is main
System for all kinds of electric power connectors in fields such as integrated circuit, electronic apparatus, intelligence equipment, auto industry and electronic connector etc.
It makes.
Specific embodiment
The present invention will be further described in detail combined with specific embodiments below.
Embodiment 1
A kind of Cu-Ni-Si series alloy strip hot dip rare earth tin-based alloy, is made of the element of following mass fraction:
0.5% Ni, 0.15% Ag, 0.05% RE, surplus are Sn and inevitable impurity element；The RE is La, Ce, Pr
With the Nd mixture of 45:30:20:5 in mass ratio；The purity of the RE is calculated as with the sum of La, Ce, Pr and Nd mass fraction
99.9% or more；
The preparation method of the rare earth tin-based alloy the following steps are included:
(1) preparation of intermediate alloy: intermediate alloy SnNi5 and intermediate alloy SnAg3.5 is all made of following method and is made: pressing
Ingredient, which is weighed, according to intermediate alloy each element mass fraction (by taking intermediate alloy SnNi5 as an example, weighs pure Sn according to the mass ratio of 95:5
With pure Ni), it is put into water cooling copper sleeve vacuum non-consumable smelting furnace, being evacuated to pressure in furnace is 0.007Pa, is then charged with argon gas extremely
0.2-0.3MPa, electric arc melting to ingredient are completely melt that closing electric arc makes melt be cooled to complete solidification, and melt after solidification is turned over
Face, repeated melting, cooling, turn-over step 3 time, obtains corresponding intermediate alloy；The purity of the intermediate alloy SnNi5 with
Mass fraction is calculated as: Ni >=4.95%, surplus Sn；The purity of the intermediate alloy SnAg3.5 is based on mass fraction are as follows: Ag
>=3.49%, surplus Sn；
(2) mass fraction of each element according to claim 1 weighs pure Sn(purity based on mass fraction are as follows: and Sn >=
99.95%), intermediate alloy SnNi5, intermediate alloy SnAg3.5 and RE, pure Sn is put into intermediate frequency vacuum melting furnace and carries out melting,
Furnace lining material is magnesia, and being evacuated to pressure in furnace is 0.008Pa, is then charged with argon gas to 0.2-0.3MPa, is warming up to 600
DEG C, heat preservation to pure Sn is completely melt (about 30-60min)；Intermediate alloy SnNi5,600 DEG C of heat preservations to intermediate alloy SnNi5 are added
It is completely melt (about 30-60min)；Intermediate alloy SnAg3.5 is added, 600 DEG C of heat preservations to intermediate alloy SnAg3.5 are completely melt
(about 30-60min)；RE is added, 600 DEG C of heat preservations to RE are completely melt (about 30-60min)；400 DEG C are cooled to, punching block is selected to make
For die casting ingot, rare earth tin-based alloy is obtained；
The performance indicator of the present embodiment rare earth tin alloy are as follows: standard electrode potential 0.3384V, 189.8 DEG C of fusing point, tension
Intensity 50.6MPa, elongation percentage 61.6%.
Embodiment 2
A kind of Cu-Ni-Si series alloy strip hot dip rare earth tin-based alloy, is made of the element of following mass fraction:
1.0% Ni, 0.2% Ag, 0.25% RE, surplus are Sn and inevitable impurity element；The RE be La, Ce, Pr and
The Nd mixture of 45:30:20:5 in mass ratio；The purity of the RE is calculated as with the sum of La, Ce, Pr and Nd mass fraction
99.9% or more；
The preparation method is the same as that of Example 1, the performance indicator of embodiment rare earth tin alloy are as follows: standard electrode potential 0.3291V melts
198.9 DEG C, tensile strength 77.8MPa of point, elongation percentage 45.2%.
Embodiment 3
A kind of Cu-Ni-Si series alloy strip hot dip rare earth tin-based alloy, is made of the element of following mass fraction:
1.5% Ni, 0.3% Ag, 0.5% RE, surplus are Sn and inevitable impurity element；The RE be La, Ce, Pr and
The Nd mixture of 45:30:20:5 in mass ratio；The purity of the RE is calculated as with the sum of La, Ce, Pr and Nd mass fraction
99.9% or more；
The preparation method is the same as that of Example 1, the performance indicator of embodiment rare earth tin alloy are as follows: standard electrode potential 0.3178V melts
208.9 DEG C, tensile strength 90.4MPa of point, elongation percentage 36.1%.
Embodiment 4
A kind of Cu-Ni-Si series alloy strip hot dip rare earth tin-based alloy, is made of the element of following mass fraction:
0.1% Ni, 0.5% Ag, 0.1% RE, surplus are Sn and inevitable impurity element；The RE be La, Ce, Pr and
The Nd mixture of 45:30:20:5 in mass ratio；The purity of the RE is calculated as with the sum of La, Ce, Pr and Nd mass fraction
99.9% or more；
The preparation method is the same as that of Example 1, the performance indicator of embodiment rare earth tin alloy are as follows: standard electrode potential 0.3341V melts
188.2 DEG C, tensile strength 55.3MPa of point, elongation percentage 47.2%.
Embodiment 5
A kind of Cu-Ni-Si series alloy strip hot dip rare earth tin-based alloy, is made of the element of following mass fraction:
2.5% Ni, 0.1% Ag, 0.35% RE, surplus are Sn and inevitable impurity element；The RE be La, Ce, Pr and
The Nd mixture of 45:30:20:5 in mass ratio；The purity of the RE is calculated as with the sum of La, Ce, Pr and Nd mass fraction
99.9% or more；
The preparation method is the same as that of Example 1, the performance indicator of embodiment rare earth tin alloy are as follows: standard electrode potential 0.31898V,
217.8 DEG C of fusing point, tensile strength 85.3MPa, elongation percentage 38.9%.
Embodiment 6
A kind of Cu-Ni-Si series alloy strip hot dip rare earth tin-based alloy, is made of the element of following mass fraction:
2.0% Ni, 0.4% Ag, 0.15% RE, surplus are Sn and inevitable impurity element；The RE be La, Ce, Pr and
The Nd mixture of 45:30:20:5 in mass ratio；The purity of the RE is calculated as with the sum of La, Ce, Pr and Nd mass fraction
99.9% or more；
The preparation method is the same as that of Example 1, the performance indicator of embodiment rare earth tin alloy are as follows: collimator electrode current potential 0.3228V, fusing point
211.39 DEG C, tensile strength 72.6MPa, elongation percentage 46.5%.
Above embodiments are only some embodiments of the invention, in the case where not departing from basic idea of the present invention,
Any replacement and improvement should all be included in protection scope of the present invention.
Claims (8)
1. a kind of copper alloy plate strip hot dip rare earth tin-based alloy, which is characterized in that be made of the element of following mass fraction:
The RE of the Ag of the Ni of 0.1-2.5%, 0.15-0.5%, 0.05-0.35%, surplus are Sn and inevitable impurity element；
The rare earth tin-based alloy is made of pure Sn, intermediate alloy SnNi5, intermediate alloy SnAg3.5 and RE；The RE is
La, Ce, Pr and Nd mixture of 45:30:20:5 in mass ratio.
2. a kind of copper alloy plate strip hot dip rare earth tin-based alloy according to claim 1, it is characterised in that: the RE
Purity be calculated as 99.9% or more with the sum of La, Ce, Pr and Nd mass fraction.
3. a kind of copper alloy plate strip hot dip rare earth tin-based alloy according to claim 1, it is characterised in that: described is pure
The purity of Sn is based on mass fraction are as follows: Sn >=99.95%.
4. a kind of copper alloy plate strip hot dip rare earth tin-based alloy according to claim 1, it is characterised in that: in described
Between alloy SnNi5 purity based on mass fraction are as follows: Ni >=4.95%, surplus Sn.
5. a kind of copper alloy plate strip hot dip rare earth tin-based alloy according to claim 1, it is characterised in that: in described
Between alloy SnAg3.5 purity based on mass fraction are as follows: Ag >=3.49%, surplus Sn.
6. a kind of copper alloy plate strip hot dip rare earth tin-based alloy according to claim 1-5, it is characterised in that:
The copper alloy plate strip is Cu-Ni-Si series alloy strip.
7. a kind of preparation method of rare earth tin-based alloy according to claim 1, which comprises the following steps:
The mass fraction of each element according to claim 1 weighs pure Sn, intermediate alloy SnNi5, intermediate alloy SnAg3.5 and RE,
Pure Sn is put into intermediate frequency vacuum melting furnace and carries out melting, being evacuated to pressure in furnace is 0.005-0.010Pa, is then charged with argon
Gas is warming up to 600 DEG C, heat preservation to pure Sn is completely melt to 0.2-0.3MPa；Intermediate alloy SnNi5 is added, heat preservation to centre is closed
Golden SnNi5 is completely melt；Intermediate alloy SnAg3.5 is added, heat preservation to intermediate alloy SnAg3.5 is completely melt；RE, heat preservation is added
It is completely melt to RE；400 DEG C of casting ingot-formings are cooled to, rare earth tin-based alloy is obtained.
8. a kind of preparation method of rare earth tin-based alloy according to claim 7, which is characterized in that intermediate alloy SnNi5
It is made with the following method at least one of intermediate alloy SnAg3.5: weighing and match according to intermediate alloy each element mass fraction
Material, is put into water cooling copper sleeve vacuum non-consumable smelting furnace, and being evacuated to pressure in furnace is 0.005-0.010Pa, is then charged with argon gas
To 0.2-0.3MPa, electric arc melting to ingredient is completely melt, closing electric arc makes melt be cooled to complete solidification, by melt after solidification
Turn-over, repeated melting, cooling, turn-over step 2-4 times, obtains corresponding intermediate alloy.
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| CN201711000131.XA CN107475563B (en) | 2017-10-24 | 2017-10-24 | One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262159A (en) * | 1999-01-28 | 2000-08-09 | 株式会社村田制作所 | Leadless solder and welding product |
| CN102337422A (en) * | 2010-07-21 | 2012-02-01 | 中国科学院金属研究所 | Low-ablation lead-free tin plating alloy under high temperature |
| CN103205601A (en) * | 2013-04-11 | 2013-07-17 | 广东普赛特电子科技股份有限公司 | Damping brazing alloy and preparation method thereof |
-
2017
- 2017-10-24 CN CN201711000131.XA patent/CN107475563B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262159A (en) * | 1999-01-28 | 2000-08-09 | 株式会社村田制作所 | Leadless solder and welding product |
| CN102337422A (en) * | 2010-07-21 | 2012-02-01 | 中国科学院金属研究所 | Low-ablation lead-free tin plating alloy under high temperature |
| CN103205601A (en) * | 2013-04-11 | 2013-07-17 | 广东普赛特电子科技股份有限公司 | Damping brazing alloy and preparation method thereof |
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