CN106282880A - A kind of antioxidation tin plating electrolyte based on yttrium bismuth phosphorus - Google Patents
A kind of antioxidation tin plating electrolyte based on yttrium bismuth phosphorus Download PDFInfo
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- CN106282880A CN106282880A CN201610790261.7A CN201610790261A CN106282880A CN 106282880 A CN106282880 A CN 106282880A CN 201610790261 A CN201610790261 A CN 201610790261A CN 106282880 A CN106282880 A CN 106282880A
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- yttrium
- tin plating
- phosphorus
- plating electrolyte
- bismuth
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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
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- 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
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
Abstract
The invention belongs to metal oxidation resistance resist technology field, specifically disclose a kind of antioxidation tin plating electrolyte based on yttrium bismuth phosphorus, comprise following component: yttrium, bismuth, phosphorus, stannum.Wherein, on the basis of the weight of described stannum, the percentage by weight of described yttrium is 0.005% 0.02%, and the percentage by weight of described bismuth is 0.004% 0.05%, and the percentage by weight of described phosphorus is 0.01% 0.05%.The present invention adds yttrium, bismuth, phosphorus in tin liquor, the oxidation that can effectively suppress tin plating electrolyte, the wettability improving tin plating electrolyte, the generation of minimizing scruff, raising stannum product lumber recovery, the productivity ratio of raising hot tinning product, and do not affect other physical and mechanical properties of tin-plated product；The antioxidation tin plating electrolyte low cost of the present invention, does not change existing production technology, does not affect existing equipment regular maintenance and maintenance, meet environmental requirement, do not affect the working environment of Workplace.
Description
Technical field
The present invention relates to metal oxidation resistance resist technology field, be specifically related to a kind of antioxidation based on yttrium bismuth phosphorus tin plating
Liquid, is mainly used in photovoltaic welding belt.
Background technology
Along with the fast development of electron trade, fusing point is low, good corrosion resistance is combined with metallic matrix because having for kamash alloy
Property the advantage such as good, be widely used in the field such as photovoltaic welding belt, Electronic Packaging.But, the liquid tin alloy pole under molten condition
Oxidizable formation scruff, block tin, wherein contain a large amount of unoxidized stannum, cause raw material to utilize insufficient, produces waste, increases
Production cost, also can affect the quality of product.Additionally, in the production process of photovoltaic welding belt, in stannum stove, the oxidation of ashbury metal is also
Aberration can be produced on welding surface, affect outward appearance, and easily form black speck during the transport and storage in later stage, cause producing
Product are scrapped.In order to ensure the reliability of welding, need to improve the antioxygenic property of kamash alloy.
The oxidation measure solving melt stannum at present mainly has melt cladding process, protective atmosphere method and melt modification method.Melt
Coverture in cladding process easily remains, and readily volatilized, the carbonization of being heated, smolders, pollutes environment, additionally, general coverture
For inorganic salts, easily production equipment is caused heavy corrosion, affect the production order.Atmosphere protection method processing equipment is huge, raw
Product cost is high.Melt modification rule only need to be on the premise of ensureing scolding tin self wettability, brazing property, by adding alloy
Element is to stannum melt modification, to improve its antioxygenic property, has that production operation is simple, input cost is low, not by external environment
The advantages such as impact.
But existing antioxidant is relatively costly on market, specific aim is relatively strong, and antioxidative effect is not satisfactory, and main
Will can bring the problem such as devil liquor recovery, environmental pollution based on organic solvent, the method added by inorganic elements improves stannum
The antioxygenic property of melt seldom has actually used case.
Summary of the invention
For problems of the prior art, it is an object of the invention to provide the base that a kind of low cost, the suitability are strong
In the antioxidation tin plating electrolyte of yttrium bismuth phosphorus, it is mainly used in photovoltaic welding belt；The antioxygenic property of this antioxidation tin plating electrolyte is high, can effectively subtract
The generation amount of few scruff/block tin, improves the utilization rate of stannum.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
A kind of antioxidation tin plating electrolyte based on yttrium bismuth phosphorus, it is characterised in that comprise following component: yttrium, bismuth, phosphorus, stannum.
Preferably, with the weight of described stannum for a hundred per cent benchmark, the percentage by weight of described yttrium is 0.005%-
0.02%, the percentage by weight of described bismuth is 0.004%-0.05%, and the percentage by weight of described phosphorus is 0.01%-0.05%.
It is further preferred that the percentage by weight of described yttrium is 0.01%-0.02%.
It is further preferred that the percentage by weight of described bismuth is 0.01%-0.04%.
It is further preferred that the percentage by weight of described phosphorus is 0.02%-0.04%.
Owing to the industrial temperature of tin liquor is relatively low, when adding anti-oxidizing elements yttrium, bismuth, phosphorus, these elements all can not be quick
Melt, accordingly, it would be desirable to be configured to the kamash alloy of certain content.
Preferably, described yttrium melts with the form of yttrium-stannum intermediate alloy and prepares described antioxidation tin plating electrolyte.
Preferably, described bismuth melts with the form of bismuth-stannum intermediate alloy and prepares described antioxidation tin plating electrolyte.
Preferably, described phosphorus melts with the form of phosphorus-stannum intermediate alloy and prepares described antioxidation tin plating electrolyte.
Preferably, the content of the yttrium of described yttrium-stannum intermediate alloy is the 1% of described yttrium-stannum intermediate alloy quality.
Preferably, the content of the bismuth of described bismuth-stannum intermediate alloy is the 1% of described bismuth-stannum intermediate alloy quality.
Preferably, the content of the phosphorus of described phosphorus-stannum intermediate alloy is the 5% of described phosphorus-stannum intermediate alloy quality.
Compared with prior art, the invention have the benefit that
The present invention adds yttrium, bismuth, phosphorus in tin plating electrolyte, can effectively suppress the oxidation of tin plating electrolyte, improve the moistening of tin plating electrolyte
Performance, the generation of minimizing scruff, raising stannum product lumber recovery, the productivity ratio of raising hot tinning product, and do not affect tin plating product
Other physical and mechanical properties of product；The antioxidation tin plating electrolyte low cost of the present invention, does not change existing production technology, does not affect existing
There are equipment regular maintenance and maintenance, meet environmental requirement, do not affect the working environment of Workplace.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the present invention.
The invention provides a kind of antioxidation tin plating electrolyte based on yttrium bismuth phosphorus, comprise following component: yttrium, bismuth, phosphorus, stannum.Its
In, on the basis of the weight of described stannum, the percentage by weight of yttrium is 0.005%-0.04%, and the percentage by weight of bismuth is
0.004%-0.05%, the percentage by weight of phosphorus is 0.01%-0.05%.
Embodiment 1
Take 100g tin plating electrolyte two parts, be designated as 1#, 2# respectively, under conditions of temperature 230 DEG C, add in 1# tin plating electrolyte simultaneously
Enter yttrium, bismuth, phosphorus；Wherein, on the basis of tin plating electrolyte weight, the yttrium that added, bismuth, the percentage by weight of phosphorus be respectively 0.02%,
0.04%, 0.02%, yttrium adds with the form of yttrium-stannum intermediate alloy, and yttrium content is described yttrium-stannum intermediate alloy quality
1%；Bismuth adds with the form of bismuth-stannum intermediate alloy, and 1% that bi content is described bismuth-stannum intermediate alloy quality；Phosphorus with phosphorus-
The form of stannum intermediate alloy adds, and 5% that phosphorus content is described phosphorus-stannum intermediate alloy quality.
2# tin plating electrolyte is blank group, and after being aoxidized respectively by 1#, 2# tin plating electrolyte 5 hours, (oxidizing condition is: room temperature heats
To 230 DEG C, constant temperature after 5 hours air cooling to room temperature), test the weight of 1#, 2# tin plating electrolyte respectively, and the weightening finish before and after being aoxidized
Amount, characterizes its antioxygenic property with gain in weight, and result of the test is as shown in table 1, as shown in Table 1, add in tin plating electrolyte yttrium,
Bismuth, phosphorus, can be obviously improved the antioxygenic property of tin liquor.
Above-mentioned 1# and 2# tin plating electrolyte is detected in copper wettability of the surface, with tin plating electrolyte the paving of anaerobic red copper surface
Developable surface amasss and characterizes, and method of testing is: the red copper sheet sand papering of annealing is gone removing oxide layer, and cleans with ethanol, take
10g tin plating electrolyte is placed on red copper sheet, covers with Colophonium or other scaling powders, is warming up to 230 DEG C, takes out, treat cold after insulation 60s
But measuring spreading area (concrete employing is taken pictures, and utilizes Imge-Pro plus computed in software area) to room temperature, 1# and 2# plates
The wettability test of tin liquor respectively does 3 groups, and spreading area takes its meansigma methods, with the wetting areas of 2# blank group is
The moistening relative area of 100% conversion 1# tin plating electrolyte, result of the test is shown in Table 1.As shown in Table 1, the wettability of 1# tin plating electrolyte with
The wettability of blank group tin plating electrolyte has been compared and has been obviously improved, it is seen that add yttrium, bismuth, phosphorus, yttrium, bismuth, phosphorus in tin liquor simultaneously
Generation effect can be worked in coordination with, and then improve the wettability of tin plating electrolyte.
Testing the fusing point of above-mentioned 1# and 2# tin plating electrolyte test specimen, fusing point uses differential scanning calorimeter (DSC) to carry out
Test, test result is shown in Table 1.As shown in Table 1, tin liquor is added yttrium, bismuth, phosphorus simultaneously, the fusing point of tin plating test specimen is not produced shadow
Ring.
Yield strength and tensile strength to above-mentioned 1# and 2# tin plating electrolyte test specimen are tested, and method of testing is routine side
Method, test result is shown in Table 1.As shown in Table 1, tin liquor is added yttrium, bismuth, phosphorus simultaneously, to the yield strength of tin plating electrolyte test specimen and anti-
Tensile strength does not the most produce impact.
Table 1
| Tin plating electrolyte is numbered | 1# | 2# |
| Gain in weight (g) after 5h oxidation | 0.185 | 0.350 |
| Sprawl relative area (%) | 140 | 100 |
| Yield strength (MPa) | 64 | 65 |
| Tensile strength (MPa) | 212 | 190 |
| Fusing point (DEG C) | 183 | 183 |
Comparative example 1
Take 100g tin plating electrolyte five parts, numbered 1#, 2#, 3#, 4#, and under conditions of temperature 230 DEG C, in 1# tin plating electrolyte
Add the yttrium of tin plating electrolyte weight 0.02%, in 2# tin plating electrolyte, add the bismuth of tin plating electrolyte weight 0.04%, add in 3# tin plating electrolyte
Enter the phosphorus of tin plating electrolyte weight 0.02%, without any element in 4# tin plating electrolyte, as blank group, aoxidize (oxidation in 5 hours
Condition is: room temperature is heated to 230 DEG C, constant temperature after 5 hours air cooling to room temperature) after test the weight of 1#, 2#, 3#, 4# tin plating electrolyte respectively
Amount, characterizes its antioxygenic property with the rate of body weight gain before and after each group of tin plating electrolyte oxidation, and result of the test is as shown in table 2.
Above-mentioned 1#, 2#, 3#, 4# tin plating electrolyte is detected in copper wettability of the surface, with tin plating electrolyte at anaerobic red copper table
The spreading area in face characterizes, and method of testing is with embodiment 1, and test result is shown in Table 2.To above-mentioned 1#, 2#, 3#, 4# tin plating electrolyte
Test specimen fusing point, yield strength and tensile strength are tested, and method of testing is with embodiment 1, and test result is shown in Table 2.
Table 2
| Tin plating electrolyte is numbered | 1# | 2# | 3# | 4# |
| Gain in weight (g) after 3h oxidation | 0.196 | 0.301 | 0.272 | 0.350 |
| Sprawl relative area (%) | 75 | 165 | 102 | 100 |
| Yield strength (MPa) | 65 | 65 | 65 | 65 |
| Tensile strength (MPa) | 190 | 190 | 190 | 190 |
| Fusing point (DEG C) | 183 | 183 | 183 | 183 |
As shown in Table 2, tin plating electrolyte adds yttrium or bismuth or phosphorus, all antioxygenic property to tin plating electrolyte have carrying by a small margin
Rise.The oxidation test result of comparative example 1 understands, the antioxygenic property of the antioxidation tin plating electrolyte based on yttrium bismuth phosphorus of the application
It is substantially better than and is individually added into the antioxygenic property of tin plating electrolyte after yttrium, bismuth, phosphorus.
As shown in Table 2, the addition of yttrium can be obviously improved the antioxygenic property of tin plating electrolyte, but under its wettability is obvious
Dropping, this may have the reason of several respects: one, the addition of yttrium reduces the surface tension of tin plating electrolyte, is of value to and improves base material
Wettability；Its two, owing to the oxidation activity of yttrium is more than other compositions in stannum and tin liquor, therefore yttrium is preferential on the surface of tin plating electrolyte
Oxidation filming, is unfavorable for moistening；Its three, excess yttrium can be at tin plating electrolyte Surface Segregation, the positive absorption on surface tends to saturated, works as yttrium
Addition when exceeding certain value, it will reduce the wettability of tin plating electrolyte, its four, yttrium is formed with other elements in tin plating electrolyte
Compound or eutectic phase are likely to reduce its wettability.
Meanwhile, from Table 2, it can be seen that tin plating electrolyte adds yttrium or bismuth or phosphorus, all fusing point and the physics to tin plating test specimen
Mechanical property no impact.
But by the result of the test of comparative example 1 compared with Example 1, it can be seen that embodiment 1 is simultaneously introduced yttrium bismuth phosphorus
Kamash alloy, while being obviously improved tin plating electrolyte non-oxidizability, be also obviously improved its wettability, do not affected tin plating simultaneously
The physical and mechanical property of product.
Embodiment 2
The present embodiment, as a example by industry tin-coated copper production line, fills the stannum melt of 20kg in the stannum stove of tin-coated copper production line,
Temperature is 225-235 DEG C, when stirring starts, adds 1% yttrium-stannum intermediate alloy in the stannum stove filling 20kg stannum melt
0.2kg-0.4kg, 1% bismuth-stannum intermediate alloy 0.2kg-0.8kg, 5% phosphorus-stannum intermediate alloy 0.08kg-0.16kg, obtains base
Antioxidation tin plating electrolyte in yttrium bismuth phosphorus；Then with 80m/min speed, anaerobic copper belt is carried out hot tinning.
Comparative example 2
The present embodiment, as a example by industry tin-coated copper production line, fills the stannum melt of 20kg in the stannum stove of tin-coated copper production line,
Temperature is 225-235 DEG C, directly to anaerobic copper belt, tin liquor is carried out hot tinning with 80m/min speed.All-in-one daily output scruff
Accounting rate 0.56%, semiautomatic loading mechanism daily output block tin accounting rate about 15.58%.
Embodiment 2 is compared with this comparative example 2, and daily output scruff accounting rate drops to about 0.25%, produces block tin accounting daily
Rate drops to about 11.5%, substantially increases the utilization rate of stannum and improves the lumber recovery of tinned wird, decreasing life simultaneously
" dragging for slag " operation during product, improves productivity ratio.
The sample of embodiment 2 and comparative example 2 is carried out salt spray test, and the condition of salt spray test is as follows: temperature 35 DEG C, humidity
More than 90%, concentration is the NaCl solution of 10%, and test period is 48 hours.The corrosion condition of each test specimen after observation accelerated corrosion
Understanding, the test specimen of comparative example 2, under salt mist environment, occurs oxidation black speck successively, and the test specimen of embodiment 2 is little 72 after 48 hours
A small amount of stain only occurred time after.
Dividing in the present invention, yttrium is affine with oxygen atom can be less, under an oxygen atmosphere, has precedence over oxygen atom and forms Y2O3, shape
Become one layer of fine and close protecting film, hinder the continuation internal diffusion of oxygen atom, prevent the oxidation of tin liquor；It addition, yttrium atom can be at crystalline substance
Deposit at boundary, " pinning " dislocation, play the effect of refined crystalline strengthening.Bismuth and phosphorus are favorably improved the wettability of copper and stannum, can be effective
Improve the antioxygenic property of stannum melt.
To sum up, in the present invention, adding yttrium, bismuth, three kinds of elements of phosphorus in tin plating electrolyte, these three element can be on tin plating electrolyte surface
Generate the oxide-film of a kind of densification, hinder oxygen atom to tin liquor diffusion inside, prevent the continuation of tin liquor from aoxidizing, thus be effectively improved
The antioxygenic property of tin plating electrolyte, meanwhile, can promote tin plating electrolyte wettability, and have substantially no effect on other physics of tin-plated product
Mechanical property；Low cost, does not change existing production technology, does not affect existing equipment regular maintenance and maintenance；Meet environmental protection to want
Ask, do not affect the working environment of Workplace.
Although, in this specification, the present invention is described in detail the most with a general description of the specific embodiments,
But on the basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
Enclose.
Claims (8)
1. an antioxidation tin plating electrolyte based on yttrium bismuth phosphorus, it is characterised in that comprise following component: yttrium, bismuth, phosphorus, stannum.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 1, it is characterised in that be with the weight of described stannum
Benchmark, the percentage by weight of described yttrium is 0.005%-0.02%, and the percentage by weight of described bismuth is 0.004%-0.05%, institute
The percentage by weight stating phosphorus is 0.01%-0.05%.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 2, it is characterised in that the weight percent of described yttrium
Ratio is 0.01%-0.02%.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 2, it is characterised in that the weight percent of described bismuth
Ratio is 0.01%-0.04%.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 2, it is characterised in that the weight percent of described phosphorus
Ratio is 0.02%-0.04%.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 1, it is characterised in that described yttrium is with in yttrium-stannum
Between the form fusing described antioxidation tin plating electrolyte based on yttrium bismuth phosphorus of preparation of alloy.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 1, it is characterised in that described bismuth is with in bismuth-stannum
Between the form fusing described antioxidation tin plating electrolyte based on yttrium bismuth phosphorus of preparation of alloy.
Antioxidation tin plating electrolyte based on yttrium bismuth phosphorus the most according to claim 1, it is characterised in that described phosphorus is with in phosphorus-stannum
Between the form fusing described antioxidation tin plating electrolyte based on yttrium bismuth phosphorus of preparation of alloy.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610790261.7A CN106282880B (en) | 2016-08-31 | 2016-08-31 | A kind of anti-oxidant tin plating electrolyte based on yttrium bismuth phosphorus |
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| CN201610790261.7A CN106282880B (en) | 2016-08-31 | 2016-08-31 | A kind of anti-oxidant tin plating electrolyte based on yttrium bismuth phosphorus |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002180226A (en) * | 2000-12-12 | 2002-06-26 | Totoku Electric Co Ltd | Lead-free tin alloy solder plated wire |
| CN102560311A (en) * | 2012-03-16 | 2012-07-11 | 鹰潭市众鑫成铜业有限公司 | Alloy used in hot plating process of tinned wire |
| CN102660723A (en) * | 2012-05-17 | 2012-09-12 | 合肥工业大学 | Rare-earth modified tin alloy for continuous hot-dip coating of copper wire and copper-coated metal composite wire, and manufacturing method thereof |
-
2016
- 2016-08-31 CN CN201610790261.7A patent/CN106282880B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002180226A (en) * | 2000-12-12 | 2002-06-26 | Totoku Electric Co Ltd | Lead-free tin alloy solder plated wire |
| CN102560311A (en) * | 2012-03-16 | 2012-07-11 | 鹰潭市众鑫成铜业有限公司 | Alloy used in hot plating process of tinned wire |
| CN102660723A (en) * | 2012-05-17 | 2012-09-12 | 合肥工业大学 | Rare-earth modified tin alloy for continuous hot-dip coating of copper wire and copper-coated metal composite wire, and manufacturing method thereof |
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