CN118600500A - Electrotinning bismuth alloy plating solution and preparation method and application thereof - Google Patents
Electrotinning bismuth alloy plating solution and preparation method and application thereof Download PDFInfo
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- CN118600500A CN118600500A CN202410816532.6A CN202410816532A CN118600500A CN 118600500 A CN118600500 A CN 118600500A CN 202410816532 A CN202410816532 A CN 202410816532A CN 118600500 A CN118600500 A CN 118600500A
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- 238000007747 plating Methods 0.000 title claims abstract description 75
- 229910001152 Bi alloy Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title abstract description 12
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 claims abstract description 62
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- 238000005282 brightening Methods 0.000 claims abstract description 17
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims abstract description 14
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- BWHOZHOGCMHOBV-UHFFFAOYSA-N Benzalacetone Natural products CC(=O)C=CC1=CC=CC=C1 BWHOZHOGCMHOBV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 12
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 12
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 12
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 claims abstract description 12
- PLTSNKHBCZEGFS-UHFFFAOYSA-N 1,3,5-trimethoxycyclohexa-2,4-diene-1-carbaldehyde Chemical compound COC1=CC(OC)=CC(C=O)(OC)C1 PLTSNKHBCZEGFS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 29
- -1 diethyl triamine pentaacetic acid Chemical compound 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- RTIXKCRFFJGDFG-UHFFFAOYSA-N chrysin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=CC=C1 RTIXKCRFFJGDFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 claims description 2
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical compound OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 claims description 2
- WSNBSXDRBHWBCS-UHFFFAOYSA-N C(C)OS(=O)(=O)O.C1(=CC=CC2=CC=CC=C12)O Chemical compound C(C)OS(=O)(=O)O.C1(=CC=CC2=CC=CC=C12)O WSNBSXDRBHWBCS-UHFFFAOYSA-N 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 2
- 229960003330 pentetic acid Drugs 0.000 claims description 2
- 238000009713 electroplating Methods 0.000 abstract description 23
- 238000003466 welding Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 66
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
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- 238000010587 phase diagram Methods 0.000 description 11
- 238000000921 elemental analysis Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
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- 230000010287 polarization Effects 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001128 Sn alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
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- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 1
- 229910020830 Sn-Bi Inorganic materials 0.000 description 1
- 229910018728 Sn—Bi Inorganic materials 0.000 description 1
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- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
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- 239000005028 tinplate Substances 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention belongs to the technical field of electroplating, and particularly relates to an electroplating tin-bismuth alloy plating solution, a preparation method and application thereof. The plating solution provided by the invention takes deionized water as a solvent and comprises 30-60 g/L of stannous sulfate, 130-165 g/L of sulfuric acid, 4-20 g/L of bismuth sulfate, 0.3-2 g/L of brightening agent, 0.5-2g/L of dispersing agent, 0.1-0.5 g/L of complexing agent and 4-7g/L of stabilizer. Wherein the brightening agent is composed of 1,3, 5-trimethoxybenzaldehyde and benzalacetone according to the weight ratio of 1:3, and the dispersing agent is polyoxyethylene ether and polyethylene glycol according to the weight ratio of 1: (0.5-1), wherein the stabilizer is sodium citrate and hydroquinone according to the weight ratio of 1: (0.5-1.5). The plating solution can be applied to tin-bismuth alloy electroplating, and can be used for preparing a tin-bismuth alloy plating layer which is pure white and uniform, fine in crystallization, smaller in grain size, good in welding performance and capable of meeting various performance requirements.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to an electroplating tin-bismuth alloy plating solution, a preparation method and application thereof.
Background
With the global improvement of environmental protection requirements, the electroplating industry is gradually reducing or eliminating the use of harmful substances such as lead. As an environment-friendly material, the tin-bismuth alloy is an ideal alternative because of no lead and good physical and chemical properties. The electroplating tin-bismuth alloy is one electroplating technology for depositing tin-bismuth alloy layer on metal surface, this technique combines the characteristics of both tin and bismuth metals to form an alloy coating with unique properties. Currently, electroplated tin-bismuth alloy is widely applied to industries such as electronics, electrical appliances, aerospace, automobiles, communication and the like. In Printed Circuit Board (PCB) manufacture, it can act as a surface coating, improving connection reliability and providing protection. In addition, the tin-bismuth alloy plating layer is also suitable for welding and packaging of heat sensitive components due to the low melting point characteristic. The lead-free nature makes it compliant with environmental regulations such as RoHS (directive for limiting the use of certain harmful substances in electrical and electronic equipment). With the global improvement of environmental protection requirements, the electroplating industry is gradually reducing or eliminating the use of harmful substances such as lead. As an environment-friendly material, the tin-bismuth alloy is an ideal alternative because of no lead and good physical and chemical properties.
Tin-bismuth alloys are valued for their low melting point characteristics, which make them far lower than pure tin or pure bismuth, which makes them advantageous in soldering and low temperature processing. In the field of electroplating, the tin-bismuth alloy coating can be used as a lead-free alternative, especially in the manufacturing industry of electronic products with high environmental requirements, to replace the traditional lead-tin alloy coating. Similar to electroplated copper-tin alloys, the color of the tin-bismuth alloy coating also varies with the alloy composition, although the specific color range may vary from copper-tin alloy, which makes the control of the content of each component in the tin-bismuth alloy extremely important.
In summary, the background of the development of the electroplated tin-bismuth alloy technology is mainly to respond to the environmental protection requirement, pursue high-performance surface treatment solutions and meet the strict requirements of the modern electronic industry. Therefore, with the progress of technology and the increasing strictness of environmental regulations, the development of an electroplating technology which is environment-friendly and has moderate content of each component in tin-bismuth alloy is important for expanding the application range of electroplated tin-bismuth alloy.
Disclosure of Invention
In order to solve the problems, the invention provides an electroplating tin-bismuth alloy plating solution. The plating solution can be applied to electroplating tin-bismuth alloy, the electroplated coating contains 1% -3% of bismuth element and 97% -99% of tin element, and the surface of the coating is white and uniform.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
The electrolytic tin bismuth alloy plating solution takes deionized water as a solvent and comprises the following components in concentration: 30-60 g/L of stannous sulfate, 130-165 g/L of sulfuric acid, 4-20 g/L of bismuth sulfate, 0.3-2 g/L of brightening agent, 0.5-2g/L of dispersing agent, 0.1-0.5 g/L of complexing agent and 4-7g/L of stabilizer.
Preferably, the brightening agent is selected from two of naphthol ethoxysulfonic acid, 1,3, 5-trimethoxybenzaldehyde, benzoylacetone, sodium sulfosuccinate salt and benzalacetone.
Preferably, the brightening agent is prepared from the following components in percentage by weight: 3, 1,3, 5-trimethoxybenzaldehyde and benzalacetone.
The inventor finds that the two brightening agents are matched to provide necessary polarization effect, help to form fine crystals, improve the brightness of the coating, provide the potential capability of a low-current area, improve the uniformity of the coating, and have certain impurity resistance to prevent impurities from affecting the quality of the coating.
Preferably, the dispersing agent comprises polyoxyethylene ether and polyethylene glycol according to the weight ratio of 1: 0.5-1.
Through multiple tests, the invention finally adopts the combination of the two dispersants, can effectively disperse the effective components in the brightening agent, prevent the effective components from gathering, and simultaneously enhance the solubility and stability of the brightening agent in the plating solution, thereby ensuring the uniformity of the plating layer.
Preferably, the complexing agent is one of ethylenediamine tetraacetic acid, 2-phenoxypropionic acid, 5, 7-dihydroxyflavone, diethylenetriamine pentaacetic acid.
Preferably, the complexing agent is diethyl triamine pentaacetic acid.
Preferably, the stabilizer comprises sodium citrate and hydroquinone in a weight ratio of 1:0.5 to 1.5 percent.
The invention adopts the coordination agent and the stabilizer of specific types to compound in pairs, and can generate excellent concentration difference polarization, so that the tin-bismuth alloy plating layer which is white and uniform, fine in crystallization, smaller in grain size, good in welding performance and capable of meeting various performance requirements can be prepared.
The invention also provides a preparation method of the electroplated tin-bismuth alloy plating solution, which comprises the following steps:
S1, dissolving stannous sulfate, sulfuric acid and bismuth sulfate in water, stirring to fully dissolve the stannous sulfate, the sulfuric acid and the bismuth sulfate, standing and cooling to obtain a solution A;
s2, dissolving the brightening agent in water, and stirring and dissolving at room temperature to obtain a solution B;
S3, dissolving the dispersing agent, the complexing agent and the stabilizing agent in water, and stirring to fully dissolve the dispersing agent, the complexing agent and the stabilizing agent to obtain a solution C;
And S4, mixing the solution A obtained in the step S1 and the solution B obtained in the step S2, the solution C obtained in the step S3, adding water to fix the volume, and further stirring and mixing uniformly to obtain the composite material.
Preferably, the stirring in the step S1 is carried out for 20-30 min at the rotating speed of 100-200 rpm; the stirring conditions in the steps S2 and S3 are stirring for 20-30 min at the rotating speed of 50-100 rpm; and (3) stirring and uniformly mixing the materials in the step S4 at a rotating speed of 500-600 rpm for 30-40 min.
The invention also provides application of the electrolytic tin-bismuth alloy plating solution in electrolytic tin-bismuth alloy plating.
The invention designs a formula aiming at the electroplated tin-bismuth alloy plating solution, and the weight proportion of the brightening agent, the dispersing agent, the specially selected complexing agent and the stabilizing agent is precisely regulated, and the optimized compounding strategy of the special complexing agent and the stabilizing agent is adopted, so that the formation of concentration difference polarization is effectively promoted, and the generated tin-bismuth alloy plating layer shows excellent characteristics: the color is white and uniform, the crystallization is fine and compact, the grain size is refined, and meanwhile, excellent welding performance is ensured, so that various severe performance indexes are met. Meanwhile, the preparation method of the plating solution is simple, is beneficial to maintenance and management of the electrolyte, and improves the stability and practicability of the process. The new process is simple and convenient to operate, is easy to dock with the traditional process, and has wide application potential and value.
Particularly, in the formula of the invention, the complexing agent, the stabilizer, the brightening agent and the dispersing agent are perfectly compatible with an organic acid system (namely stannous sulfate, sulfuric acid and bismuth sulfate), so that the toxicity of the plating solution is greatly reduced, the wastewater treatment process is greatly simplified, and the environment-friendly effect of the whole electroplating process is ensured.
Compared with the prior art, the invention has the following advantages:
(1) The electroplating tin-bismuth alloy plating solution provided by the invention has reasonable formula, moderate tin-bismuth content in the tin-bismuth alloy plating layer generated by electroplating, white and uniform plating color, fine and compact crystallization, fine grain size and strong welding performance;
(2) The preparation method of the electroplated tin-bismuth alloy plating solution is simple, is beneficial to maintenance and management of the electrolyte, and reduces the production cost of the plating solution;
(3) The components in the tin-bismuth alloy of the electroplating solution provided by the invention are perfectly compatible, so that the toxicity of the electroplating solution is reduced, the wastewater treatment process is simplified, the environmental protection performance of the electroplating process is improved, and the application range of the tin-bismuth alloy of the electroplating solution is enlarged.
Drawings
FIG. 1 is a crystalline phase diagram of an electroplated tin-bismuth alloy coating obtained using the plating solution of example 1 at a magnification of 1000 times;
FIG. 2 is an elemental analysis result of an electroplated tin-bismuth alloy coating prepared using the plating solution of example 1;
FIG. 3 is a crystalline phase diagram of the electroplated tin-bismuth alloy coating obtained using the plating solution of example 2 at a magnification of 1000 times;
FIG. 4 is an elemental analysis result of an electroplated tin-bismuth alloy coating prepared using the plating solution of example 2;
FIG. 5 is a crystalline phase diagram of the electroplated tin-bismuth alloy coating obtained using the plating solution of example 3 at a magnification of 1000 times;
FIG. 6 is an elemental analysis result of an electroplated tin-bismuth alloy coating prepared using the plating solution of example 3;
FIG. 7 is a crystal phase diagram of an electroplated tin-bismuth alloy coating obtained by using the plating solution of comparative example 1 at a magnification of 1000 times;
FIG. 8 is an elemental analysis result of an electroplated tin-bismuth alloy coating prepared using the plating solution of comparative example 1;
FIG. 9 is a crystal phase diagram of an electroplated tin-bismuth alloy coating obtained by using the plating solution of comparative example 2 at a magnification of 1000 times;
FIG. 10 is an elemental analysis result of an electroplated tin-bismuth alloy coating prepared using the plating solution of comparative example 2.
Detailed Description
The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. Molecular biology experimental methods not specifically described in the following examples are all carried out with reference to the specific methods listed in the "guidelines for molecular cloning experiments" (third edition) j. Sambrook, or according to the kit and product instructions; the reagents and biological materials, unless otherwise specified, are commercially available.
Example 1 an electrolytic tin bismuth alloy plating solution
The electrolytic tin bismuth alloy plating solution takes deionized water as a solvent and comprises the following components in concentration: 45g/L of stannous sulfate, 145g/L of sulfuric acid (98% concentration), 10g/L of bismuth sulfate, 0.2g/L of 1,3, 5-trimethoxybenzaldehyde, 0.6g/L of benzalacetone, 0.5g/L of polyoxyethylene ether, 0.5g/L of polyethylene glycol, 0.3g/L of diethyl triamine pentaacetic acid, 3g/L of sodium citrate and 4g/L of hydroquinone.
The preparation method of the electrotinning bismuth alloy plating solution comprises the following steps:
S1, adding stannous sulfate, sulfuric acid (98%) and bismuth sulfate in the formula amount into 500mL of deionized water, stirring for 30min at a rotating speed of 100rpm, fully dissolving, standing and cooling to obtain a solution A;
S2, adding 1,3, 5-trimethoxybenzaldehyde and benzalacetone with the formula amount into 100mL of deionized water, stirring for 30min at room temperature at a rotating speed of 50rpm, fully dissolving, standing and cooling to obtain solution B;
s3, adding 100mL of deionized water, adding polyoxyethylene ether, polyethylene glycol, diethyl triamine pentaacetic acid, sodium citrate and hydroquinone according to the formula amount, and stirring at 30 ℃ for 30min at a rotating speed of 50r/min to fully dissolve the polyoxyethylene ether, the polyethylene glycol, the diethyl triamine pentaacetic acid, the sodium citrate and the hydroquinone to obtain a solution C;
S4, mixing the solution A obtained in the step S1 and the solution B obtained in the step S2, adding deionized water to the volume of 1L, stirring for 40min at the rotating speed of 500rpm, and uniformly mixing to obtain the aqueous solution C.
Example 2 an electrolytic tin bismuth alloy plating solution
The electrolytic tin bismuth alloy plating solution takes deionized water as a solvent and comprises the following components in concentration: 30g/L of stannous sulfate, 145g/L of sulfuric acid (98%), 20g/L of bismuth sulfate, 0.3g/L of 1,3, 5-trimethoxybenzaldehyde, 0.9g/L of benzalacetone, 0.6g/L of polyoxyethylene ether, 0.3g/L of polyethylene glycol, 0.2g/L of diethyl triamine pentaacetic acid, 2g/L of sodium citrate and 2g/L of hydroquinone.
The preparation method of the electrotinning bismuth alloy plating solution comprises the following steps:
s1, adding stannous sulfate, sulfuric acid (98%) and bismuth sulfate in the formula amount into 500mL of deionized water, stirring for 20min at a rotating speed of 200rpm, fully dissolving, standing and cooling to obtain a solution A;
S2, adding 1,3, 5-trimethoxybenzaldehyde and benzalacetone with the formula amount into 100mL of deionized water, stirring for 20min at room temperature at a rotating speed of 100rpm, fully dissolving, standing and cooling to obtain solution B;
S3, adding 100mL of deionized water, adding polyoxyethylene ether, polyethylene glycol, diethyl triamine pentaacetic acid, sodium citrate and hydroquinone according to the formula amount, and stirring at 30 ℃ for 20min at a rotating speed of 100r/min to fully dissolve the polyoxyethylene ether, the polyethylene glycol, the diethyl triamine pentaacetic acid, the sodium citrate and the hydroquinone to obtain a solution C;
s4, mixing the solution A obtained in the step S1 and the solution B obtained in the step S2, adding deionized water to the volume of 1L, stirring for 30min at the rotating speed of 600rpm, and uniformly mixing to obtain the aqueous solution.
Example 3 an electrolytic tin bismuth alloy plating solution
The electrolytic tin bismuth alloy plating solution takes deionized water as a solvent and comprises the following components in concentration: 60g/L of stannous sulfate, 145g/L of sulfuric acid (98%), 5g/L of bismuth sulfate, 0.3-2 g/L of brightening agent, 0.4g/L of 1,3, 5-trimethoxybenzaldehyde, 1.2g/L of benzalacetone, 0.7g/L of polyoxyethylene ether, 0.7g/L of polyethylene glycol, 0.5g/L of diethyl triamine pentaacetic acid, 3g/L of sodium citrate and 3g/L of hydroquinone.
The preparation method of the electrotinning bismuth alloy plating solution comprises the following steps:
s1, adding stannous sulfate, sulfuric acid (98%) and bismuth sulfate in the formula amount into 500mL of deionized water, stirring for 25min at a rotating speed of 150rpm, fully dissolving, standing and cooling to obtain a solution A;
s2, adding 1,3, 5-trimethoxybenzaldehyde and benzalacetone with the formula amount into 100mL of deionized water, stirring for 25min at room temperature at a rotating speed of 75rpm, fully dissolving, standing and cooling to obtain solution B;
S3, adding 100mL of deionized water, adding polyoxyethylene ether, polyethylene glycol, diethyl triamine pentaacetic acid, sodium citrate and hydroquinone according to the formula amount, and stirring at 30 ℃ for 25min at a rotating speed of 75r/min to fully dissolve the polyoxyethylene ether, the polyethylene glycol, the diethyl triamine pentaacetic acid, the sodium citrate and the hydroquinone to obtain a solution C;
S4, mixing the solution A obtained in the step S1 and the solution B obtained in the step S2, adding deionized water to the volume of 1L, stirring for 35min at the rotating speed of 650rpm, and uniformly mixing to obtain the aqueous solution C.
Comparative example 1 an electrolytic tin bismuth alloy plating solution
The components and preparation method of the electrotinning bismuth alloy plating solution are similar to those of the embodiment 3;
the difference from example 3 is that the brightening agent in comparative example 1 is benzalacetone.
Comparative example 2A tin bismuth alloy plating solution for electroplating
The components and preparation method of the electrotinning bismuth alloy plating solution are similar to those of the embodiment 3;
The difference from example 3 is that the stabilizer in comparative example 2 is sodium citrate.
Test example Performance test
1. Test sample: the electrolytic Sn-Bi alloy plating solutions prepared in examples 1-3 and comparative examples 1-2;
2. The test method comprises the following steps: the same batch of polished brass test pieces (100 mm. Times.65 mm. Times.0.2 mm, manufactured by Hongwei technologies, guangzhou) was taken, a tin plate was used as an anode, the polished brass test pieces were used as a cathode, and the plating solutions of examples and comparative examples were used to plate, respectively, with plating parameters of: the plating bath temperature is 25 ℃, the cathode current density is 2A/dm 2, the electroplating time is 5min, and the stirring mode is mechanical stirring, so as to obtain the tinned copper sheet.
The specific judgment criteria are as follows:
appearance: and adopting visual inspection to judge that the plating layer is fine, continuous, white and uniform, and the product is qualified.
Microscopic crystalline phase: and photographing and amplifying the crystal phase diagram of 1000 by using a scanning electron microscope, wherein the crystal phase is clear, the crystal is fine and has no cavity, and the qualified crystal is obtained.
Bismuth content: and testing the tin-bismuth content by using a scanning electron microscope. The bismuth content is 1-3% w/w, and the product is qualified.
Weldability test: the tin-plated copper sheets obtained in the first test of examples 1 to 3 and comparative examples 1 to 2 were immersed in the flux respectively, then immersed in molten tin at 250 ℃ for 5 seconds, taken out, and then inspected to be qualified in terms of no pinholes, bubbles, black spots, no tin plating, and the like.
3. Test results: the crystal phase diagrams and the elemental analysis results of the plating layers prepared in example 1 are shown in fig. 1 to 2, the crystal phase diagrams and the elemental analysis results of the plating layers prepared in example 2 are shown in fig. 3 to 4, the crystal phase diagrams and the elemental analysis results of the plating layers prepared in example 3 are shown in fig. 5 to 6, the crystal phase diagrams and the elemental analysis results of the plating layers prepared in comparative example 1 are shown in fig. 7 to 8, and the crystal phase diagrams and the elemental analysis results of the plating layers prepared in comparative example 2 are shown in fig. 9 to 10. The properties of the finally obtained plating layer are shown in Table 1.
TABLE 1 results of coating Performance test made with different plating solutions
| Electroplating example | Appearance of | Microscopic crystalline phases | Bismuth content (% w/w) | Solderability test |
| Example 1 | Qualified product | Smaller grains | 1.58 | Qualified product |
| Example 2 | Qualified product | Smaller grains | 2.31 | Qualified product |
| Example 3 | Qualified product | Smaller grains | 1.17 | Qualified product |
| Comparative example 1 | Failure to pass | The grains are larger | 0.27 | Qualified product |
| Comparative example 2 | Failure to pass | The grains are larger | 0.56 | Qualified product |
The results show that the plating solution of the electroplated tin-bismuth alloy compounded by the invention has excellent plating performance and completely meets the requirements of electroplated tin-bismuth alloy. In the comparative examples 1 and 2, the plating layer is slightly rough, the surface is uneven, the appearance is unqualified, the crystal grains are relatively large, and the bismuth content does not reach the standard, which further proves the coordination effect of the components in the technology of the patent.
Finally, it should be noted that the above-mentioned embodiments are merely illustrative of the principles, performances and effects of the present invention, and are not meant to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. The electrotinning bismuth alloy plating solution takes deionized water as a solvent and is characterized by comprising the following components in concentration: 30-60 g/L of stannous sulfate, 130-165 g/L of sulfuric acid, 4-20 g/L of bismuth sulfate, 0.3-2 g/L of brightening agent, 0.5-2g/L of dispersing agent, 0.1-0.5 g/L of complexing agent and 4-7g/L of stabilizer.
2. The electrolytic tin bismuth alloy plating bath as claimed in claim 1, wherein the brightening agent is selected from two of naphthol ethoxysulfonic acid, 1,3, 5-trimethoxybenzaldehyde, benzoylacetone, sodium sulfosuccinate, and benzalacetone.
3. The electrolytic tin bismuth alloy plating solution according to claim 2, wherein the brightening agent is 1:3, 1,3, 5-trimethoxybenzaldehyde and benzalacetone.
4. The electroplated tin-bismuth alloy plating solution according to claim 1, wherein the dispersing agent comprises polyoxyethylene ether and polyethylene glycol according to the weight ratio of 1: 0.5-1.
5. The electrolytic tin bismuth alloy plating solution as claimed in claim 1, wherein the complexing agent is one of ethylenediamine tetraacetic acid, 2-phenoxypropionic acid, 5, 7-dihydroxyflavone, diethylenetriamine pentaacetic acid.
6. The electrolytic tin bismuth alloy plating solution as claimed in claim 5, wherein said complexing agent is diethyl triamine pentaacetic acid.
7. The electrolytic tin-bismuth alloy plating solution according to claim 1, wherein the stabilizer comprises sodium citrate and hydroquinone in a weight ratio of 1:0.5 to 1.5 percent.
8. A method for preparing the electrolytic tin-bismuth alloy plating solution as claimed in any one of claims 1 to 7, comprising the steps of:
S1, dissolving stannous sulfate, sulfuric acid and bismuth sulfate in water, stirring to fully dissolve the stannous sulfate, the sulfuric acid and the bismuth sulfate, standing and cooling to obtain a solution A;
s2, dissolving the brightening agent in water, and stirring and dissolving at room temperature to obtain a solution B;
S3, dissolving the dispersing agent, the complexing agent and the stabilizing agent in water, and stirring to fully dissolve the dispersing agent, the complexing agent and the stabilizing agent to obtain a solution C;
And S4, mixing the solution A obtained in the step S1 and the solution B obtained in the step S2, the solution C obtained in the step S3, adding water to fix the volume, and further stirring and mixing uniformly to obtain the composite material.
9. The process according to claim 8, wherein the stirring in step S1 is carried out at a speed of 100 to 200rpm for 20 to 30 minutes; the stirring conditions in the steps S2 and S3 are stirring for 20-30 min at the rotating speed of 50-100 rpm; and (3) stirring and uniformly mixing the materials in the step S4 at a rotating speed of 500-600 rpm for 30-40 min.
10. Use of the electrolytic tin-bismuth alloy plating solution according to any one of claims 1 to 6 for electrolytic tin-bismuth alloy plating.
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