CN105002529A - Bismuth-plating electroplating liquid and pulse plating method for bismuth thin film - Google Patents
Bismuth-plating electroplating liquid and pulse plating method for bismuth thin film Download PDFInfo
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- CN105002529A CN105002529A CN201510519706.3A CN201510519706A CN105002529A CN 105002529 A CN105002529 A CN 105002529A CN 201510519706 A CN201510519706 A CN 201510519706A CN 105002529 A CN105002529 A CN 105002529A
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Abstract
The invention discloses a bismuth-plating electroplating liquid and a pulse plating method for a bismuth thin film. The bismuth-plating electroplating liquid comprises components in concentration as follows: 40-80 g/L of bismuth sulfate, 100-150 g/L of sodium potassium tartrate tetrahydrate, 30-40 g/L of sodium citrate, 0.15-0.20 g/L of antimony potassium tartrate or ethylenediamine tetraacetic acid disodium salt, 40-50 g/L of sodium gluconate, 5-7 ml/L of a stabilizer and the balance of a solvent A, wherein the solvent A is water; the stabilizer comprises 2-5 g/L of polyethylene glycol, 2-4 g/L of vitamin C, 15-20 g/L of sodium hypophosphite and the balance of a solvent B which is water. Compared with the prior art, the bismuth-plating electroplating liquid is better in stability and long in service life and has higher dispersion and covering capacity as well as high conduction performance, concentration polarization is reduced due to use of a pulsed power supply, and the current efficiency is improved.
Description
Technical field
The present invention relates to kind of a plating bismuth electroplate liquid, the invention still further relates to a kind of pulse plating method of bismuth thin film.
Background technology
Develop pulse plating techniques in recent years rapidly and fully show the incomparable superiority of many conventional electroplating method, pulse plating process can make coating crystallization refinement, arrangement closely, hole reduces, hardness increases.The electrochemistry preparation of all kinds of monometallic or alloy layer film is widely used in view of above advantage.
Electroplate liquid divides containing cyanide bath and cyanide-free plating bath, wherein containing cyanogen electroplate liquid reliable and stable, current efficiency is high, have good dispersive ability and covering power, the crystallization of gained coating is careful and bright, is generally adopted by countries in the world.But due to prussiate strong toxicity, a lot of problem is there is in operating environment, liquid waste disposal, particularly along with the raising of people's environmental consciousness, hypotoxic cyanideless electro-plating technology obtains the great attention of countries in the world just gradually, so the research promotion of cyanide-free plating bath system is imperative.
Bismuth is the rhombic system metal of transition state, both there is covalent linkage, again there is metallic bond, this structure makes it have a series of special physics-chem characteristic, is widely used in multiple fields such as fusible alloy, metallurgical addition agent, pharmacy, chemical preparations, semi-conductor, superconducting material, plating, battery.Under normal temperature, bismuth all has oxidation-resistance under dry, wet condition, and during anaerobic, bismuth is insoluble to hydrochloric acid, not by H
2s and cold dilute sulphuric acid effect, so plating bismuth can make ornamental or protectiveness coating.In recent years, along with bismuth industrial expansion, and people are to the attention of environment protection, and green, environmental protection, unleaded trend provide good development prospect by for the deep processing of bismuth series product.Report at present about bismuth thin film preparation method does not almost have, therefore, research prepare bismuth thin film to the Application and Development of " green metal " bismuth and new material research significant.
Summary of the invention
First technical problem to be solved by this invention is the plating bismuth electroplate liquid providing a kind of environmental protection for the state of the art.
Second technical problem to be solved by this invention is to provide a kind of pulse plating method of bismuth thin film.
The present invention solves the technical scheme that above-mentioned first technical problem adopt: a kind of plating bismuth electroplate liquid, it is characterized in that, comprise the component of following concentration: bismuth sulfate 40 ~ 80g/L, Seignette salt 100 ~ 150g/L, Trisodium Citrate 30 ~ 40g/L, antimonypotassium tartrate or disodium ethylene diamine tetraacetate 0.15 ~ 0.20g/L, Sunmorl N 60S 40 ~ 50g/L, stablizer 5 ~ 7ml/L, all the other are solvent orange 2 A, and described solvent orange 2 A is water;
Described stablizer comprises polyoxyethylene glycol 2 ~ 5g/L, Catergen ~ 4g/L, inferior sodium phosphate 15 ~ 20g/L, and all the other are solvent B, and described solvent B is water.
The present invention adopts cyanide-free plating bath system, environmental protection and stable performance, and select bismuth sulfate as the main salt of plating solution, Sunmorl N 60S is conducting salt, with tartrate for main coordination agent, reduces the Bi of free state in plating solution
3+the existence of ion, solves the facile hydrolysis problem of bismuth salt.Thus make plating solution can under pH value is the condition of 7.5 ~ 11.5 stable existence, also improve cathodic polarization ability simultaneously.
Wherein, described stablizer is prepared as follows and obtains, and inferior sodium phosphate is soluble in water, under agitation adds vitamins C; Polyoxyethylene glycol is dissolved in hot water, is then cooled to room temperature; Under agitation polyglycol solution is added in inferior sodium phosphate and ascorbic mixing solutions, obtains described stablizer.
Wherein, described plating bismuth electroplate liquid also comprises tensio-active agent 0.008 ~ 0.012g/L, and described tensio-active agent is sodium lauryl sulphate.
The present invention solves the technical scheme that above-mentioned second technical problem adopt: a kind of pulse plating method using the bismuth thin film of above-mentioned plating bismuth electroplate liquid, comprises the steps:
A. by proportioning preparation electroplate liquid;
B. pulse plating, injects electroplating device by electroplate liquid, and take copper sheet as negative electrode, proof gold plate is anode, electroplate, the bismuth thin film that namely film being deposited on negative electrode copper sheet surface obtains, electroplating technique condition is, current density is 0.6 ~ 0.8A/dm
2, frequency is 600 ~ 650Hz, dutycycle is 1:8 ~ 1:10, temperature of electroplating solution is 30 ~ 40 DEG C, pH value is 8 ~ 10.
Wherein, the spacing distance between described negative electrode and positive electrode is 6 ~ 7cm.
Wherein, described electroplating source is monopulse electroplating power supply.
Wherein, golden in described anode mass percentage >=99.99%.
Wherein, solvent orange 2 A described in step a is distilled water or deionized water.
Compared with prior art, the invention has the advantages that: the present invention plate bismuth electroplate liquid stability better, long service life, and have higher dispersion and covering power, conductivity is strong; The use of the pulse power, reduces concentration polarization, improves current efficiency; Adopt that the present invention can prepare that surface compact is smooth, porosity is low, bonding force is good, film thickness can bismuth thin film material more than 5 μm.In addition, simple, the easily operation of preparation technology of the present invention, practical.Bismuth is as " green metal " that can use safely, and the bismuth thin film of high-quality has broad application prospects in the Application Areass such as electronically materials and component industry.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
A method for preparing bismuth film by pulse plating process, comprises the following steps:
A, preparation electroplate liquid, main press bismuth sulfate 40g/L, Seignette salt 100g/L, Trisodium Citrate 30g/L, antimonypotassium tartrate 0.15g/L, Sunmorl N 60S 40g/L, sodium lauryl sulphate 0.008g/L, the composition of stablizer 5ml and content, get each component, mix with solvent orange 2 A water, with potassium hydroxide aqueous solution (can be mass percent concentration be 40% potassium hydroxide aqueous solution, the pH value regulating afterwards together) mixing solutions is 7.5 ~ 8.5, obtained electroplate liquid;
Stablizer in electroplate liquid presses polyoxyethylene glycol 2g/L, Catergen g/L, the composition of inferior sodium phosphate 15g/L and content, gets each component, mixes with solvent B water; And stablizer is prepared as follows and obtains, inferior sodium phosphate is soluble in water, under agitation add vitamins C; Polyoxyethylene glycol is dissolved in hot water, is then cooled to room temperature; Under agitation polyglycol solution is added in inferior sodium phosphate and ascorbic mixing solutions, obtains stablizer;
B, pulse plating, inject electroplating device by electroplate liquid, and taking copper sheet as negative electrode, proof gold plate is anode, is 0.6A/dm in current density
2, frequency is 600Hz, dutycycle is 1:8, temperature of electroplating solution is 30 DEG C, interpole gap is 6cm, pH value is electroplate under the processing condition of 7.5 ~ 8.5, the bismuth thin film that namely film being deposited on negative electrode copper sheet surface obtains.
After testing, surface compact is smooth, porosity is low, bonding force is good for gained bismuth thin film, and thickness can more than 5 μm.
Embodiment 2
A method for preparing bismuth film by pulse plating process, comprises the following steps:
A, preparation electroplate liquid, main press bismuth sulfate 60g/L, Seignette salt 130g/L, Trisodium Citrate 35g/L, antimonypotassium tartrate 0.18g/L, Sunmorl N 60S 45g/L, the composition of stablizer 6ml and content, get each component, mix with solvent orange 2 A water, the pH value regulating mixing solutions with potassium hydroxide aqueous solution is 8.5 ~ 9.5, obtained electroplate liquid;
Stablizer in electroplate liquid presses polyoxyethylene glycol 3.5g/L, vitamins C 3.0g/L, the composition of inferior sodium phosphate 18g/L and content, gets each component, mixes with solvent B water; And stablizer is prepared as follows and obtains, inferior sodium phosphate is soluble in water, under agitation add vitamins C; Polyoxyethylene glycol is dissolved in hot water, is then cooled to room temperature; Under agitation polyglycol solution is added in inferior sodium phosphate and ascorbic mixing solutions, obtains stablizer;
B, pulse plating, inject electroplating device by electroplate liquid, and taking copper sheet as negative electrode, proof gold plate is anode, is 0.7A/dm in current density
2, frequency is 620Hz, dutycycle is 1:9, temperature of electroplating solution is 35 DEG C, interpole gap is 7cm, pH value is electroplate under the processing condition of 8.5 ~ 9.5, the bismuth thin film that namely film being deposited on negative electrode copper sheet surface obtains.
After testing, surface compact is smooth, porosity is low, bonding force is good for gained bismuth thin film, and thickness can more than 5 μm.
Embodiment 3
A method for preparing bismuth film by pulse plating process, comprises the following steps:
A, preparation electroplate liquid, main press bismuth sulfate 80g/L, Seignette salt 150g/L, Trisodium Citrate 40g/L, Sunmorl N 60S 50g/L, EDTA (disodium ethylene diamine tetraacetate) 0.2g/L, the composition of stablizer 7ml and content, get each component, mix with solvent orange 2 A water, the pH value regulating mixing solutions with potassium hydroxide aqueous solution is 9.5 ~ 11.5, obtained electroplate liquid;
Stablizer in electroplate liquid presses polyoxyethylene glycol 5g/L, vitamins C 4g/L, the composition of inferior sodium phosphate 20g/L and content, gets each component, mixes with solvent B water; And stablizer is prepared as follows and obtains, inferior sodium phosphate is soluble in water, under agitation add vitamins C; Polyoxyethylene glycol is dissolved in hot water, is then cooled to room temperature; Under agitation polyglycol solution is added in inferior sodium phosphate and ascorbic mixing solutions, obtains stablizer;
B, pulse plating, inject electroplating device by electroplate liquid, and taking copper sheet as negative electrode, proof gold plate is anode, is 0.8A/dm in current density
2, frequency is 650Hz, dutycycle is 1:10, temperature of electroplating solution is 40 DEG C, interpole gap is 7cm, pH value is electroplate under the processing condition of 9.5 ~ 11.5, the bismuth thin film that namely film being deposited on negative electrode copper sheet surface obtains.
After testing, surface compact is smooth, porosity is low, bonding force is good for gained bismuth thin film, and thickness can more than 5 μm.
Above content is only preferred embodiment of the present invention, and for those of ordinary skill in the art, according to thought of the present invention, all will change in specific embodiments and applications, this description should not be construed as limitation of the present invention.
Claims (8)
1. a plating bismuth electroplate liquid, it is characterized in that, comprise the component of following concentration: bismuth sulfate 40 ~ 80g/L, Seignette salt 100 ~ 150g/L, Trisodium Citrate 30 ~ 40g/L, antimonypotassium tartrate or disodium ethylene diamine tetraacetate 0.15 ~ 0.20g/L, Sunmorl N 60S 40 ~ 50g/L, stablizer 5 ~ 7ml/L, all the other are solvent orange 2 A, and described solvent orange 2 A is water;
Described stablizer comprises polyoxyethylene glycol 2 ~ 5g/L, vitamins C 2 ~ 4g/L, inferior sodium phosphate 15 ~ 20g/L, and all the other are solvent B, and described solvent B is water.
2. plating bismuth electroplate liquid according to claim 1, is characterized in that: described stablizer is prepared as follows and obtains, and inferior sodium phosphate is soluble in water, under agitation adds vitamins C; Polyoxyethylene glycol is dissolved in hot water, is then cooled to room temperature; Under agitation polyglycol solution is added in inferior sodium phosphate and ascorbic mixing solutions, obtains described stablizer.
3. plating bismuth electroplate liquid according to claim 1, is characterized in that: described plating bismuth electroplate liquid also comprises tensio-active agent 0.008 ~ 0.012g/L, and described tensio-active agent is sodium lauryl sulphate.
4. use a pulse plating method for the bismuth thin film of the plating bismuth electroplate liquid according to any one of claim 1 to 3, it is characterized in that, comprise the steps:
A. by proportioning preparation electroplate liquid;
B. pulse plating, injects electroplating device by electroplate liquid, and take copper sheet as negative electrode, proof gold plate is anode, electroplate, the bismuth thin film that namely film being deposited on negative electrode copper sheet surface obtains, electroplating technique condition is, current density is 0.6 ~ 0.8A/dm
2, frequency is 600 ~ 650Hz, dutycycle is 1:8 ~ 1:10, temperature of electroplating solution is 30 ~ 40 DEG C, pH value is 8 ~ 10.
5. pulse plating method according to claim 4, is characterized in that: the spacing distance between described negative electrode and positive electrode is 6 ~ 7cm.
6. pulse plating method according to claim 4, is characterized in that: described electroplating source is monopulse electroplating power supply.
7. pulse plating method according to claim 4, is characterized in that: mass percentage >=99.99% of gold in described anode.
8. pulse plating method according to claim 4, is characterized in that: solvent orange 2 A described in step a is distilled water or deionized water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200469A (en) * | 2015-10-30 | 2015-12-30 | 无锡市嘉邦电力管道厂 | Tin-copper alloy electroplate liquid and electroplating method thereof |
| CN105220187A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of pulse plating method plating bismuth electroplate liquid and bismuth thin film |
| CN108070886A (en) * | 2017-11-30 | 2018-05-25 | 沈阳工业大学 | A kind of Preparation method and use of bimetallic Cu-Bi electro-catalysis denitrification electrode |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380445A (en) * | 2002-01-23 | 2002-11-20 | 武汉大学 | Electroplating tin-bithmuth alloy plating liquor and its preparation method |
| CN1385556A (en) * | 2002-01-23 | 2002-12-18 | 武汉大学 | Stabilizer for plating tin-bismuth alloy and preparation method thereof |
| CN101942683A (en) * | 2010-09-19 | 2011-01-12 | 西南科技大学 | Method for preparing bismuth film by pulse plating process |
-
2015
- 2015-08-21 CN CN201510519706.3A patent/CN105002529A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1380445A (en) * | 2002-01-23 | 2002-11-20 | 武汉大学 | Electroplating tin-bithmuth alloy plating liquor and its preparation method |
| CN1385556A (en) * | 2002-01-23 | 2002-12-18 | 武汉大学 | Stabilizer for plating tin-bismuth alloy and preparation method thereof |
| CN101942683A (en) * | 2010-09-19 | 2011-01-12 | 西南科技大学 | Method for preparing bismuth film by pulse plating process |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105200469A (en) * | 2015-10-30 | 2015-12-30 | 无锡市嘉邦电力管道厂 | Tin-copper alloy electroplate liquid and electroplating method thereof |
| CN105220187A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of pulse plating method plating bismuth electroplate liquid and bismuth thin film |
| CN108070886A (en) * | 2017-11-30 | 2018-05-25 | 沈阳工业大学 | A kind of Preparation method and use of bimetallic Cu-Bi electro-catalysis denitrification electrode |
| CN108070886B (en) * | 2017-11-30 | 2019-10-29 | 沈阳工业大学 | A kind of Preparation method and use of bimetallic Cu-Bi electro-catalysis denitrification electrode |
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