CN109652829B - Rare earth-free Bi-based magnetic electroplating solution and preparation method thereof - Google Patents
Rare earth-free Bi-based magnetic electroplating solution and preparation method thereof Download PDFInfo
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- CN109652829B CN109652829B CN201910007967.5A CN201910007967A CN109652829B CN 109652829 B CN109652829 B CN 109652829B CN 201910007967 A CN201910007967 A CN 201910007967A CN 109652829 B CN109652829 B CN 109652829B
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
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Abstract
The invention relates to the technical field of electroplating, in particular to a rare earth-free Bi-based magnetic electroplating solution and a preparation method thereof. The electroplating solution comprises 2-20g/L of nickel salt, 20-80g/L of boric acid, 10-80g/L of sodium hypophosphite, 10-60g/L of complexing agent and 2-10g/L of bismuth salt. The plating layer obtained by using the magnetic electroplating solution has beautiful color and good magnetic property, and can meet the requirements of plating layers with different thicknesses.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a rare earth-free Bi-based magnetic electroplating solution and a preparation method thereof.
Background
The electroplating has the advantages of low cost, simple process, easy operation and the like, and is widely applied in life. The electroplated single metal is far from meeting the requirements of modernization on functional materials. Therefore, the electroplating multi-component alloy is rapidly developed in recent years, can obtain surfaces with special properties, has a plurality of varieties and wider application, and is applied to industries such as magnetic materials and the like at present. At present, the methods for preparing the bismuth-based alloy mainly comprise a high-energy ball milling method, a vacuum evaporation method and a sputtering deposition method, and the preparation methods have the defects of complex equipment, high cost, long time, difficulty in large-scale production and application and the like.
Meanwhile, with the increasingly decrease of rare earth resources and the rapid increase of rare earth prices in the world, the cost of the rare earth magnetic material is greatly increased. Therefore, the seeking of low-cost electrodeposition technology for preparing bismuth-based multi-element alloy with excellent magnetic property has important significance.
A Chinese patent with application publication No. CN 104790000A and application publication No. 2015.07.22 discloses a manganese-bismuth-iron-phosphorus permanent magnet alloy electroplating solution and a preparation method thereof, the electroplating solution contains ferrous chloride, manganese chloride, bismuth chloride and a proper amount of water, and the formula also contains boric acid, sodium hypophosphite, sodium citrate and ascorbic acid; the weight parts of the components are respectively as follows: 35-45 parts of boric acid, 30-45 parts of sodium hypophosphite, 5-15 parts of ferrous chloride, 55-65 parts of manganese chloride, 2-10 parts of bismuth chloride, 35-45 parts of sodium citrate and 1-5 parts of ascorbic acid; the manganese-bismuth-iron-phosphorus permanent magnet alloy prepared by the formula comprises 2-27% of manganese, 3-20% of bismuth, 50-75% of iron and 10-21% of phosphorus by mass percent.
The patent provides a manganese bismuth iron phosphorus permanent magnet alloy electroplating solution, which adopts iron salt and rare earth elements, thereby improving the use cost.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a rare earth-free Bi-based magnetic plating solution and a method for producing the same. The electroplating solution avoids using rare earth elements, reduces the cost, does not contain corrosive substances, is safe and environment-friendly, has high chemical stability, simple and controllable preparation process and good stability, and simultaneously adopts nickel salt to improve the performance of an electroplated layer.
In order to achieve the purpose, the invention adopts the following technical scheme:
the rare earth-free Bi-based magnetic electroplating solution contains boric acid, sodium hypophosphite, a complexing agent and a proper amount of water, and also contains nickel salt and bismuth salt, wherein the components and the contents of the components of the electroplating solution are 20-80g/L of boric acid, 10-80g/L of sodium hypophosphite, 10-60g/L of the complexing agent, 2-20g/L of nickel salt and 2-10g/L of bismuth salt.
Furthermore, the components and the contents of the electroplating solution are 40g/L boric acid, 30g/L sodium hypophosphite, 60g/L complexing agent, 10g/L nickel salt and 5g/L bismuth salt.
Further, the nickel salt is a sulfate or chloride.
Further, the bismuth salt is a sulfate or a chloride.
Further, the complexing agent is sodium acetate, tartaric acid, citric acid or ethylenediamine tetraacetic acid.
Further, the pH value of the electroplating solution is 0.5-3.5.
Further, the working temperature of the electroplating solution is 10-50 ℃.
Furthermore, the electroplating solution also comprises additives, wherein the additives are benzotriazole and stannous chloride, and the specific contents of the benzotriazole are 2-5g/L and the stannous chloride is 6-10 g/L.
Specifically, benzotriazole and stannous chloride are used for improving the stability of the plating solution, and simultaneously, when the plating solution is used for electroplating, the stress on the surface of an electroplated layer can be eliminated, so that the flatness and the smoothness can be still kept when the thickness of the electroplated layer is larger.
A preparation method of rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
(1) adding 20-80g of boric acid, 10-80g of sodium hypophosphite and 10-60g of complexing agent into deionized water, and stirring and dissolving to prepare a mixed solution;
(2) adjusting the pH of the mixed solution to 1.0-3.0 with acid;
(3) adding 2-20g of nickel salt and 2-10g of bismuth salt into the mixed solution, stirring and dissolving, adding the rest of deionized water to a constant volume of 1L, and adjusting the pH of the mixed solution to 0.5-3.5 to obtain the rare earth-free bismuth-based magnetic electroplating solution.
Further, the bismuth salt in the step (3) is firstly acidified and then added into the mixed solution.
Further, the acid in the step (2) is hydrochloric acid or sulfuric acid.
Further, 1-3g of sodium pyrophosphate and 20-30g of dimethylformamide are added thereto.
Compared with the prior art, the invention has the beneficial effects that: the stability of the electroplating solution is good; the plating layer obtained by using the magnetic electroplating solution has beautiful color and good magnetic property, and can meet the requirements of plating layers with different thicknesses. The NiBiP alloy without rare earth obtained by the electroplating method has good magnetic property and good stability of electroplating solution, and can obtain a uniform coating.
Detailed Description
The technical solution of the present invention is further described below by means of specific examples.
The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1:
the preparation method of the rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
adding 20g of boric acid, 10g of sodium hypophosphite and 10g of complexing agent (sodium acetate) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 1.0 by using HCl, adding 2g of acidified bismuth chloride and 2g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 0.5 to obtain the rare-earth-free Bi-based magnetic electroplating solution.
Example 2:
the preparation method of the rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
adding 80g of boric acid, 80g of sodium hypophosphite and 40g of complexing agent (tartaric acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 1.5 by using HCl, adding 5g of acidified bismuth sulfate and 5g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 1.0 to obtain the rare-earth-free Bi-based magnetic electroplating solution.
Example 3:
the preparation method of the rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
adding 40g of boric acid, 40g of sodium hypophosphite and 40g of complexing agent (citric acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 3.0 by using HCl, adding 10g of acidified bismuth sulfate and 20g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 2.0 to obtain the rare-earth-free Bi-based magnetic electroplating solution.
Example 4:
the preparation method of the rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
adding 40g of boric acid, 60g of sodium hypophosphite and 40g of complexing agent (ethylene diamine tetraacetic acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 3.0 by using HCl, adding 10g of acidified bismuth chloride and 10g of nickel sulfate into the mixed solution, stirring and dissolving, adding the rest deionized water until the total volume is 1L, and adjusting the pH to 3.0 to obtain the rare-earth-free Bi-based magnetic electroplating solution.
Example 5:
the preparation method of the rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
adding 40g of boric acid, 30g of sodium hypophosphite and 60g of complexing agent (sodium acetate) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 3.0 by using HCl, adding 5g of acidified bismuth chloride and 10g of nickel sulfate into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 1.5 to obtain the rare-earth-free Bi-based magnetic electroplating solution.
Example 6:
the preparation method of the rare earth-free Bi-based magnetic electroplating solution comprises the following steps:
adding 40g of boric acid, 30g of sodium hypophosphite and 60g of complexing agent (ethylene diamine tetraacetic acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 2.5 by using HCl, adding 5g of acidified bismuth chloride and 10g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest deionized water until the total volume is 1L, and adjusting the pH to 1.0 to obtain the rare-earth-free Ni-Bi-P magnetic electroplating solution.
Example 7:
2g/L of benzotriazole and 10g/L of stannous chloride are added on the basis of the embodiment 5.
Example 8:
5g/L of benzotriazole and 6g/L of stannous chloride are added on the basis of the embodiment 6.
The rare earth-free Bi-based magnetic plating solutions obtained in examples 1 to 8 were stable during use and storage; the electroplating solution of each embodiment is electroplated, and the obtained plating layer is uniform and beautiful in color.
In the electroplating process of each plating solution of the above examples, the plating is carried out by the same process, and the plating layer is stable when the plating layer is 0 to 50 microns.
When the plating layer is more than 50 microns, particularly more than 80 microns, the plating layers of examples 1-6 are not flat, while examples 7 and 8 show better stability and the plating film is smooth and flat.
The specific expression is that when the thickness is more than 80 microns, the mirror surface effect is poor, and pockmarks, spots, small bubble points and raised particle points are easy to appear on the surface of the plating layer. There are 1-3 defect points less than 0.1mm within 10000 square millimeters.
Magnetic Property test results of the magnetic property tests of the plating layers obtained in examples 1 to 6 are shown below:
| item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| retentivity/Oe | 16.5 | 18.0 | 22.0 | 21.5 | 19.6 | 21.2 |
Magnetic Property test results of the magnetic property tests of the plating layers obtained in examples 7 to 8 are shown in the following table:
| item | Example 7 | Example 8 |
| retentivity/Oe | 21.5 | 22.4 |
As can be seen from the above table, the plating layer obtained by using the plating solution of the present invention has low coercive force, shows good soft magnetic properties, and has slight influence on the coercive force after the addition of the additive.
The rare earth-free Bi-based magnetic electroplating solution has good stability; the plating layer obtained by using the rare earth-free Bi-based magnetic electroplating solution has beautiful color and good magnetic property.
Meanwhile, in the preparation process, 1-3g of sodium pyrophosphate and 20-30g of dimethylformamide are added, so that the storage stability of the electroplating solution can be improved, and the working pH range can be expanded to 2.5-6. Thereby reducing the use conditions of the plating solution.
3g of sodium pyrophosphate and 20g of dimethylformamide were added to the preparation process of example 5, and the pH thereof was adjusted to 4 for use.
In addition to the preparation process of example 6, 1g of sodium pyrophosphate and 30g of dimethylformamide were added, and the pH thereof was adjusted to 6, thereby preparing for use.
The foregoing is considered as illustrative of the preferred embodiments of the invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.
Claims (6)
1. A rare earth-free bismuth-based magnetic electroplating solution with a smooth and flat plating layer comprises the following components: 20-80g/L of boric acid, 10-80g/L of sodium hypophosphite, 10-60g/L of complexing agent, 2-20g/L of nickel salt, 2-10g/L of bismuth salt, 2-5g/L of benzotriazole and 6-10g/L of stannous chloride, wherein the thickness of the plating layer is more than 50 microns.
2. The rare-earth-free bismuth-based magnetic plating solution as recited in claim 1, wherein the nickel salt is a sulfate or chloride.
3. The rare-earth-free bismuth-based magnetic electroplating solution as claimed in claim 1, wherein the bismuth salt is a sulfate or chloride.
4. The rare-earth-free bismuth-based magnetic electroplating solution as claimed in claim 1, wherein the complexing agent is sodium acetate, tartaric acid, citric acid or ethylenediamine tetraacetic acid.
5. The rare-earth-free bismuth-based magnetic plating solution as claimed in claim 1, wherein the plating solution has a pH of 0.5 to 3.5.
6. The rare-earth-free bismuth-based magnetic plating solution as claimed in claim 1, wherein the plating solution has an operating temperature of 10 to 50 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937732A (en) * | 2009-07-02 | 2011-01-05 | 国家纳米科学中心 | Nano cable made of magnetic material and half-metallic material and preparation method thereof |
| CN105951125A (en) * | 2016-06-08 | 2016-09-21 | 中国计量大学 | Novel manganese-based magnetic electroplate liquid and preparation method thereof |
| CN109023452A (en) * | 2018-08-22 | 2018-12-18 | 山西师范大学 | A kind of electroplate liquid and its electro-deposition method preparing low-temperature phase manganese bismuth alloy |
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| KR101234429B1 (en) * | 2006-01-06 | 2013-02-18 | 엔쏜 인코포레이티드 | Electrolyte and process for depositing a matt metal layer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101937732A (en) * | 2009-07-02 | 2011-01-05 | 国家纳米科学中心 | Nano cable made of magnetic material and half-metallic material and preparation method thereof |
| CN105951125A (en) * | 2016-06-08 | 2016-09-21 | 中国计量大学 | Novel manganese-based magnetic electroplate liquid and preparation method thereof |
| CN109023452A (en) * | 2018-08-22 | 2018-12-18 | 山西师范大学 | A kind of electroplate liquid and its electro-deposition method preparing low-temperature phase manganese bismuth alloy |
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