CN111926356A - Cobalt alloy electroplating solution and use method thereof - Google Patents
Cobalt alloy electroplating solution and use method thereof Download PDFInfo
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- CN111926356A CN111926356A CN202010773919.XA CN202010773919A CN111926356A CN 111926356 A CN111926356 A CN 111926356A CN 202010773919 A CN202010773919 A CN 202010773919A CN 111926356 A CN111926356 A CN 111926356A
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- C—CHEMISTRY; METALLURGY
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
Abstract
The invention relates to the technical field of electroplating, and particularly provides a cobalt alloy electroplating solution and a using method thereof. In a first aspect, the present invention provides a cobalt alloy electroplating bath comprising the following components in the following concentrations: 200-300 g/L cobalt salt, 50-130 g/L inorganic acid and salt thereof, and 10-40 g/L complexing agent. By selecting specific cobalt salt, inorganic acid and salt thereof and limiting the concentration of the cobalt salt, the performances of hardness, corrosion resistance, wear resistance and the like of a coating can be effectively improved under the action of a specific complexing agent, and meanwhile, the magnetic conductivity of the coating is less than 1.1, the resistance value of the coating is less than 1.0, and the coating can be better applied to electroplating treatment of ABS plastic surfaces of mobile phones and camera frames.
Description
Technical Field
The invention relates to the technical field of electroplating, and particularly provides a cobalt alloy electroplating solution and a using method thereof.
Background
Electroplating is a metal electrodeposition mode, and refers to a process of reducing metal ions in an electrolyte under the action of direct current and depositing the metal ions on the surface of a workpiece to form a metal coating with certain performance. Compared with other surface treatment technologies such as coating and vapor deposition, electroplating has the advantages of high deposition speed, uniform coating thickness and thin coating, and thus becomes a common metal corrosion prevention mode at present. The electroplating solution is a liquid which can expand the range of the cathodic current density of metal, improve the appearance of a plating layer, increase the stability of the solution against oxidation and the like. At present, the electroplating is carried out only by people and nickel plating is common, but the single electroplating layer cannot meet the market demand, so that the seeking of an alloy electroplating solution is a trend of the development of the electroplating industry.
Cobalt alloys are alloys formed by adding other alloying elements on the basis of cobalt. Common cobalt alloys include platinum-cobalt alloys, samarium-cobalt alloys, zirconium-cobalt alloys, tungsten-cobalt alloys, and the like. However, in the deposition process of many currently used cobalt alloy electroplating solutions, unstable plating solution and uneven plating thickness easily occur, so that the characteristics of the plating such as hardness and corrosion resistance are affected, and the resistance value and magnetic conductivity of the obtained plating are also high, so that the use of the plating is limited.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a cobalt alloy electroplating solution, comprising the following components in concentration: 200-300 g/L cobalt salt, 50-130 g/L inorganic acid and salt thereof, and 10-40 g/L complexing agent.
As a preferable technical scheme of the invention, the cobalt salt is selected from one or a combination of more of cobalt sulfate, basic cobalt carbonate, cobalt sulfamate, cobalt acetate, cobalt methane sulfonate, cobalt chloride, cobalt nitrate and cobalt acetate.
In a preferred embodiment of the present invention, the inorganic acid and the salt thereof are a phosphorus-containing inorganic acid and a corresponding phosphorus-containing inorganic acid salt.
As a preferred technical scheme of the invention, the inorganic acid containing phosphorus is selected from one or a combination of several of phosphorous acid, hypophosphorous acid and orthophosphoric acid.
As a preferable technical scheme of the invention, the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: (1-1.5).
As a preferred technical scheme of the invention, the complexing agent is organic acid; the organic acid is selected from one or more of citric acid, malic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetraacetic acid.
As a preferable technical scheme of the invention, the concentration of the citric acid is 5-15 g/L.
As a preferable technical scheme of the invention, the concentration of the malic acid is 5-25 g/L.
The second aspect of the invention provides a method for using a cobalt alloy electroplating solution, wherein the electroplating temperature is 55-65 ℃ and the pH value of the electroplating solution is 2-3.5 during electroplating.
As a preferred technique of the present inventionThe technical scheme is that during electroplating, the cathode material is ABS, and the cathode current density is 0.2-2A/dm2。
Has the advantages that: the invention provides a cobalt alloy electroplating solution, which can effectively improve the performances of hardness, corrosion resistance, wear resistance and the like of a plating layer under the action of a specific complexing agent by selecting specific cobalt salt, inorganic acid and salt thereof and limiting the concentration of the cobalt salt, can realize that the magnetic conductivity is less than 1.1 and the resistance value is less than 1.0, and can be better applied to electroplating treatment of ABS plastic surfaces of mobile phones and camera frames; in addition, the electroplating solution can bring more excellent performance under specific electroplating temperature and electroplating solution pH during the use process.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
In order to solve the above technical problems, a first aspect of the present invention provides a cobalt alloy electroplating solution, comprising the following components in concentration: 200-300 g/L cobalt salt, 50-130 g/L inorganic acid and its salt, 10-40 g/L organic acid.
In a preferred embodiment, the cobalt alloy electroplating bath comprises the following components in the following concentrations: 250g/L of cobalt salt, 90g/L of inorganic acid and salt thereof and 25g/L of organic acid.
<Cobalt salt>
The cobalt salt is selected from one or a combination of more of cobalt sulfate, basic cobalt carbonate, cobalt sulfamate, cobalt acetate, cobalt methane sulfonate, cobalt chloride, cobalt nitrate and cobalt acetate.
In a preferred embodiment, the cobalt salt is cobalt sulfate.
The method for preparing the cobalt-plated alloy layer by using the electroplating method is characterized in that cobalt sulfate is used as a main salt to provide cobalt metal, ammonium salt cannot be used, and the problem that the pH value of a system is changed rapidly in the construction process so as to influence the stability of a plating solution is solved, mainly because the electroplating is carried out at 55-65 ℃, the ammonium salt is unstable so as to cause the instability of the pH value in an electroplating solution system so as to influence the uniform formation of a plating layer, and when the pH value is too low, a large amount of hydrogen is generated so as to influence the deposition of cobalt.
<Inorganic acids and salts thereof>
The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and salt thereof.
In a preferred embodiment, the phosphorus-containing inorganic acid and its salt are meant to include phosphorus-containing inorganic acids and their corresponding phosphorus-containing inorganic acid salts.
Based on the double consideration of the pH value buffering effect of the plating solution and the magnetism of the obtained plating layer, the applicant finds in the experimental process that not all inorganic acids and salts thereof have good pH buffering effect in the system of the application and can simultaneously enable the magnetic permeability of the obtained plating layer to be low, the technical effect is good when phosphorus-containing inorganic acids and salts thereof are adopted, and when boric acid and salts thereof are adopted in the system, the obtained plating solution system is unstable in the electroplating process, the obtained plating layer is easy to have the problems of hardness and wear resistance reduction, probably because hydrogen ions in the system are consumed in the electroplating process, the hydrogen ions in the system are subjected to great concentration change in a short time, the pH of the system is increased, impurities with high content are formed, the mechanical property of the obtained plating layer is influenced, and the change degree of the pH can be reduced by the phosphorus-containing inorganic acids and salts thereof, the impurity content in the coating is reduced, so that the influence of the impurity content on the obtained coating is reduced; in addition, the magnetic permeability of the obtained product is also reduced, and probably because the obtained coating contains phosphorus, part of the structure of the formed cobalt-phosphorus coating has no symmetry and periodic repeatability, so that the amorphous isotropy of the part of the structure is formed, and the magnetic permeability of the obtained coating is reduced.
In a more preferred embodiment, the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: (1-1.5); more preferably, the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.2.
in a more preferred embodiment, the phosphorus-containing inorganic acid is selected from one or a combination of phosphorous acid, hypophosphorous acid and orthophosphoric acid.
In a more preferred embodiment, the phosphorus-containing inorganic acid is phosphorous acid and/or hypophosphorous acid.
In a more preferred embodiment, the phosphorus-containing inorganic acid is hypophosphorous acid; more preferably, the phosphorus-containing inorganic acid salt is a hypophosphite salt; more preferably, the hypophosphite salt is sodium/potassium hypophosphite.
The phosphorous acid, the phosphite, the hypophosphorous acid and the hypophosphite are adopted, so that the inorganic acid and the inorganic acid salt have synergistic effect and are used as components of the electroplating solution to provide a source for phosphorus of a plating layer, and the hardness and the corrosion resistance of the plating layer are improved.
<Complexing agents>
The complexing agent is organic acid.
In a preferred embodiment, the organic acid is selected from one or more of citric acid, malic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetraacetic acid.
In a more preferred embodiment, the organic acid comprises citric acid and malic acid.
In a more preferred embodiment, the concentration of the citric acid is 5-15 g/L; the concentration of the malic acid is 5-25 g/L.
In a more preferred embodiment, the citric acid is present at a concentration of 10g/L citric acid; the concentration of the malic acid is 15 g/L.
The malic acid is D-malic acid (CAS number 636-61-3).
The concentration of the cobalt alloy plating solution is the concentration of the cobalt alloy plating solution; the solvent of the cobalt alloy electroplating solution is deionized water.
Although the specific phosphorus-containing inorganic acid and the salt thereof are added into the main salt of the cobalt sulfate to be beneficial to reducing the magnetic permeability of the product, the applicant also finds that the reduction degree of the magnetic permeability is variable, the mechanical property, the wear resistance, the corrosion resistance and the like of the obtained plating layer are not ideal, the resistance value of the obtained plating layer is high, and the plating layer is not very suitable for being applied to the formation of the plating layer of a mobile phone camera frame, when citric acid and malic acid are added into the system, particularly when the concentration of the citric acid is 5-15 g/L and the concentration of the malic acid is 5-25 g/L, the obtained plating layer can realize the low magnetic permeability and the low resistance value, the magnetic permeability is less than 1.1 and the resistance value is less than 1.0, and the hardness, the corrosion resistance and the wear resistance of the plating layer are improved, probably because hypophosphorous acid or hypophosphite is oxidized into a phosphorous substance in the system under the condition that the pH is 2, the phosphorous acid substance can keep the valence state and is further complexed with cobalt in the system, but because the solubility of a complex compound in the system is limited, the complex compound is easy to form colloid to be separated out, and simultaneously, the formation of crystal grains of the cobalt is influenced, so that the hardness or compactness of a plating layer is influenced, and even the plating layer is cracked; the malic acid and the citric acid with specific concentration are added into the system to act together, so that a better complex can be formed with cobalt, colloid precipitation is avoided, refinement and reduction of cobalt in a plating layer are promoted, the dispersibility of cobalt and phosphorus in the plating layer is improved, phosphorus content in the plating layer is moderate based on the synergistic effect of phosphorus content with specific content and the malic acid and the citric acid, the great influence of impurities on the resistance of the plating layer is reduced, and the formation of an asymmetric and periodic repetitive structure in the plating layer structure is promoted.
The cobalt alloy electroplating solution also comprises 0.1-0.8 g/L bis (hydroxyethyl) disulfide and 0.5-1.5 g/L polyether.
In a preferred embodiment, the cobalt alloy electroplating solution further comprises 0.45g/L bis (hydroxyethyl) disulfide and 1g/L polyether.
<Polyether>
The polyether is selected from one or a combination of a plurality of polyethylene glycol diglycidyl ether, glycerol triglycidyl ether, poly (propylene glycol) diglycidyl ether and 1, 4-butanediol diglycidyl ether.
In a preferred embodiment, the polyether is polyethylene glycol diglycidyl ether.
In a more preferred embodiment, the polyethylene glycol diglycidyl ether has a viscosity of 45 to 80mPa.s at 25 ℃ and an epoxy equivalent weight of 260 to 340 g/eq.
In a more preferred embodiment, the polyethylene glycol diglycidyl ether has a viscosity of 50 to 70mPa.s at 25 ℃ and an epoxy equivalent of 263 to 333 g/eq.
In a more preferred embodiment, the polyethylene glycol diglycidyl ether is purchased from Wuhanhaishan family , Inc.
The applicant finds that adding a trace amount of bis (hydroxyethyl) disulfide and polyethylene glycol diglycidyl ether into a system is beneficial to wear resistance and low-temperature resistance of a coating material, particularly when the viscosity of polyethylene glycol diglycidyl ether is controlled to be 50-70 mPa.s at 25 ℃, and the epoxy equivalent is 263-333, and when the epoxy content is more in the system, the effect is rather reduced, which may be because cobalt is more brittle than nickel, and the applicant adds two substances with different molecular weight grades, namely bis (hydroxyethyl) disulfide and polyethylene glycol diglycidyl ether, into the system, and is beneficial to promoting the refinement of cobalt, so that the coating is more delicate; meanwhile, polyethylene glycol diglycidyl ether with certain viscosity and bis (hydroxyethyl) disulfide can be well adsorbed on the surface of a plating layer in a cobalt plating solution, and form the plating layer together with a complex and cobalt phosphorus, so that the connection is established among different particles, the density and flexibility of the plating layer are improved, the low-temperature resistance of the plating layer is improved, and when the epoxy value is higher or the content is more, on one hand, the polarity is increased, the adhesion with the plating layer is reduced, and simultaneously, the deposition of metal or phosphorus can be influenced, so that the overall performance of the plating layer is influenced.
The second aspect of the invention provides a method for using a cobalt alloy electroplating solution, wherein the electroplating temperature is 55-65 ℃ and the pH value of the electroplating solution is 2-3.5 during electroplating.
In a preferred embodiment, the cobalt alloy electroplating solution is used in the electroplating process, the electroplating temperature is 55-65 ℃, the pH value of the electroplating solution is 2-3.5, the cathode material is a target workpiece, the target workpiece is ABS which is purchased from ABS 920 of New materials of Europe, Inc. of Dongguan city, and the cathode current density is 0.2-2A/dm2Anode materialThe material can be any one of carbon, platinum plated and cobalt.
In a more preferred embodiment, the cobalt alloy electroplating solution is used at an electroplating temperature of 55-65 ℃, a pH of the electroplating solution of 2-3.5, an electroplating time of 5-15 min, a cathode material as a target workpiece, and the target workpiece as ABS (acrylonitrile butadiene styrene) which is purchased from ABS 920 of New materials of Europe, Inc. of Dongguan city, and a cathode current density of 0.2-2A/dm2The anode material is platinum.
The electroplating conditions with the pH of 2.0-3.5 and the temperature of 55-65 ℃ are adopted to interact with the specific electroplating solution, so that the technical effects of low magnetic conductivity and resistance value of the obtained plating layer are realized, the comprehensive performance of the obtained plating layer is better, and when the pH is lower or higher, the stability of the electroplating solution system is influenced, the solubility of phosphorus-containing inorganic acid and salt thereof is influenced, the deposition of a cobalt complex compound is also influenced, the structure of the plating layer is influenced, and the resistance value, the magnetic conductivity and the comprehensive performance of the plating layer are influenced; the problem of plating leakage or partial non-plating layer can occur due to low temperature in the electroplating process, and the deposition speed of the plating layer can be accelerated when the temperature is high, so that the refining degree and the dispersion condition of metal can be influenced, and the comprehensive performance is deteriorated.
The third aspect of the invention provides application of a cobalt alloy electroplating solution, which is applied to electroplating treatment of ABS plastic surfaces of mobile phone and camera frames.
Examples
In order to better understand the above technical solutions, the following detailed descriptions will be provided with reference to specific embodiments. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
Example 1 of the present invention provides a cobalt alloy electroplating bath comprising the following components in the following concentrations: 210g/L of cobalt salt, 60g/L of phosphorus-containing inorganic acid and salt thereof and 15g/L of organic acid.
The cobalt salt is cobalt sulfate.
The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.
The complexing agent is organic acid; the organic acid comprises 6g/L citric acid and 7g/L malic acid.
The malic acid is D-malic acid.
The pH value of the cobalt alloy electroplating solution is 2-3.5.
Example 2
Embodiment 2 of the present invention provides a cobalt alloy electroplating solution including the following components in concentrations: 290g/L of cobalt salt, 120g/L of phosphorus-containing inorganic acid and salt thereof and 35g/L of organic acid.
The cobalt salt is cobalt sulfate.
The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.5; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.
The complexing agent is organic acid; the organic acid comprises 14g/L of citric acid and 23g/L of malic acid.
The malic acid is D-malic acid.
The pH value of the cobalt alloy electroplating solution is 2-3.5.
Example 3
Example 3 of the present invention provides a cobalt alloy electroplating bath comprising the following components in the following concentrations: 250g/L of cobalt salt, 90g/L of phosphorus-containing inorganic acid and salt thereof and 250g/L of organic acid.
The cobalt salt is cobalt sulfate.
The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.2; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.
The complexing agent is organic acid; the organic acid comprises 10g/L of citric acid and 15g/L of malic acid.
The malic acid is D-malic acid.
The pH value of the cobalt alloy electroplating solution is 2-3.5.
Example 4
Embodiment 4 of the present invention provides a cobalt alloy electroplating solution including the following components in concentrations: 250g/L of cobalt salt, 90g/L of phosphorus-containing inorganic acid and salt thereof and 250g/L of organic acid.
The cobalt alloy plating solution also included 0.45g/L bis (hydroxyethyl) disulfide and 1g/L polyether.
The cobalt salt is cobalt sulfate.
The inorganic acid and the salt thereof are phosphorus-containing inorganic acid and corresponding phosphorus-containing inorganic acid salt; the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 1.2; the phosphorus-containing inorganic acid is hypophosphorous acid; the phosphorus-containing inorganic acid salt is hypophosphite; the hypophosphite is sodium hypophosphite.
The complexing agent is organic acid; the organic acid comprises 10g/L of citric acid and 15g/L of malic acid.
The malic acid is D-malic acid.
The pH value of the cobalt alloy electroplating solution is 2-3.5.
The polyether is polyethylene glycol diglycidyl ether; the polyethylene glycol diglycidyl ether has a viscosity of 50 to 70mPa.s at 25 ℃ and an epoxy equivalent of 263 to 333g/eq, and is purchased from GmbH of Hippocrate, Wuhan.
Comparative example 1
Comparative example 1 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 3 in the following embodiments, except that the inorganic acid and its salt are boric acid and its corresponding sodium borate; the weight ratio of the boric acid to the sodium borate is 1: 1.2.
comparative example 2
Comparative example 2 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 3 in the following embodiments, except that the phosphorus-containing inorganic acid is orthophosphoric acid; the phosphorus-containing inorganic acid salt is sodium orthophosphate.
Comparative example 3
Comparative example 3 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 3 except that the concentration of the phosphorus-containing inorganic acid or salt thereof is 150 g/L.
Comparative example 4
Comparative example 4 of the present invention provides a cobalt alloy plating solution, which is similar to example 3, except that the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: 10; the pH of the cobalt alloy electroplating solution is greater than 3.5.
Comparative example 5
Comparative example 5 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 3 except that malic acid is replaced with lactic acid.
Comparative example 6
Comparative example 6 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 3 except that malic acid is replaced with ethylenediaminetetraacetic acid.
Comparative example 7
Comparative example 7 of the present invention provides a cobalt alloy electroplating bath, which was similar in embodiment 3 except that citric acid was replaced with gluconic acid.
Comparative example 8
Comparative example 8 of the present invention provides a cobalt alloy electroplating bath, which was similar to example 3 except that the concentration of malic acid was 2 g/L.
Comparative example 9
Comparative example 9 of the present invention provides a cobalt alloy electroplating solution, which is the same as in example 4, except that polyethylene glycol diglycidyl ether has a viscosity of 20 to 30mpa.s at 25 ℃, an epoxy equivalent of 149 to 178g/eq, and is purchased from chenghong chemical co.
Comparative example 10
Comparative example 10 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 4 except that the concentration of polyethylene glycol diglycidyl ether is 3 g/L.
Comparative example 11
Comparative example 11 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 4 except that polyethylene glycol diglycidyl ether is not included.
Comparative example 12
Comparative example 12 of the present invention provides a cobalt alloy electroplating bath, which is similar to example 4 except that bis (hydroxyethyl) disulfide is not present.
The cathode material was a target workpiece, the target workpiece was ABS, which was purchased from ABS 920, a company, new materials, inc, of polya, guan, and the anode material was carbon, which was treated according to the following electroplating process: (1) coarsening: the solution is prepared from 400g/L chromic anhydride and 385g/L sulfuric acid at 70 ℃ for 11 min; (2) neutralizing: the solution is chloride ion 300g/L, the temperature is 25 ℃, and the time is 2 min; the chloride ion source is hydrochloric acid; (3) activating palladium: the solution is 21ppm of palladium ions, 270ml/L of hydrochloric acid and 4g/L of stannous chloride; the temperature is 29 ℃, and the time is 4 min; the source of the palladium ions is tetraamminepalladium sulfate; (4) and (3) gel releasing: the solution is 90ml/L hydrochloric acid; the temperature is 42 ℃, and the time is 3 min; (5) chemical plating: the formula of the plating solution is 80ml/L formaldehyde, 60g/L copper sulfate, 7g/L sodium citrate and 3.5g/L sodium gluconate; the temperature is 51 ℃, and the time is 5 min; (6) engraving: forming a pattern by using laser engraving marks; (7) copper plating: the formula of the plating solution is 185g/L of copper sulfate and 70g/L of sulfuric acid; the plating voltage is 3V, and the plating current density is 0.2A/dm2Electroplating temperature is 30 ℃ and time is 10 min; (8) plating a cobalt alloy: the above implementationThe cobalt alloy plating solutions of examples 1 to 4 and comparative examples 1 to 12; current density 1.1A/dm2(ii) a The pH value of the electroplating solution is 2-3.5, the electroplating temperature is 60 ℃, and the electroplating time is 10 min; (9) and (3) chromium plating: the formula of the plating solution is 55g/L of trivalent chromium and 55g/L of hydrochloric acid; the plating voltage is 4V and the plating current is 4A/dm2Electroplating temperature is 50 ℃ and time is 10 min; (10) drying: and (3) drying the electroplated workpiece in a 37 ℃ oven for 20 min.
Comparative example 13
Comparative example 13 of the present invention provides a cobalt alloy plating solution, which was similar to example 3 except that the plating temperature was 75 ℃ during plating.
Comparative example 14
Comparative example 14 of the present invention provides a cobalt alloy plating solution, which was similar to example 3 except that the plating temperature was 45 ℃.
Performance testing
The following performance tests 1-13 were performed on the samples of the electroplated workpieces prepared in the above examples 1-4 and comparative examples 9-12; the samples of the plated workpieces prepared in comparative examples 1 to 8 and comparative examples 13 to 14 above were subjected to the following performance tests 1, 2, 5, 12 and 13. Appearance no anomaly in the following tests means: no discoloration, no bubbling, no cracking, no corrosion, no delamination and no shedding; otherwise, recording an exception.
1. Pencil hardness test
Marking 3 lines with the length of 1.0 +/-0.2 cm on the surface of a sample from different directions at an angle of 45 degrees under the load of 500gf by using a Mitsubishi pencil (UNI series), wiping off the trace of the pencil by using an eraser, sequentially testing from hard to soft from the hardest pencil until a pencil with a coating which is not scratched is found, and recording the hardness value at the moment, wherein the hardness value is A above 7H, B above 5-7H, C below 4-5H (excluding 5H), and D below 4H.
2. Rubber rub test
A500 g load was applied to the sample and a special rubber was used to rub the surface of the material back and forth for 200 cycles. The lateral edges are subjected to 100 cycles, wherein 45 +/-5 times per minute and 20mm of stroke are carried out, the rubber cannot be separated from the sample, the rubber is exposed by 30-40% when the rubber moves to two ends in the small product stroke, and whether the plating layer falls off or not and whether the substrate texture is exposed or not are observed and recorded; wherein, the texture of the coating at the wear-resistant part which does not fall off and expose the substrate is recorded as qualified, otherwise, the coating is unqualified; 10 parallel samples were set and the number was recorded as acceptable.
3. Red ink test
Taking a 3PCS decorative ring, sticking auxiliary materials (double-sided adhesive tape), loading the auxiliary materials into a lens of a camera, and compacting the lens (4-5Kg) by using a battery cover rear lens re-pressing tool; then, dripping DYKM red ink to the periphery of the decoration hole (ensuring that the red ink is completely covered), and standing for 2H; placing the sample after standing in an oven (80 +/-5 ℃) to bake for 2H; taking out the sample, and dismantling the lens; checking whether the double-sided adhesive tape is impregnated by red ink; wherein, the red ink can not completely permeate the double faced adhesive tape until the edge of the camera hole is marked as qualified, and the red ink can not completely permeate the double faced adhesive tape until the edge of the camera hole is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.
4. Alcohol resistance test
Rubbing the sample surface with 99.8% absolute ethanol under 500g pressure at 50 + -5 times/min for 200 times while keeping the flannel moist; observing whether the film is decolorized, falls off or shows the phenomenon of exposing the substrate; wherein, the base material without decolorization, falling off and exposure is marked as qualified, otherwise, the base material is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.
5. Salt spray test
Using a NaCl solution with the pH value of 6.5-7.2 and the concentration of 5 wt%, the temperature of a test groove is 33-37 ℃, the test time is 96h, cleaning with clear water after the test, and drying at 50-60 ℃; the coating adhesion was tested using 3M610 gummed paper, where no appearance abnormality and adhesion above 3B was designated A, no appearance abnormality and adhesion between 2B and 3B was designated B, appearance abnormality or adhesion between 1B and 2B (excluding 2B) was designated C, and appearance abnormality or adhesion below 1B was designated D.
6. High temperature storage test
Standing at 73-77 ℃ for 48h, standing at normal temperature for at least 2h, and observing the appearance, wherein no abnormal appearance is recorded as qualified, and abnormal appearance is recorded as unqualified; 10 parallel samples were set and the number was recorded as acceptable.
7. Cosmetic resistance test
The surface of the product is wiped clean by cotton cloth, and cosmetics are uniformly coated on the surface of the sample, wherein each cosmetic is coated with 2 samples. The cosmetics are as follows: nivea sunscreen SPF30PA + +; nivea hand cream; q1a yulan oil sun SPF15PA +; d. liushen mosquito-repellent toilet water; e. baique Ling olive essential oil. Temperature: 55. + -.1 ℃ humidity: 93% -95% RH; time: 48H; after at least 2H is recovered at normal temperature, checking whether the surface of the sample is foamed or not, whether a paint film is obviously abnormal such as falling and separation or not, and whether the appearance of the product is abnormally changed or not; wherein, the sample surface has no bubble, the paint film has no shedding, no separation, no abnormal change of the appearance is marked as qualified, otherwise, the sample surface is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.
8. Artificial sweat resistance test
Preparing a solution according to an artificial juice preparation instruction, wherein the pH value is 4.6 +/-0.1; the dust-free cloth for soaking the solution is stuck on the surface of the sample and sealed in a constant temperature and humidity box by a sealing rubber bag; temperature: 55. + -.2 ℃ humidity: 93 plus or minus 2 percent; storage time: 48 h; after the test, wiping the solution on the surface of the product, standing for at least 2h at room temperature, observing the appearance, and carrying out an adhesion test; wherein, no bubble, no plating corrosion, no paint film falling, no separation, no black spot with the diameter less than 0.5mm on the silver edge, no flake black block on the silver edge are marked as qualified, otherwise, the silver edge is marked as unqualified; 10 parallel samples were set and the number was recorded as acceptable.
9. Temperature impact resistance test
Keeping at-40 deg.C + -2 deg.C for 1h, and transferring to 75 deg.C + -2 deg.C within 1min and keeping for 1 h; the samples were tested for 20 cycles for 40 h; after the test, the sample is kept stand at normal temperature for at least 2h, and then the appearance is observed, and the adhesive force is tested; directly sticking the plastic water electroplated part on the surface of the sample crystal by using a 3M610 adhesive tape for 3 times without marking grids; wherein, the appearance is not abnormal and the adhesive force is more than 3B and is marked as A, the appearance is not abnormal and the adhesive force is 2B to 3B and is marked as B, the appearance is abnormal or the adhesive force is 1B to 2B (excluding 2B) and is marked as C, and the appearance is abnormal or the adhesive force is less than 1B and is marked as D.
10. Ultraviolet aging test
Sticking black gummed paper or wrapping the non-irradiated surface of the sample by a dark thick paperboard; setting the power of the lamp tube to be 0.63W/m2, placing a sample into a test box, directly irradiating ultraviolet rays on the surface of the paint for 4 hours at the temperature of 60 ℃, then condensing for 4 hours at the temperature of 50 ℃, wherein the cycle is one cycle, taking out the sample after 12 cycles (96 hours), cooling for at least 2 hours at normal temperature, and then inspecting the surface of the paint; the paint surface is not faded, discolored, grains, cracked or peeled, the adhesive force is more than 3B and is marked as A, the paint surface is not faded, discolored, grains, cracked or peeled, the adhesive force is 2B-3B and is marked as B, the paint surface is faded, discolored, grains, cracked or peeled, the adhesive force is less than 1B-2B (excluding 2B) and is marked as C, and the paint surface is faded, discolored, grains, cracked, peeled or adhered, the adhesive force is less than 1B and is marked as D.
11. Low temperature storage resistance test
Standing at-42 to-38 ℃ for 48h, standing at normal temperature for at least 2h after the test, and observing the appearance; wherein, the appearance is qualified without abnormity, hardening, cracking, layering and key falling, otherwise, the appearance is unqualified; 10 parallel samples were set and the number was recorded as acceptable.
12. Permeability test
And testing the magnetic permeability of the sample by using an inductance test, wherein the magnetic permeability is less than Q and not equal to 1.01 and is recorded as A, the magnetic permeability is 1.01-1.1 and is recorded as B, the magnetic permeability is 1.1-1.6 and is recorded as C, and the magnetic permeability is more than 1.6 and is recorded as D.
13. Resistance value test
And (3) performing a resistance value test on the sample according to GB/T6146-2010, wherein the resistance value is less than 1 omega and is recorded as A, the resistance value is 1-1.5 omega and is recorded as B, the resistance value is 1.5-2 omega and is recorded as B, and the resistance value is more than 2 omega and is recorded as C.
TABLE 1
TABLE 2
| Hardness of pencil | Rubber friction | Salt fog | Magnetic permeability | Resistance value | |
| Comparative example 1 | D | 1 | D | D | D |
| Comparative example 2 | B | 7 | B | B | B |
| Comparative example 3 | C | 4 | C | C | C |
| Comparative example 4 | C | 4 | C | C | C |
| Comparative example 5 | C | 5 | C | C | C |
| Comparative example 6 | C | 6 | C | C | C |
| Comparative example 7 | C | 5 | C | C | C |
| Comparative example 8 | C | 6 | C | C | C |
| Comparative example 13 | C | 4 | C | C | C |
| Comparative example 14 | D | 2 | D | D | D |
TABLE 3
| Rubber friction | Low temperature storage resistance | |
| Comparative example 11 | 7 | 7 |
| Comparative example 12 | 7 | 7 |
As can be seen from the data in the table above, the cobalt alloy electroplating solution prepared by the invention is applied to electroplated workpieces, can effectively improve the performances of the plating layer such as hardness, corrosion resistance, wear resistance and the like, and can realize that the magnetic conductivity is less than 1.1 and the resistance value is less than 1.0; in addition, in the using process, under the specific electroplating temperature and the pH value of the electroplating solution, the ABS plastic electroplating solution can bring more excellent performance, and can be better applied to the electroplating treatment of the ABS plastic surface of mobile phones and camera frames.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A cobalt alloy electroplating bath comprising the following components in the following concentrations: 200-300 g/L cobalt salt, 50-130 g/L inorganic acid and salt thereof, and 10-40 g/L complexing agent.
2. The cobalt alloy electroplating solution according to claim 1, wherein the cobalt salt is selected from one or more of cobalt sulfate, cobalt carbonate hydroxide, cobalt sulfamate, cobalt acetate, cobalt methanesulfonate, cobalt chloride, cobalt nitrate and cobalt acetate.
3. The cobalt alloy electroplating bath as claimed in claim 1, wherein the inorganic acid and its salt is a phosphorus-containing inorganic acid and its corresponding phosphorus-containing inorganic acid salt.
4. The cobalt alloy electroplating solution as set forth in claim 3, wherein the phosphorus-containing inorganic acid is selected from the group consisting of phosphorous acid, hypophosphorous acid and orthophosphoric acid.
5. The cobalt alloy electroplating bath as claimed in claim 3 or 4, wherein the weight ratio of the phosphorus-containing inorganic acid to the phosphorus-containing inorganic acid salt is 1: (1-1.5).
6. The cobalt alloy electroplating bath as set forth in claim 1, wherein the complexing agent is an organic acid; the organic acid is selected from one or more of citric acid, malic acid, tartaric acid, citric acid, lactic acid, succinic acid, maleic acid, hydroxyethylidene diphosphonic acid and ethylenediamine tetraacetic acid.
7. The cobalt alloy electroplating solution according to claim 6, wherein the concentration of the citric acid is 5 to 15 g/L.
8. The cobalt alloy electroplating solution according to claim 6, wherein the concentration of malic acid is 5 to 25 g/L.
9. The method of using a cobalt alloy plating solution as defined in claim 1 to 9, wherein the plating temperature is 55 to 65 ℃ and the pH of the plating solution is 2 to 3.5.
10. The use method of a cobalt alloy electroplating solution as claimed in claim 9, wherein the cathode material is ABS and the cathode current density is 0.2-2A/dm during electroplating2。
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