CN110923766B - Color-changing-resistant matte black chromium composite coating and preparation method thereof - Google Patents
Color-changing-resistant matte black chromium composite coating and preparation method thereof Download PDFInfo
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
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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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
The invention discloses a discoloration-resistant matte black chromium composite coating and a preparation method thereof. In addition, a preparation method of the composite plating layer is also disclosed.
Description
Technical Field
The invention relates to the technical field of composite coatings, in particular to a color-changing-resistant matte black chromium composite coating on an alloy substrate and a preparation method thereof.
Background
In modern kitchen and bathroom products, new materials are often coated on the surfaces of the products for the purposes of corrosion resistance, wear resistance, color value and the like. The black color has the characteristics of being solemn, never outdated, easy to match and the like, and has more and more applications in the life of people, such as black shower heads, black water faucets and the like for kitchens and bathrooms, and the black color has attractive appearance and various practical purposes. The black coating on the surface of the kitchen and bath products is usually a black chromium layer or a black paint layer.
At present, the black chromium layer of the kitchen and bath products is mainly realized by adopting the technology of directly plating hexavalent black chromium by electroplating. For example, in patent CN2018115436280, a black automobile decoration is prepared on an injection molding by surface pretreatment, copper electroplating, nickel electroplating, hexavalent black chromium electroplating and other processes. However, the electroplated hexavalent black chromium of the application is a top layer material, and the hexavalent black chromium material contains C, O, F and other elements. When the hexavalent black chromium product is subjected to a color change resistance test, the product is placed at a high temperature of 180 ℃ and 280 ℃ for baking for 30min, and the surface of the hexavalent black chromium coating is easy to discolor.
The present invention has been made in order to overcome the above problem of discoloration of black chromium products upon baking at high temperatures.
Disclosure of Invention
The invention mainly aims to provide a discoloration-resistant matte black chromium composite coating on an alloy (such as copper alloy, zinc alloy, stainless steel and the like) base material and a preparation method thereof.
Specifically, the invention provides a discoloration-resistant matte black chromium composite coating on an alloy (comprising copper alloy, zinc alloy, stainless steel and the like) base material, wherein the surface of the alloy base material is sequentially provided with an electroplated copper layer, a semi-gloss nickel layer and a hexavalent black chromium layer, and a matte transparent paint surface layer is sprayed on the surface of the hexavalent black chromium layer, so that the discoloration-resistant matte black chromium composite coating is obtained. Wherein, the matte transparent paint layer comprises the following raw materials: 100-400g/L of polyurethane, 40-140 g/L of curing agent HDI, 50-150 g/L, UV-5151 of acrylic extinction emulsion leveling agent, 3-15g/L of composite light stabilizer, 30-200g/L of dithiocarbamate antistatic agent and 50-400 g/L of dimethylbenzene.
Preferably, the content of the UV-5151 composite light stabilizer in the raw material of the matte transparent paint layer is 4-12 g/L.
The discoloration resistance is that the composite plating layer is baked for 30min at the high temperature of 280 ℃ without discoloration.
The thickness range of the electroplated copper layer is 30-45 mu m, the thickness range of the semi-gloss nickel layer is 20-30 mu m, the thickness range of the hexavalent black chromium layer is 0.5-5 mu m, and the thickness of the matte transparent paint layer is 20-40 mu m.
The electroplated copper layer comprises three layers of priming copper, copper pyrophosphate and copper sulfate, and the thickness range of each layer is 10-15 mu m.
The 'matte transparent paint' refers to paint with a softer paint surface, a little fog and glossiness below 20 (60 degrees).
The invention also provides a preparation method of the discoloration-resistant matte black chromium composite coating, which comprises the following steps:
(i) electroplating pretreatment, namely cleaning the surface of the alloy;
(ii) (ii) electroplating a copper layer, namely electroplating the copper layer on the clean base material obtained in the step (i);
(iii) electroplating a semi-gloss nickel layer, and performing electroplating semi-gloss nickel treatment on the clean copper sulfate layer obtained in the step (ii);
(iv) (iv) electroplating a black chromium layer, and performing black chromium electroplating treatment on the clean semi-bright nickel layer obtained in the step (iii);
(v) and (3) spraying a full-matte transparent paint layer, and spraying full-matte transparent paint on the clean black chromium layer obtained in the step (iv).
Preferably, in the matte clear paint in the step (v), the content of the UV-5151 composite light stabilizer is 4-12g/L, and more preferably, the content of the UV-5151 composite light stabilizer is 6-10 g/L.
Wherein, (i) the electroplating pretreatment comprises a substrate mirror polishing treatment and a substrate cleaning treatment; here, the polishing process may include a peeling, grinding, leveling, and mirror finish polishing process; the base material cleaning treatment comprises the step of realizing surface fine cleaning by means of ultrasonic wax removal, ultrasonic oil removal, electrolysis, pure water cleaning and the like.
In the discoloration-resistant matte black chromium composite plating layer on the alloy base material, the electroplated copper layer consists of bottoming copper, copper pyrophosphate and copper sulfate, wherein the concentration of the electroplating solution of the bottoming copper is 35-45g/L of cuprous cyanide, and the concentration of free sodium cyanide is 9-16 g/L; the process conditions are as follows: the temperature is 35-55 ℃, the pH value is 11.5-13, the voltage is 2-5V, the current is 150-;
preferably, the concentration of the electroplating solution of the bottom copper is 35-45g/L of cuprous cyanide and 10-14g/L of free sodium cyanide; the process conditions are as follows: the temperature is 35-55 ℃, the pH value is 11.5-13, the voltage is 2-5V, the current is 200-;
the copper pyrophosphate electroplating solution has a potassium pyrophosphate concentration of 200-300g/L, a copper pyrophosphate concentration of 50-80g/L and an ammonia water concentration of 2-5mL/L, and the process conditions are as follows: the temperature is 50-60 ℃, the pH value is 7-9, the voltage is 1.5-3.5V, the current is 100-;
preferably, the electroplating solution of copper pyrophosphate has a potassium pyrophosphate concentration of 220-280g/L, a copper pyrophosphate concentration of 55-75g/L and an ammonia water concentration of 2-5mL/L, and the process conditions are as follows: the temperature is 50-60 ℃, the pH value is 7-9, the voltage is 1.5-3.5V, the current is 100-;
the copper sulfate electroplating solution is CuSO4 & 5H2O with the concentration of 180-220g/L and H2SO4 with the concentration of 60-80g/L, and the process conditions are as follows: the temperature is 20-30 ℃, the pH value is 7-9, the voltage is 2-6V, the current is 400-1800A, the Baume degree is 18-22Be, and the time is 1200-1800 s.
Preferably, the copper sulfate electroplating solution is CuSO4 & 5H2O with the concentration of 180-220g/L and H2SO4 with the concentration of 60-80g/L, and the process conditions are as follows: the temperature is 20-30 ℃, the pH value is 7-9, the voltage is 2-6V, the current is 500-1000A, the Baume degree is 18-22Be, and the time is 1200-1500 s.
In the anti-discoloration matte black chromium composite coating on the alloy substrate, the electroplating solution of the semi-gloss nickel layer is NiSO4Concentration of 260-2Concentration of 55-65g/L, H3BO3The concentration is 40-50g/L, the concentration of the Pre-ORIO softener is 3-5mL/L, the concentration of the Pre-ORIO leveling agent is 0.8-1.6mL/L, the temperature is 50-60 ℃, the pH value is 3.8-4.2, the voltage is 4-8V, and the time is 1200-1800 s.
Preferably, the electroplating solution of the semi-gloss nickel layer is NiSO4Concentration of 260-2Concentration of 55-65g/L, H3BO3The concentration is 40-50g/L, the concentration of the Pre-ORIO softener is 3-5mL/L, the concentration of the Pre-ORIO leveling agent is 0.8-1.6mL/L, the temperature is 50-60 ℃, the pH value is 3.8-4.2, the voltage is 4-8V, and the time is 1200-1500 s.
In the discoloration-resistant matte black chromium composite plating layer on the alloy base material, the electroplating solution of the hexavalent black chromium layer is prepared from chromic acid with the concentration of 400-450g/L, a decorative black chromium BK additive B40-80mL/L, a decorative black chromium BK additive AA 10-20mL/L, a decorative black chromium BK reducing agent 10-30mL/L and barium carbonate 10-30 g/L; the process conditions are as follows: the temperature is 15-25 ℃, the current density is 10-50A/dm2, and the time is 900-2400 s;
preferably, the electroplating solution of the hexavalent black chromium layer is prepared from 420g/L of chromic acid concentration, 60mL/L of decorative black chromium BK additive B, 15mL/L of decorative black chromium BK additive AA, 20mL/L of decorative black chromium BK reducing agent and 20g/L of barium carbonate; the process conditions are as follows: the temperature is 20 ℃, the current density is 30A/dm2, and the time is 1200-1800 s.
In the discoloration-resistant matte black chromium composite coating on the alloy substrate, the process conditions of the matte paint layer are as follows: primer coating: the voltage is 60-80KV, the air pressure is 5-10kg/cm, the paint amount is 30-60cc/min, and the UV-5151 composite light stabilizer is 4-12 g/L; leveling: the linear speed is 1-2m/min and 15-30 min; finishing paint: the voltage is 60-80KV, the air pressure is 5-10kg/cm, the paint amount is 30-60cc/min, and the UV-5151 composite light stabilizer is 4-12 g/L; leveling: the linear speed is 1-2m/min and 20-40 min; and (3) curing: the temperature is 100 ℃, the linear speed is 1-2m/min, and the time is 30-60 min. Wherein, the priming paint and the finishing paint are both matte transparent paint. By adopting the process conditions of the paint layer, the paint layer and the black chromium can be well combined.
In the discoloration-resistant matte black chromium composite plating layer on the alloy base material, the composite plating layer sequentially comprises an electroplated copper layer, a semi-gloss nickel layer and a hexavalent black chromium layer on the surface of the alloy base material, and a matte transparent paint surface layer is sprayed on the surface of the hexavalent black chromium layer, so that the discoloration-resistant matte black chromium composite plating layer is obtained;
the copper electroplating layer consists of copper cyanide, copper pyrophosphate and copper sulfate, wherein the copper cyanide electroplating solution has the concentration of 35-45g/L cuprous cyanide and the concentration of 10-14g/L free sodium cyanide; the process conditions are as follows: the temperature is 35-55 ℃, the pH value is 11.5-13, the voltage is 2-5V, the current is 200-400A, the Baume degree is 9-13Be, and the time is 1200-1300 s;
the copper pyrophosphate electroplating solution has a potassium pyrophosphate concentration of 220-280g/L, a copper pyrophosphate concentration of 55-75g/L and an ammonia water concentration of 2-5mL/L, and the process conditions are as follows: the temperature is 50-60 ℃, the pH value is 7-9, the voltage is 1.5-3.5V, the current is 100-;
the copper sulfate electroplating solution is CuSO4 & 5H2O with the concentration of 180-220g/L and H2SO4 with the concentration of 60-80g/L, and the process conditions are as follows: the temperature is 20-30 ℃, the pH value is 7-9, the voltage is 2-6V, the current is 500-1000A, the Baume degree is 18-22Be, and the time is 1200-1300 s;
the semi-bright nickel layer is electrically connectedThe plating solution is NiSO4Concentration of 260-2Concentration of 55-75g/L, H3BO3The concentration is 40-50g/L, the concentration of the Pre-ORIO softener is 3-5mL/L, the concentration of the Pre-ORIO leveling agent is 0.8-1.6mL/L, the temperature is 50-60 ℃, the pH value is 3.8-4.2, the voltage is 4-8V, and the time is 1200-;
the electroplating solution of the hexavalent black chromium layer is prepared from 420g/L chromic acid concentration, 60mL/L decorative black chromium BK additive B, 15mL/L decorative black chromium BK additive AA, 20mL/L decorative black chromium BK reducing agent and 20g/L barium carbonate; the process conditions are as follows: the temperature is 20 ℃, the current density is 30A/dm2, and the time is 1200-;
the components of the matte paint layer are polyurethane primer, curing agent HDI (Pasteur), acrylic extinction emulsion flatting agent, UV-5151 composite light stabilizer, dithiocarbamic acid antistatic agent and xylene solvent; the process conditions are as follows: primer coating: the voltage is 70KV, the air pressure is 8kg/cm, the paint amount is 40cc/min, and the UV-5151 composite light stabilizer is 8-10 g/L; leveling: the linear speed is 1.5m/min and 20 min; finishing paint: the voltage is 70KV, the air pressure is 8kg/cm, the paint amount is 40cc/min, and the UV-5151 composite light stabilizer is 8-10 g/L; leveling: the linear speed is 1.5m/min and 20 min; and (3) curing: the temperature is 100 ℃, and the linear speed is 1.5m/min and 40 min; wherein, the priming paint and the finishing paint are both matte transparent paint. By adopting the process conditions of the paint layer, the paint layer combined with black chromium can be optimally obtained.
Before the existing black chromium electroplating, the semi-gloss nickel is electroplated, because the semi-gloss nickel grows transversely in the electroplating process, the corrosion resistance can be effectively improved, and meanwhile, the potential difference of the plating solution can be modulated by the semi-gloss nickel, so that the binding force between the plating layers is better; in addition, the UV-5151 composite light stabilizer is added into the formula of the matte transparent paint, and is matched with components such as polyurethane primer, curing agent HDI (Baschiv), acrylic extinction emulsion leveling agent, UV-5151 composite light stabilizer, dithiocarbamate antistatic agent and the like, so that the color-change-resistant matte transparent paint layer is obtained, the matte transparent paint layer can prevent the black chromium coating from acting with the external high temperature, and the stability of the black chromium quality is enhanced.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the example serve to explain the principles of the invention and not to limit the invention.
FIG. 1 is a schematic diagram of a matte black chromium composite coating resistant to discoloration on an alloy substrate according to the present invention. Wherein, the mark 1 is an alloy base material comprising copper alloy, zinc alloy and stainless steel; mark 2 is a priming copper layer; reference 3 is a copper pyrophosphate layer; mark 4 is a copper sulfate layer; mark 5 is a semigloss nickel layer; mark 6 is a hexavalent black chromium layer; the reference 7 is a matt transparent lacquer layer.
FIG. 2 is a comparison of the stainless steel dome black chrome product of comparative example 1, which is not resistant to discoloration at high temperatures, and the stainless steel dome black chrome product of inventive example 1, which is resistant to discoloration at high temperatures, wherein the left is the product of comparative example 1 and the right is the product of inventive example 1. The test result shows that the product of the comparative example 1 is baked at the high temperature of 280 ℃ for 30min, the black coating on the surface of the product is discolored, and the product of the example 1 is baked at the high temperature of 280 ℃ for 30min, and the surface of the product keeps black.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
The invention provides a preparation method of a discoloration-resistant matte black chromium composite coating on an alloy substrate, which is characterized in that on the basis of an electroplated copper layer, semi-gloss nickel and hexavalent black chromium are prepared by adopting electroplating deposition, and a matte transparent paint layer is prepared by adopting a spraying technology, so that the discoloration-resistant matte black chromium composite coating is obtained, specifically, the surface of the alloy substrate is sequentially electroplated with the copper layer, the semi-gloss nickel layer and the hexavalent black chromium layer, and the surface of the hexavalent black chromium layer is sprayed with a matte transparent paint surface layer, so that the discoloration-resistant matte black chromium composite coating is obtained; the composite plating layer has the advantages of color change resistance, matte property, corrosion resistance and the like. The following is an example of electroplating of a stainless steel substrate.
The method mainly comprises the following steps:
1. the electroplating pretreatment comprises substrate mirror polishing treatment and substrate cleaning treatment
The polishing treatment mainly relates to the processes of peeling, grinding, leveling and mirror finish polishing, and the cleaning treatment realizes the surface fine cleaning by ultrasonic wave wax removal, ultrasonic wave oil removal, electrolysis and pure water cleaning respectively.
2. Electroplating black chromium composite layer
Plating a layer of priming copper, copper pyrophosphate, copper sulfate, semigloss nickel and hexavalent black chromium on the clean base material respectively.
(1) And (3) bottom copper plating: the concentration of cuprous cyanide is 45g/L, and the concentration of free sodium cyanide is 14 g/L; the process conditions are as follows: the temperature is 50 ℃, the pH value is 12.5, the voltage is 3V, the current is 200, the baume degree is 103Be, and the time is 1300 s;
(2) copper pyrophosphate: the concentration of potassium pyrophosphate is 260g/L, the concentration of copper pyrophosphate is 70g/L, the concentration of ammonia water is 5mL/L, and the process conditions are as follows: the temperature is 60 ℃, the pH value is 8, the voltage is 2V, the current is 200A, the baume degree is 30Be, and the time is 1300 s;
(3) copper sulfate: the concentration of CuSO4 & 5H2O is 220g/L, the concentration of H2SO4 is 80g/L, and the process conditions are as follows: the temperature is 30 ℃, the pH value is 8, the voltage is 3V, the current is 500A, the baume degree is 22Be, and the time is 1300 s;
(4) semi-gloss nickel: NiSO4NiCl at a concentration of 300g/L2The concentration is 70, the temperature is 60 ℃, the PH value is 4.2, the voltage is 4V, and the time is 1300 s;
(5) hexavalent black chromium: the chromic acid concentration is 420g/L, the decorative black chromium BK additive B is 60mL/L, the decorative black chromium BK additive AA is 15mL/L, the decorative black chromium BK reducing agent is 20mL/L, and the barium carbonate is 20 g/L; the process conditions are as follows: the temperature is 20 ℃, the current density is 30A/dm2, and the time is 1500 s; the decorative black chromium BK additive B, the decorative black chromium BK additive AA and the decorative black chromium BK reducing agent are products of Anmet chemical company Limited.
3. Spraying a matte transparent paint layer
And (3) spraying a matte transparent paint layer on the clean hexavalent chromium layer.
(1) A matte transparent paint layer: polyurethane primer, curing agent HDI (HDI), acrylic extinction emulsion leveling agent, UV-5151 composite light stabilizer, dithiocarbamic acid antistatic agent and xylene solvent; the process conditions are as follows: primer coating: the voltage is 70KV, the air pressure is 8kg/cm, the paint amount is 40cc/min, and the UV-5151 composite light stabilizer is 8 g/L; leveling: the linear speed is 1.5m/min and 20 min; finishing paint: the voltage is 70KV, the air pressure is 8kg/cm, the paint amount is 40cc/min, and the UV-5151 composite light stabilizer is 8 g/L; leveling: the linear speed is 1.5m/min and 20 min; and (3) curing: the temperature is 100 ℃, and the linear speed is 1.5m/min and 40 min; the UV-5151 composite light stabilizer is a product of BASF corporation.
Example 2
The preparation method is basically the same as that of example 1, except that the content of the UV-5151 composite light stabilizer is changed to 4g/L when the matte transparent paint layer is sprayed.
Example 3
The preparation method is basically the same as that of example 1, except that the content of the UV-5151 composite light stabilizer is changed to 12g/L when the matte transparent paint layer is sprayed.
Example 4
The preparation method is basically the same as that of example 1, except that the content of the UV-5151 composite light stabilizer is changed to 3g/L when the matte transparent paint layer is sprayed.
Example 5
The preparation method is basically the same as that of example 1, except that the content of the UV-5151 composite light stabilizer is changed when the matte transparent paint layer is sprayed, and the content of the UV-5151 composite light stabilizer is 13 g/L.
Comparative example 1
The preparation process was essentially the same as in example 1, except that after the hexavalent black chromium layer was plated, the matte transparent paint layer was not continuously sprayed.
TABLE I relevant test results and observations for inventive and comparative examples
From the data of table one above, it can be seen that:
when the content of the UV-5151 composite light stabilizer is gradually increased (such as example 2, example 3 and example 1), the black chromium composite product is baked at the high temperature of 280 +/-2 ℃ for 30min, and the surface plating layer has no color change; when the content of the UV-5151 composite light stabilizer is 3g/L (as in example 4), the black chromium composite product is baked for 30min at the high temperature of 280 +/-2 ℃, and the surface plating layer is discolored; when the content of the UV-5151 composite light stabilizer is 13g/L (as in example 5), the black chromium composite product is baked for 30min at the high temperature of 280 +/-2 ℃, the surface plating layer does not change color, but the matte degree of the prepared black chromium plating layer changes (before test); when a copper layer, a semi-gloss nickel layer and a hexavalent black chromium layer are directly electroplated on a stainless steel product, the surface plating layer is obviously discolored after being baked for 30min at the high temperature of 280 +/-2 ℃. The composite plating layer of the alloy substrate, the copper layer, the semi-gloss nickel layer, the hexavalent black chromium layer and the matte transparent paint layer has the advantages of color change resistance, matte property and corrosion resistance in the range of 4-12g/L of the UV-5151 composite light stabilizer.
Although the embodiments of the present invention have been described above, the above description is only for the convenience of understanding the present invention, and is not intended to limit the present invention. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The color-changing resistant matte black chromium composite coating is characterized by comprising an alloy substrate, wherein the surface of the alloy substrate is sequentially plated with an electroplated copper layer, a semi-gloss nickel layer, a hexavalent black chromium layer and a matte transparent paint layer,
the raw materials of the matte transparent paint layer comprise the following components: 100-400g/L of polyurethane, 40-140 g/L of curing agent HDI, 50-150 g/L, UV-5151 g/L of acrylic extinction emulsion leveling agent, 4-12g/L of composite light stabilizer, 30-200g/L of dithiocarbamate antistatic agent and 50-400 g/L of dimethylbenzene.
2. The composite coating of claim 1 wherein the electroplated copper layer has a thickness in the range of 30 μm to 45 μm, the semi-gloss nickel layer has a thickness in the range of 20 μm to 30 μm, the hexavalent black chromium layer has a thickness in the range of 0.5 μm to 5 μm, and the matte clear coat layer has a thickness in the range of 20 μm to 40 μm.
3. The composite plating layer of claim 2, wherein the electroplated copper layer comprises three layers of priming copper, copper pyrophosphate and copper sulfate, and the thickness of each layer is in the range of 10 μm to 15 μm.
4. The method for preparing the discoloration-resistant matte black chromium composite coating according to any one of claims 1 to 3, comprising the following steps:
(i) electroplating pretreatment, namely cleaning the surface of the alloy;
(ii) (ii) electroplating a copper layer, namely electroplating the copper layer on the clean base material obtained in the step (i);
(iii) electroplating a semi-gloss nickel layer, and performing electroplating semi-gloss nickel treatment on the clean copper sulfate layer obtained in the step (ii);
(iv) (iv) electroplating a black chromium layer, and performing black chromium electroplating treatment on the clean semi-bright nickel layer obtained in the step (iii);
(v) and (3) spraying a full-matte transparent paint layer, and performing matte transparent paint spraying treatment on the clean black chromium layer obtained in the step (iv).
5. The preparation method of the discoloration-resistant matte black chromium composite coating according to claim 4, characterized in that: the technological conditions of the matte paint layer are as follows: 4-12g/L curing of the UV-5151 composite light stabilizer: the temperature is 95-105 ℃.
6. The preparation method of the discoloration-resistant matte black chromium composite coating according to claim 4, characterized in that: the technological conditions of the matte paint layer are as follows: 6-10g/L of UV-5151 composite light stabilizer; and (3) curing: the temperature was 100 ℃.
7. The method for preparing the discoloration-resistant matte black chromium composite coating according to claim 4, wherein the copper electroplating layer is composed of priming copper, copper pyrophosphate and copper sulfate, wherein the electroplating solution of the priming copper is cuprous cyanide with a concentration of 35-45g/L and free sodium cyanide with a concentration of 9-16 g/L; the process conditions are as follows: the temperature is 35-55 ℃, the pH value is 11.5-13, the voltage is 2-5V, the current is 150-;
the copper pyrophosphate electroplating solution has potassium pyrophosphate concentration of 200-300g/L, copper pyrophosphate concentration of 50-80g/L and ammonia water concentration of 2-5mL/L, and the technological conditions are as follows: the temperature is 50-60 ℃, the pH value is 7-9, the voltage is 1.5-3.5V, the current is 100-;
the copper sulfate electroplating solution is CuSO4·5H2O concentration of 180-2SO4The concentration is 60-80g/L, and the process conditions are as follows: the temperature is 20-30 ℃, the pH value is 7-9, the voltage is 2-6V, the current is 400-1800A, the Baume degree is 18-22Be, and the time is 1200-1800 s.
8. The preparation method of the discoloration-resistant matte black chromium composite coating according to claim 4, characterized in that: wherein the electroplating solution of the semi-gloss nickel layer is NiSO4Concentration of 260-2Concentration of 55-65g/L, H3BO3The concentration is 40-50g/L, the concentration is 3-5mL/L for the Pre-ORIO softener, the concentration is 0.8-1.6mL/L for the Pre-ORIO leveling agent, the temperature is 50-60 ℃, the p H value is 3.8-4.2, the voltage is 4-8V, and the time is 1200-1800 s.
9. The preparation method of the discoloration-resistant matte black chromium composite coating according to claim 4, characterized in that: wherein the electroplating solution of the hexavalent black chromium layer is prepared from chromic acid with concentration of 400-450g/L, decorative black chromium BK additive B40-80mL/L, decorative black chromium BK additive AA 10-20mL/L, decorative black chromium BK reducing agent 10-30mL/L and barium carbonate 10-30 g/L; the process conditions are as follows: the temperature is 15-25 ℃, and the current density is 10-50A/dm2Time 900-2400s。
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