CN115012008B - Environment-friendly composite coating layer capable of improving adhesive force and preparation method thereof - Google Patents
Environment-friendly composite coating layer capable of improving adhesive force and preparation method thereof Download PDFInfo
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- CN115012008B CN115012008B CN202210332911.9A CN202210332911A CN115012008B CN 115012008 B CN115012008 B CN 115012008B CN 202210332911 A CN202210332911 A CN 202210332911A CN 115012008 B CN115012008 B CN 115012008B
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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
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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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
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention discloses a preparation method of an environment-friendly composite coating layer for improving adhesive force, which is characterized in that a nano inorganic compound is introduced in the electroplating process of a workpiece to prepare the composite coating layer, then the nano inorganic compound is subjected to grafting modification treatment and then is sprayed with a functional coating, the surface of the grafted modified nano inorganic compound contains organic short chains, the adhesive force between a base material of the workpiece and a top coating in the subsequent process is improved, and the functional coating is used for a longer time. The invention does not damage the surface structure of the workpiece, has strong process controllability and is suitable for practical production and application.
Description
Technical Field
The invention relates to the technical field of surface plating, in particular to an environment-friendly composite coating layer for improving adhesive force and a preparation method thereof.
Background
The use of kitchen and bathroom hardware products is very common, but the surface of the kitchen and bathroom hardware products is not resistant to dirt and is easy to grow bacteria, so the kitchen and bathroom hardware products are always pain points in the kitchen and bathroom industry. The existing kitchen and bathroom hardware product surface realizes easy-cleaning and antibacterial function effects, and is usually obtained by spraying a coating with easy-cleaning and antibacterial effects on the surface of electroplated metal bright chromium. However, the surface of the metal bright chromium coating is smooth, and the adhesive force of the coating on the top layer is poor, so that the coating such as an easy-cleaning coating, an antibacterial coating and the like on the surface of the kitchen and bathroom hardware product is easy to fall off, the durability is poor, and the use effect of the product is affected.
In order to improve the adhesion of the substrate to the top layer material, the prior art has:
in the patent CN 103434196A, the rough plating on the surface of a base material is improved by preparing flat anchor lines on the surface of the metal, so that the anti-corrosion layer is connected with the surface of the metal in a biting manner, and the mechanical binding force is exerted to the maximum; however, by preparing flat anchor lines on the metal surface, the metal surface layer structure is easy to damage, and a subsequent series of surface treatment methods are easy to cover up rough plating on the surface of the base material;
in patent CN 103820792B, siO is realized at lower temperature by plasma enhanced chemical vapor deposition 2 The deposition temperature of the film is reduced, the deposition rate is accelerated, and a surface treatment method of the preplating layer with good binding force is provided for subsequent treatment; however, the method has the problems that the thickness of the generated film is difficult to control, a certain covering power exists, and SiO 2 The coating technology has high cost and great difficulty in process control, and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to overcome the defects of poor binding force of a coating layer, damage to a metal surface layer structure, high cost, high process control difficulty and the like in the prior art, and provides an environment-friendly composite coating layer for improving adhesive force and a preparation method thereof.
In order to achieve the above object, the technical scheme of the present invention is as follows:
the preparation method of the environment-friendly composite coating layer for improving the adhesive force comprises the following steps:
1) Adding a cationic dispersing agent into an ethanol water solution with the weight percent of 40-60%, uniformly mixing, and then adding a nano inorganic compound with the particle size of 30-80 nm for uniformly dispersing to form a first mixed solution, wherein the adding amount of the nano inorganic compound is 0.5-5% of the ethanol water solution, and the adding amount of the cationic dispersing agent is 0.5-10% of the nano inorganic compound; the dispersion is uniform, and ultrasonic treatment can be adopted for 10min-30min;
2) Adding the first mixed solution into an electroplating bath solution, and uniformly mixing to form a composite electroplating solution, wherein the content of the nano inorganic compound in the composite electroplating solution is 0.5g/L-2g/L;
3) Placing a workpiece in a composite electroplating solution, taking the workpiece as an electroplating cathode, and forming a composite electroplated layer on the surface of the workpiece after electroplating treatment;
4) Providing 50-70 wt% ethanol water solution or methanol water solution, regulating the pH of the solution to 8-12, adding a grafting modifier, and uniformly mixing to form a second mixed solution, wherein the adding amount of the grafting modifier is 1-5 g/L;
5) Immersing the electroplated workpiece in a second mixed solution after cleaning and drying, and performing ultrasonic vibration for 2-4 hours to finish cleaning and drying the grafted and modified workpiece; the drying can be baking at 90-100 ℃ for 30-60 min.
6) And forming a functional coating on the surface of the workpiece by adopting a spraying process.
Optionally, the cationic dispersant is one or more of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and octadecyldimethylbenzyl ammonium chloride.
Optionally, the grafting modifier is one or more of gamma-glycidyl ether propyl trimethoxy silane, 3-amino propyl triethoxy silane and 3-glycidyl ether oxygen propyl trimethoxy silane.
Alternatively, the nano inorganic compound is SiO 2 、Al 2 O 3 、TiO 2 Through repeated grinding-dissolving-drying treatments.
Optionally, in step 3), the process parameters used for the electroplating are as follows: pH of the composite plating solution: 3.3-3.8, temperature: 50-60 ℃, current density: 4A/dm 2 -6A/dm 2 Electroplating time: 300s-720s, deposition rate: 0.01 μm/min-0.05 μm/min.
Optionally, the plating bath is a trivalent chromium based plating bath.
Optionally, the plating bath solution comprises the following components:
optionally, the functional coating is an easy-to-clean nano coating or an antibacterial nano coating based on an organic substrate, and is baked for 20-40 min at 140-160 ℃ after spraying.
The environment-friendly composite coating prepared by the preparation method comprises a composite electroplated layer formed on the surface of a workpiece and a functional coating formed on the surface of the composite electroplated layer.
Alternatively, the thickness of the composite electroplated layer is 0.2 μm to 0.5 μm, and the thickness of the functional coating layer is 3nm to 5 μm.
Optionally, the workpiece is a metal substrate, and conventional pretreatment such as polishing treatment, fine cleaning treatment and the like is performed; further, before forming the composite electroplated layer, one or more intermediate coatings are formed on the surface of the workpiece.
The functional coating is an easy-to-clean nano coating or an antibacterial nano coating based on an organic substrate, and is formed by spraying a mixed functional liquid containing the organic substrate for film formation, optional functional nano particles, optional auxiliary agents and solvents on the surface of a composite electroplated layer and drying the mixed functional liquid to form a film. The organic substrate is, for example, a perfluoropolyether, fluorosilane system, silane system, epoxy resin system, acrylic-urethane resin system, or the like. The surface of the grafted and modified nano inorganic compound contains organic short chains, so that the adhesive force between the base material and the functional coating of the subsequent process is improved.
The beneficial effects of the invention are as follows:
1) The nano inorganic compound is introduced in the electroplating process to prepare a composite electroplated layer, and the surface treatment is carried out on the nano inorganic compound, so that the electroplating efficiency and stability of the nano inorganic compound are improved, and the composite electroplated layer with uniformly dispersed nano inorganic compound is obtained; the surface of the grafted and modified nano inorganic compound contains organic short chains, so that the adhesive force between the base material and the functional coating is improved, and the functional coating can be used for a longer time;
2) The surface structure of the workpiece is not damaged, the process controllability is strong, and the method is suitable for actual production and application.
Drawings
FIG. 1 is a photograph of a sample of the adhesion test piece of the coating layer of example 1 (a), example 2 (b) and comparative example (c); the net structure in the figure is a coated hundred lattice test shape;
fig. 2 is a schematic view of water contact angles after the functional coatings of example 1 (a), example 2 (b) and comparative example (c) were abrasion-resistant 1 ten thousand times.
Detailed Description
The invention is further explained below with reference to the drawings and specific embodiments.
Example 1
1. And (3) electroplating pretreatment:
pre-treating a workpiece of a copper alloy substrate, including a substrate polishing treatment and a fine cleaning treatment, wherein the fine cleaning treatment comprises known processes such as wax removal, oil removal, electrolysis, pure water cleaning and the like; the workpiece base material may be stainless steel, zinc alloy, or the like;
the pretreated workpiece can be subjected to conventional electroplating technology to form an Ni-containing intermediate plating layer on the surface of the workpiece.
2. Preparation of environment-friendly composite electroplating solution for nano materials
Adding 30kg of 50wt% ethanol water solution into a reaction device, adding 15g of cationic dispersant cetyl trimethyl ammonium bromide in the ultrasonic dispersion process for ultrasonic dispersion for 30min, then mixing 300g of nano silicon dioxide with the particle size of 30-80 nm after repeated grinding, dissolving and baking, and performing ultrasonic dispersion for 15min to form uniform and stable solution (CDNC); the CDNC solution prepared above was added to 300L of the plating bath solution,
plating bath solution comprises the following components in percentage by weight:
and uniformly mixing in a vibration dispersion mode to form the composite electroplating solution.
3. Composite electroplating
Placing a workpiece in a plating bath filled with a composite plating solution, taking the workpiece as a plating cathode, taking lead-tin alloy as an anode, and forming a composite plating layer on the surface of the workpiece after plating treatment, wherein the plating process parameters are set as follows:
pH:3.5，
temperature: 55 c,
current density: 5A/dm 2 ，
Electroplating time: 600s of the time required for the preparation,
deposition rate: 0.03 μm/min;
the thickness of the composite plating layer was about 0.3. Mu.m.
4. Graft modification
Adding 300L of 65wt% ethanol water solution into a reaction device, adjusting the pH of the solution to 8-12, and then adding 300g of gamma-glycidyl ether propyl trimethoxysilane (gamma-EP) under an ultrasonic vibration mode to prepare a uniform and stable solution;
and (3) washing and drying the electroplated workpiece in the step (3), and then placing the workpiece in the solution, and continuously vibrating for 2 hours by ultrasound.
And taking out the workpiece after grafting, cleaning, and baking at 100 ℃ for 45min.
5. Spraying
Spraying easy-cleaning nano-liquid on the surface of the workpiece after drying in the step 4, and baking at 150 ℃ for 30min to form a functional coating. The easy-to-clean nano-liquid contains components such as perfluoropolyether, perfluorohexane, HFE-7200 and the like, and the spraying technological parameters are as follows: the workshop temperature is 25+/-3 ℃, the spraying time is 30-60 s, the distance between a spray gun and the spray gun is 150-300 mm, the moving speed is 0.3-0.6 m/s, and the thickness of the functional coating is about 3nm.
Example 2
The preparation method is basically the same as in example 1, except that 300g of nano silicon dioxide compound is added, and the grafting modifier is gamma-glycidyl ether propyl trimethoxysilane (gamma-EP) with the addition amount of 600g; the cationic dispersant cetyl trimethylammonium bromide (CB) was added in an amount of 15g.
Comparative example
The same pretreatment process was performed on the same work piece as in example 1, and the work piece was placed in a plating bath solution, which was:
the electroplating was performed using the same process parameters as in example 1. The surface spraying treatment of the workpiece after the electroplating is completed is as in step 5 of example 1).
The compositional differences and water contact angle tests (chrome plated surface raw water contact angle 85 °) of examples 1-2 and comparative examples are shown in fig. 1-2 and the following table:
as can be seen from fig. 1, the functional coatings of examples 1 to 2 have good adhesion on the surface of the composite electroplated layer, while the functional coating obtained by the comparative example has the conditions of poor adhesion, easy falling off, and the like on the surface of the common electroplated layer; as can be seen from fig. 2 and the table above, the water contact angle of the functional coatings of examples 1-2 after wear resistance for 1 ten thousand times still exceeds 105 °, while the comparative example is 94 °, which shows that the adhesion of the coating is further improved by spraying the functional coating after composite plating and graft modification.
The above embodiment is only used for further illustrating an environment-friendly composite coating layer for improving the adhesion and a preparation method thereof, but the invention is not limited to the embodiment, and any simple modification, equivalent variation and modification of the above embodiment according to the technical substance of the invention falls within the protection scope of the technical proposal of the invention.
Claims (9)
1. The preparation method of the environment-friendly composite coating layer for improving the adhesive force is characterized by comprising the following steps of:
1) Adding a cationic dispersing agent into an ethanol water solution with the weight percent of 40-60%, uniformly mixing, and then adding a nano inorganic compound with the particle size of 30-80 nm for uniformly dispersing to form a first mixed solution, wherein the adding amount of the nano inorganic compound is 0.5-5% of the ethanol water solution, and the adding amount of the cationic dispersing agent is 0.5-10% of the nano inorganic compound; the nano inorganic compound is SiO 2 、Al 2 O 3 、TiO 2 One or more of the following;
2) Adding the first mixed solution into an electroplating bath solution, and uniformly mixing to form a composite electroplating solution, wherein the content of the nano inorganic compound in the composite electroplating solution is 0.5g/L-2g/L;
3) Placing a workpiece in a composite electroplating solution, taking the workpiece as an electroplating cathode, and forming a composite electroplated layer on the surface of the workpiece after electroplating treatment;
4) Providing 50-70 wt% ethanol water solution or methanol water solution, regulating the pH of the solution to 8-12, adding a grafting modifier, and uniformly mixing to form a second mixed solution, wherein the adding amount of the grafting modifier is 1-5 g/L; the grafting modifier is one or more of gamma-glycidyl ether propyl trimethoxy silane, 3-amino propyl triethoxy silane and 3-glycidyl ether oxygen propyl trimethoxy silane;
5) Immersing the electroplated workpiece in a second mixed solution after cleaning and drying, and performing ultrasonic vibration for 2-4 hours to finish cleaning and drying the grafted and modified workpiece; the surface of the grafted and modified nano inorganic compound contains an organic short chain;
6) And forming a functional coating on the surface of the workpiece by adopting a spraying process, wherein the functional coating is an easy-to-clean nano coating or an antibacterial nano coating based on an organic substrate.
2. The method for preparing the environment-friendly composite coating layer for improving the adhesive force according to claim 1, which is characterized in that: the cationic dispersing agent is one or more of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride and octadecyldimethylbenzyl ammonium chloride.
3. The method for preparing the environment-friendly composite coating layer for improving the adhesive force according to claim 1, which is characterized in that: the nano inorganic compound is subjected to repeated grinding-dissolving-drying treatment.
4. The method for preparing the environment-friendly composite coating layer for improving the adhesive force according to claim 1, which is characterized in that: in step 3), the process parameters adopted in the electroplating are as follows: pH of the composite plating solution: 3.3-3.8, temperature: 50-60 ℃, current density: 4A/dm 2 - 6A/dm 2 Electroplating time: 300s-720s, deposition rate: 0.01 μm/min-0.05 μm/min.
5. The method for preparing the environment-friendly composite coating layer for improving the adhesive force according to claim 1, which is characterized in that: the plating bath solution is a trivalent chromium based plating bath solution.
6. The method for preparing an environmentally friendly composite coating layer for improving adhesion according to claim 5, wherein the electroplating bath solution comprises the following components:
200g/L to 350g/L of trivalent chromium conductive salt;
10g/L to 20g/L of trivalent chromium cylinder opener;
trivalent chromium wetting agent 0.5ml/L-2ml/L;
trivalent chromium 20g/L-23g/L;
60g/L-65g/L boric acid.
7. The method for preparing the environment-friendly composite coating layer for improving the adhesive force according to claim 1, which is characterized in that: and the functional coating is baked for 20-40 min at 140-160 ℃ after being sprayed.
8. An environmental protection composite coating prepared by the preparation method of any one of claims 1 to 7, which is characterized by comprising a composite electroplated layer formed on the surface of a workpiece and a functional coating formed on the surface of the composite electroplated layer.
9. The environmentally friendly composite coating according to claim 8, wherein the thickness of the composite plating layer is 0.2 μm to 0.5 μm and the thickness of the functional coating is 3nm to 5 μm.
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- 2022-03-31 CN CN202210332911.9A patent/CN115012008B/en active Active
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| US4775600A (en) * | 1986-03-27 | 1988-10-04 | Nippon Kokan Kabushiki Kaisha | Highly corrosion-resistant surface-treated steel plate |
| CN102066622A (en) * | 2008-07-15 | 2011-05-18 | 埃托特克德国有限公司 | Method for electrochemically depositing a metal on a substrate |
| CN102127793A (en) * | 2011-03-28 | 2011-07-20 | 上海大学 | Composite electroplating method of chrome-nano silicon dioxide of steel |
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| WO2020251573A1 (en) * | 2019-06-12 | 2020-12-17 | Oceanit Laboratories, Inc. | Composition and method for preparing corrosion resistant multifunctional coatings |
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