Super-durable energy storage and light-emitting anticorrosive coating and preparation method thereof

Abstract

The application provides an ultra-durable energy storage luminescent anticorrosive coating and a preparation method, and relates to the technical field of energy storage luminescent materials. According to the weight parts, the coating comprises 30-65 parts of energy storage luminescent particles, 10-35 parts of clay particles, 1-2 parts of hydrophobic fumed silica, 10-35 parts of resin and 1-4 parts of curing agent, and the energy storage luminescent particles and the clay particles are both modified by a hydrophobic modifier. The energy storage luminescent particles are MeOxAl2O3:Eu, wherein Me is any one of Ca, Mg and Sr, and x=0.5-2.0, and the clay particles are kaolin particles or sepiolite particles. The coating provided by the application has good luminescent performance, and has good anticorrosive performance, water resistance and salt water permeation resistance. The preparation process is simple, the cost is low, and the coating can be used for the protection and emergency display of metal facilities such as steel piles, lighthouses, warning signs, ships or ocean platforms.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of energy storage luminescent materials, and particularly relates to an ultra-durable energy storage luminescent anticorrosive coating and a preparation method. BACKGROUND

[0002] Energy storage luminescent materials are materials capable of absorbing and storing energy and emitting visible light under excitation. They can store energy when irradiated by natural light or illumination light sources, and slowly release the stored energy in the form of light after stopping the light source irradiation without consuming energy such as electricity, thereby realizing electric-free luminescence. Since energy storage luminescent materials generally realize luminescence by absorbing natural energy or through short-term excitation and have the characteristics of long afterglow, they are widely used in safety signs, emergency signals and persistent pigments, and have the advantages of no pollution and green environmental protection.

[0003] The luminescent coating with the characteristic of long afterglow can replace electric signal lamps to play a warning and indicating role in special environments where power supply is not timely or unavailable. In the environment near the sea, the sea and the open sea, due to the imperfect infrastructure, the identification with the functions of night warning and indication will lose effectiveness due to the erosion and damage of some seawater, and it is difficult to find and repair in time. Especially in islands where power facilities are imperfect, the lighthouse set for a long time in the corrosion environment will cause great safety hazards to ships, personnel and facilities in the open sea if the indicating function is lost due to circuit failure.

[0004] Due to the particularity of the marine environment, once the navigation facilities such as lighthouses and beacons fail, a long maintenance period is required, and the identification for navigation needs high brightness to facilitate recognition, so when the energy storage luminescent material is used for night warning and indication in the marine environment, the material has high requirements for the luminescence duration, brightness and durability of the material. The existing energy storage luminescent materials are mostly used in relatively stable environments such as clocks and indoor indicator lights, and do not have anticorrosive effect, so they have problems such as insufficient recognition and poor durability in the marine environment and are easily corroded and damaged. Therefore, in order to improve the durability and recognition of the identification in special service environments and prevent the substrate from being corroded, it is of great significance to prepare a multifunctional coating with anticorrosive, hydrophobic and luminescent properties by combining the characteristics of inorganic fillers when preparing protective coatings. SUMMARY

[0005] The purpose of the present application is to provide an ultra-durable energy storage luminescent anticorrosive coating and a preparation method to solve the problem that the existing coatings cannot provide corrosion protection and night recognition for metals at the same time in the marine environment.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] An ultra-durable energy storage and light-emitting anticorrosion coating, comprising, by weight parts: energy storage and light-emitting particles 30-65, clay particles 10-35, hydrophobic fumed silica 1-2, resin 10-35, curing agent 1-4, wherein the energy storage and light-emitting particles and the clay particles are both modified by a hydrophobic modifier.

[0008] Preferably, the energy storage and light-emitting particles are MeO xAl2O3:Eu, wherein Me is selected from any one of Ca, Mg and Sr, and x = 0.5-2.0.

[0009] Preferably, the particle size of the energy storage and light-emitting particles is 5-20 μm, the particle size of the hydrophobic clay particles is less than 5 μm, and the particle size of the hydrophobic fumed silica is 7-100 nm.

[0010] Preferably, the resin is selected from epoxy resin and / or polydimethylsiloxane resin, and the curing agent is selected from polyamide curing agent and / or polydimethylsiloxane curing agent.

[0011] Preferably, the hydrophobic modifier used for modifying the energy storage and light-emitting particles and the clay particles is independently selected from fatty acid type, coupling agent type and siloxane type hydrophobic modifier.

[0012] Preferably, by weight parts, the ratio of clay particles to fatty acid type hydrophobic modifier is 1:0.1-1, the ratio of clay particles to coupling agent type hydrophobic modifier is 1:0.025-0.1, and the ratio of clay particles to siloxane type hydrophobic modifier is 1:0.02-0.1.

[0013] Preferably, the clay particles are kaolin particles or sepiolite particles.

[0014] The application also provides a preparation method of the ultra-durable energy storage and light-emitting anticorrosion coating, comprising the following steps:

[0015] Step one: take the energy storage and light-emitting particles, hydrophobic clay particles and hydrophobic fumed silica in proportion, add them to excess organic solvent, and ultrasonically shake for 1-2 h to obtain a dispersion liquid;

[0016] Step two: add organic resin to the dispersion liquid obtained in step one, and fully stir to obtain component A;

[0017] Step three: add the curing agent to component A, fully stir, then coat on the surface of a substrate, and dry to obtain the ultra-durable energy storage and light-emitting anticorrosion coating.

[0018] Preferably, in step three, the substrate is metal, glass, wood board or paper board, and the coating method is spraying or brushing.

[0019] Preferably, in step three, the coating thickness is 200-500 μm.

[0020] Advantages:

[0021] (1) The super-durable energy storage luminescent anticorrosive coating provided by the present application comprises energy storage luminescent particles, hydrophobic clay, hydrophobic silicon dioxide and organic resin. The energy storage luminescent particles are uniformly dispersed in the organic resin together with the hydrophobic clay and the hydrophobic silicon dioxide after surface modification, and then solidified into a film, so that the coating has good luminescent performance, and also has good anticorrosive performance, water resistance and salt water permeation resistance. The preparation process is simple, the cost is low, the present application can be used for the protection and emergency display of metal facilities such as steel piles, lighthouses, warning signs, ships or ocean platforms, can effectively reduce the corrosion of these metal facilities and the resulting failure, and can play an emergency display role when failure occurs.

[0022] (2) The self-made hydrophobic clay particles in the coating of the present application reduce the manufacturing cost of the coating, and the modifier used also has the characteristics of low price and green environmental protection. In addition, compared with TiO2, SiO2, ZnO and other artificial raw materials, the clay particles have the advantages of environmental protection and abundant raw materials, which can reduce the manufacturing cost in the construction of the anticorrosive coating, and the surface of the clay particles has multiple functional groups, which is beneficial to grafting hydrophobic functional groups on the material surface. The modified clay particles can provide hydrophobic performance for the anticorrosive coating. BRIEF DESCRIPTION OF DRAWINGS

[0023] The drawings accompanying the specification of this application form a part thereof, serve to provide further understanding of the present application, and together with the description of the exemplary embodiments of the present application and their description serve to explain the present application, and do not constitute improper limitations on the present application. Among them:

[0024] Figure 1 The hydrophobic angle diagram of the yellow-green luminescent anticorrosive coating provided for Comparative Example 1 of the present application;

[0025] Figure 2 The hydrophobic angle diagram of the blue-green luminescent anticorrosive coating provided for Comparative Example 2 of the present application;

[0026] Figure 3 The hydrophobic angle diagram of the yellow-green luminescent anticorrosive coating provided for Comparative Example 3 of the present application;

[0027] Figure 4 The infrared spectrograms of the energy storage luminescent particles before and after surface modification provided for the embodiments of the present application;

[0028] Figure 5 The luminescent effect photos of the yellow-green energy storage luminescent particles before and after soaking in NaCl solution;

[0029] Figure 6Appearance change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 15 days;

[0030] Figure 7 Appearance change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 15 days;

[0031] Figure 8 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0032] Figure 9 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0033] Figure 10 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0034] Figure 11 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0035] Figure 12 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0036] Figure 13 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0037] Figure 14 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0038] Figure 15 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph;

[0039] Figure 16 Impedance spectroscopy change graph of the yellow-green luminescent anticorrosive coating provided for the present application comparative example 1 in a salt spray environment for 60 days, wherein the right graph is an enlarged view of the dotted line frame at the origin of the left graph; DETAILED DESCRIPTION

[0040] The technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments in the present application belong to the scope of protection of the present application.

[0041] The application will be described in detail below with reference to the embodiments. It should be noted that the embodiments in the application and the features in the embodiments can be combined with each other without conflict.

[0042] The application aims at the problem that the current energy storage luminescent material cannot provide effective corrosion protection and has poor night recognition, and provides an ultra-durable energy storage luminescent corrosion protection coating, which is suitable for protecting metal facilities in marine environment and has the characteristics of corrosion resistance and long afterglow, and can maintain the super-hydrophobic effect for a long time in outdoor environment.

[0043] The ultra-durable energy storage luminescent corrosion protection coating provided by the application comprises, by weight fraction, 30-65 parts (for example, 31 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 64 parts) of energy storage luminescent particles, 10-35 parts (for example, 11 parts, 15 parts, 20 parts, 25 parts, 30 parts, 34 parts) of clay particles, 1-2 parts (for example, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts) of hydrophobic fumed silica, 10-35 parts (for example, 11 parts, 15 parts, 20 parts, 25 parts, 30 parts, 34 parts) of resin, and 1-4 parts (for example, 1.1 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 3.9 parts) of curing agent, wherein the energy storage luminescent particles and the clay particles are both modified by a hydrophobic modifier.

[0044] The application uniformly disperses the energy storage luminescent particles, the hydrophobic clay and the hydrophobic fumed silica into the organic resin after surface modification of the energy storage luminescent particles, and then solidifies the film, so that the coating has good luminescent performance, and also has good corrosion protection performance, water resistance and salt water penetration resistance, and can be used for protecting metal facilities such as steel piles, lighthouses, warning signs, ships or offshore platforms, can effectively reduce the corrosion of these metal facilities and the resulting failures, and the coating produces long afterglow fluorescence after excitation, and can play an emergency display role.

[0045] In the preferred embodiment of the application, the energy storage luminescent particles are MeO·xAl2O3:Eu, wherein Me is selected from any one of Ca, Mg and Sr, and x = 0.5-2.0 (for example, x = 0.6, 0.8, 1.0, 1.2, 1.4, 1.6, 1.8, 1.9).

[0046] In the preferred embodiment of the present application, the particle size of the energy-storing and light-emitting particles is 5-20 μm (for example, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 19 μm), the particle size of the hydrophobic clay particles is less than 5 μm (for example, 4 μm, 3 μm, 2 μm, 1 μm), and the particle size of the hydrophobic fumed silica is 7-100 nm (for example, 8 μm, 10 μm, 15 μm, 20 μm, 30 μm, 50 μm, 70 μm, 90 μm, 99 μm).

[0047] In the preferred embodiment of the present application, the resin is selected from the group consisting of epoxy resin and / or polydimethylsiloxane resin, and the curing agent is selected from the group consisting of polyamide curing agent and / or polydimethylsiloxane curing agent.

[0048] In the preferred embodiment of the present application, the hydrophobic modifier used for the modification of the energy-storing and light-emitting particles and the clay particles is independently selected from the group consisting of fatty acid type, coupling agent type, and siloxane type hydrophobic modifier.

[0049] In the preferred embodiment of the present application, the ratio of the clay particles to the fatty acid type hydrophobic modifier is 1:0.1-1 (for example, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9) by weight, the ratio of the clay particles to the coupling agent type hydrophobic modifier is 1:0.025-0.1 (for example, 1:0.026, 1:0.030, 1:0.040, 1:0.050, 1:0.070, 1:0.090, 1:0.099), and the ratio of the clay particles to the siloxane type hydrophobic modifier is 1:0.02-0.1 (for example, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09).

[0050] In the preferred embodiment of the present application, the clay particles are kaolin particles or sepiolite particles.

[0051] The present application also provides a preparation method of the super-durable energy-storing and light-emitting anticorrosive coating.

[0052] Step one: the energy-storing and light-emitting particles, the hydrophobic clay particles, and the hydrophobic fumed silica are taken in a proportion, added to an excess of organic solvent, and ultrasonically oscillated for 1-2 h (for example, 1.0 h, 1.2 h, 1.5 h, 1.7 h, 1.9 h) to uniformly disperse them and obtain a dispersion liquid;

[0053] Step two: the organic resin is added to the dispersion liquid obtained in step one, and stirred to obtain component A;

[0054] Step three: the curing agent is added to component A, stirred to obtain a super-durable energy-storing and light-emitting anticorrosive coating.

[0055] In a preferred embodiment of the present invention, in step three, the substrate is metal, glass, wood, or cardboard, and the coating method is spraying or brushing.

[0056] In a preferred embodiment of the present invention, in step three, the coating thickness is 200μm to 500μm (e.g., 210μm, 250μm, 300μm, 350μm, 400μm, 450μm, 490μm).

[0057] The following detailed description of the present invention, including an ultra-durable energy-storing luminescent anti-corrosion coating and its preparation method, is provided through specific embodiments.

[0058] The sources of each raw material in the following embodiments are as follows:

[0059] Kaolin, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0060] Stearic acid, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0061] Ethanol, purchased from Sinopharm Chemical Reagent Co., Ltd.;

[0062] Titanate coupling agent 101 was purchased from Nanjing Chuangshi Chemical Additives Co., Ltd.

[0063] Tetraethyl silicate, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0064] Yellow-green energy-storing luminescent particles were purchased from Dalian Luming Luminescent Technology Co., Ltd.

[0065] Blue-green energy-storing luminescent particles were purchased from Dalian Luming Lumin Light Technology Co., Ltd.

[0066] Octadecyltrimethoxysilane was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0067] Hydrophobic fumed silica, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0068] Xylene was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0069] Epoxy resin E44 was purchased from Zhenjiang Danbao Resin Co., Ltd.

[0070] Diethylenetriamine, Sinopharm Chemical Reagent Co., Ltd.;

[0071] Polydimethylsiloxane resin, purchased from Dow Corning (China) Silicones Co., Ltd.;

[0072] Sylgard 184 curing agent was purchased from Dow Corning (China) Silicones Co., Ltd.

[0073] The energy storage luminescent particles have a molecular formula of MeO x Al 2 O 3 :Eu, wherein Me is selected from any one of Ca, Mg and Sr, and x = 0.5-2.0. The energy storage luminescent particles used in the following examples should not be considered as limiting the technical solutions of the present application, and it should be understood that other colors and manufacturers of energy storage luminescent particles can be used to replace the energy storage luminescent particles in the present application.

[0074] Example 1

[0075] Preparation of hydrophobic kaolin particles

[0076] The present example provides a hydrophobic clay particle, which is obtained by modifying kaolin particles with a hydrophobic modifier. The specific preparation method is as follows:

[0077] 5 g of kaolin, 1 g of stearic acid and 40 ml of ethanol were placed in a container, then placed in a constant temperature water bath at 60°C for 4 h of stirring, after stirring, centrifugation, removal of supernatant, drying at 80°C for 8 h, then grinding to obtain hydrophobic kaolin particles.

[0078] Example 2

[0079] Preparation of hydrophobic sepiolite particles

[0080] The present example provides a hydrophobic clay particle, which is obtained by modifying sepiolite particles with a hydrophobic modifier. The specific preparation method is as follows:

[0081] 5 g of sepiolite, 0.2 g of titanate coupling agent 101, 4 ml of tetraethyl silicate and 40 ml of ethanol were placed in a container, then placed in a constant temperature water bath at 30°C for 12 h of stirring, centrifugation to remove the supernatant, drying at 60°C for 6 h, and then grinding to obtain hydrophobic sepiolite particles.

[0082] Example 3

[0083] Preparation of stearic acid modified yellow-green energy storage luminescent particles

[0084] The present example provides a hydrophobic clay particle, which is obtained by modifying sepiolite particles with a hydrophobic modifier. The specific preparation method is as follows:

[0085] 2 g of stearic acid and 10 g of yellow-green energy storage luminescent particles were dissolved in 40 ml of ethanol, and stirred at 60°C for 6 h, then the solution was removed, and the reaction was dried in an oven at 50°C for 8 h, and then ground and sieved to obtain stearic acid modified yellow-green energy storage luminescent particles.

[0086] Example 4

[0087] Preparation of silane modified yellow-green energy storage luminescent particles

[0088] The present example provides a luminescent energy storage particle, which is obtained by modifying the yellow-green luminescent energy storage particle with octadecyltrimethoxysilane, and the specific preparation method is as follows:

[0089] 1ml of octadecyltrimethoxysilane and 10g of yellow-green luminescent energy storage particles are dissolved in 40ml of ethanol, and magnetic stirring is carried out at room temperature for 4h. After the reaction is completed, the solution is removed, and the reaction product is dried in an oven at 50°C for 8h. Grinding and sieving are performed to obtain the silane-modified yellow-green luminescent energy storage particles.

[0090] Example 5

[0091] Preparation of a yellow-green luminescent anticorrosive coating:

[0092] The present example provides a yellow-green luminescent anticorrosive coating, and the specific preparation method is as follows:

[0093] 0.15g of hydrophobic fumed silica, 1g of hydrophobic kaolin, and 4g of stearic acid-modified yellow-green luminescent energy storage particles are dispersed in 6ml of dimethylbenzene, ultrasonic dispersion is carried out for 1h, and magnetic stirring is carried out at room temperature for 3h to fully disperse the particles in the solution. Then, 1g of epoxy resin E44 and 0.1g of the curing agent diethylenetriamine thereof are added, and stirring is continued for 1h. The solution is brushed on a steel sheet, and after curing at room temperature for 2h, the steel sheet is placed in an oven at 60°C for further curing for 8h to obtain a yellow-green luminescent anticorrosive coating, and the dry film thickness is about 200μm.

[0094] Example 6

[0095] Preparation of a yellow-green luminescent anticorrosive coating:

[0096] The present example provides a yellow-green luminescent anticorrosive coating, and the specific preparation method is as follows:

[0097] 0.15g of hydrophobic fumed silica, 1g of hydrophobic kaolin, and 4g of stearic acid-modified yellow-green luminescent energy storage particles are dispersed in 6ml of dimethylbenzene, ultrasonic dispersion is carried out for 1h, and magnetic stirring is carried out at room temperature for 3h to fully disperse the particles in the solution. Then, 1g of epoxy resin E44 and 0.1g of the curing agent diethylenetriamine thereof are added, and stirring is continued for 1h. The solution is brushed on a steel sheet, and after curing at room temperature for 2h, the steel sheet is placed in an oven at 60°C for further curing for 8h to obtain a yellow-green luminescent anticorrosive coating.

[0098] Example 7

[0099] Preparation of a yellow-green luminescent anticorrosive coating:

[0100] 0.2g of hydrophobic fumed silica, 2g of hydrophobic kaolin, 6g of silane-modified yellow-green energy-storing luminescent particles, and 12ml of xylene were mixed. The mixture was first sonicated for 1 hour, and then magnetically stirred at room temperature for 6 hours to fully disperse the particles. Next, 1.5g of epoxy resin E44, 0.15g of curing agent diethylenetriamine, 2g of polydimethylsiloxane resin, and 0.2g of curing agent Sylgard184 were added. The mixture was then magnetically stirred for 2 hours. The stirred solution was sprayed onto a steel plate with an airbrush and cured at 100℃ for 3 hours to obtain a yellow-green luminescent anti-corrosion coating with a dry film thickness of approximately 100μm.

[0101] Example 8

[0102] Preparation of stearic acid-modified blue-green energy-storing luminescent particles:

[0103] 2g of stearic acid and 10g of blue-green energy-storing luminescent particles were dissolved in 40ml of ethanol and magnetically stirred at 60℃ for 6h. After the reaction was complete, the solution was removed, and the reactants were dried in an oven at 50℃ for 8h. The mixture was then ground and sieved to obtain stearic acid-modified blue-green energy-storing luminescent particles.

[0104] Example 9

[0105] Preparation of blue-green luminescent anti-corrosion coating:

[0106] 0.15g of hydrophobic fumed silica, 1g of hydrophobic sepiolite, and 4g of stearic acid-modified blue-green energy-storing luminescent particles were dispersed in 6ml of xylene and ultrasonically dispersed for 1h. The mixture was then magnetically stirred at room temperature for 3h to ensure complete dispersion of the particles. Subsequently, 1g of epoxy resin E44 and 0.1g of its curing agent diethylenetriamine were added, and stirring was continued for 1h. The solution was then brushed onto a steel sheet and cured at room temperature for 2h. Finally, the sheet was placed in a 60℃ oven for another 8h to obtain a blue-green luminescent anti-corrosion coating.

[0107] Comparative Example 1

[0108] Preparation of the yellow-green luminescent coating:

[0109] 0.2g of hydrophobic fumed silica, 2g of unmodified kaolin, 6g of silane-modified yellow-green energy-storing luminescent particles, and 12ml of xylene were mixed. The mixture was first sonicated for 1 hour, then magnetically stirred at room temperature for 6 hours to ensure complete particle dispersion. Next, 1.5g of epoxy resin E44, 0.15g of curing agent diethylenetriamine, 2g of polydimethylsiloxane resin, and 0.2g of curing agent Sylgard 184 were added. The mixture was then stirred for 2 hours. The solution was sprayed onto a steel plate and cured at 100℃ for 3 hours to obtain a yellow-green luminescent anti-corrosion coating. This coating has a hydrophobic angle of 114.6° and does not possess good waterproofing properties. Figure 1 As shown.

[0110] Comparative Example 2

[0111] Preparation of blue-green luminescent coating:

[0112] 0.15 g hydrophobic fumed silica, 1 g unmodified sepiolite and 4 g stearic acid modified blue-green energy storage luminescent particles and 6 ml xylene were mixed, ultrasonic dispersion for 1 h, magnetic stirring at room temperature for 3 h, the particles in the solution were fully dispersed, then 1 g of epoxy resin E44 and 0.1 g of its curing agent diethylene triamine were added, and stirring was continued for 1 h. The solution was brushed on the steel sheet with a brush, and after curing at room temperature for 2 h, it was placed in a 60°C oven for 8 h of further curing to obtain a blue-green luminescent anticorrosive coating. The hydrophobic angle of the coating was 120.2°, which did not have good waterproof effect, as shown in Figure 2 .

[0113] Comparative Example 3

[0114] Preparation of yellow-green luminescent coating:

[0115] 0.2 g hydrophobic fumed silica, 2 g unmodified kaolin, 6 g unmodified yellow-green energy storage luminescent particles and 12 ml xylene were mixed, ultrasonic dispersion for 1 h, then magnetic stirring at room temperature for 6 h to fully disperse the particles. Next, 1.5 g of epoxy resin E44 and 0.15 g of curing agent diethylene triamine and 2 g of polydimethylsiloxane resin and 0.2 g of curing agent Sylgard 184 were added, followed by stirring for 2 h. The stirred solution was sprayed on a steel plate with a spray pen and cured at 100°C for 3 h to obtain a yellow-green luminescent anticorrosive coating. The hydrophobic angle of the coating was 121.5°, which did not have good waterproof effect, as shown in Figure 3 .

[0116] Comparative Example 4

[0117] This comparative example provides a yellow-green luminescent anticorrosive coating, which is prepared as follows:

[0118] 0.15 g hydrophobic fumed silica, 1 g unmodified kaolin and 4 g stearic acid modified yellow-green energy storage luminescent particles were dispersed in 6 ml xylene, ultrasonic dispersion for 1 h, magnetic stirring at room temperature for 3 h to fully disperse the particles in the solution. Then 1 g of epoxy resin E44 and 0.1 g of its curing agent diethylene triamine were added, and stirring was continued for 1 h. The solution was brushed on the steel sheet with a brush, and after curing at room temperature for 2 h, it was placed in a 60°C oven for 8 h of further curing to obtain a yellow-green luminescent anticorrosive coating.

[0119] Property analysis:

[0120] (1) Modification of particle characterization:

[0121] The yellow-green energy storage luminescent particles before modification, the modified yellow-green energy storage luminescent particles prepared in Examples 3 and 4 were subjected to infrared characterization, as shown in Figure 4 .

[0122] It can be seen from Figure 1 that the luminescent particles modified by stearic acid and the luminescent particles modified by silane have new peaks in the range of 2850 cm -1 -3000 cm -1 compared with the original particles, and the peaks in this part are mainly methyl and methylene groups, which come from stearic acid and octadecyltrimethoxysilane, and these groups have hydrophobic function, indicating that the modification of stearic acid and octadecyltrimethoxysilane on the luminescent particles is successful.

[0123] (2) Comparison of modification effect:

[0124] 1g of the stearic acid modified yellow-green energy storage luminescent particles prepared in Example 3 was dispersed in 100ml of simulated seawater with 3.5wt.% NaCl solution to simulate seawater and adjusted to pH=7 for 7 days. The luminescent effect was compared before and after soaking for 7 days, and compared with the unmodified yellow-green energy storage luminescent particles, as shown in Figure 5 , the yellow-green energy storage luminescent particles modified by stearic acid can still emit obvious fluorescence after soaking for 7 days, and the luminescent intensity does not decrease obviously, which proves that the yellow-green energy storage luminescent particles modified by stearic acid have good resistance to salt water environment.

[0125] In addition, it can also be seen from Figure 5 that the unmodified yellow-green energy storage luminescent particles are turbid and opaque as a whole when soaked in 3.5wt.% NaCl solution for 0 days, indicating that part of the particles are quickly dissolved in the solution, while the stearic acid modified yellow-green energy storage luminescent particles still have good transparency after soaking for 7 days, indicating that even in the environment of long-term salt water soaking, the yellow-green energy storage luminescent particles modified by stearic acid also show good water resistance.

[0126] (2) Anticorrosion performance test

[0127] The application of the yellow-green luminescent anticorrosive coating prepared in Example 5 in the simulated atmospheric environment was evaluated in a salt spray environment with a temperature of 35℃ and a salt water concentration of 5wt.% NaCl, and compared with the yellow-green luminescent coating prepared in Comparative Example 1, as shown in Figure 6 , 7 .

[0128] It can be seen from Figure 6 that the surface of the coating of Comparative Example 1 is obviously rusted after 15 days of salt spray, and has poor corrosion resistance; while from Figure 7It can be seen that the surface of the coating of Example 5 has little change after 15 days of salt spray, and the coating has excellent corrosion resistance.

[0129] The mechanism of the yellow-green luminescent anticorrosive coating of Example 5 was analyzed by electrochemical impedance spectroscopy using an Autolab PGSTAT302N electrochemical workstation from Switzerland, and the Nyquist plot of the coating is shown in Figure 8 The larger the diameter of the semicircle, the greater the resistance of ion diffusion from the solution to the metal substrate, and the better the corrosion resistance of the coating.

[0130] As shown in Figure 8 , the radius of the semicircle of the yellow-green luminescent anticorrosive coating of Example 5 can reach 10 11 Ω·cm 2 Ω·cm 10 Ω·cm 2 Ω·cm

[0131] A 3.5wt.% NaCl solution was used to simulate seawater, and the pH was adjusted to pH=7, pH=4 and pH=10, and the corrosion resistance of the silane-modified yellow-green luminescent anticorrosive coating prepared in Example 7 was evaluated, as shown in Figures 9-10 From which it can be seen that after the coating is immersed in different solutions for 10 days, although the impedance value of the coating decreases, it still remains at a high impedance of about 10 8 Ω·cm 2 Ω·cm

[0132] In order to better verify the durability of the yellow-green luminescent anticorrosive coating of Example 7 in actual environment, a 60-day outdoor exposure experiment was conducted, and the wettability results of the coating are shown in Figure 12 It can be found that the contact angle of the coating is gradually decreasing, but it still remains in a super-hydrophobic state above 150°.

[0133] At the same time, from the electrochemical impedance spectrum of Figure 13 , it can be seen that the impedance of the coating after 60 days is maintained at about 10 9 Ω·cm 2 Ω·cm

[0134] (3) Luminescent performance test

[0135] The residual luminescence decay brightness of the coating was tested using the X-Rite SM208 screen brightness meter, and the process was as follows: the coating was placed under a xenon lamp for 5 min, the excitation illuminance was 1000 lx, and the excitation time was 5 min.

[0136] From Figure 14 It can be seen that the yellow-green luminescent anticorrosive coating provided in Example 5 has little change in luminescent performance in the 30-minute residual luminescence test after 60 days of salt spray testing; from Figure 15 It can be seen that the yellow-green luminescent anticorrosive coating provided in Example 7 has a small decrease in luminescent performance compared to the initial performance after 60 days of outdoor exposure, which is due to the dust adhering to the surface of the coating during outdoor exposure, reducing the residual luminescence time of the coating.

[0137] (4) Abrasion performance test

[0138] Test method: the surface of the coating was placed on a 600-mesh sandpaper loaded with a 100g weight, and the sample was slowly pulled forward, and 25cm was one cycle, and the water contact angle (WCA) and the rolling angle (SA) of the coating were tested every 2 cycles.

[0139] From Figure 16 It can be seen from the above that the WCA of the yellow-green luminescent anticorrosive coating of Example 3 remains greater than 150° and the SA is less than 10° after 20 cycles of abrasion, maintaining the super-hydrophobic state. At the same time, when the abrasion test is less than 15 cycles, the hydrophobic angle of the coating increases and the rolling angle decreases with the increase of the cycle number, that is, with the continuous abrasion of the coating, the hydrophobic performance of the coating is improved, which is due to the fact that the hydrophobicity of the film-forming components such as epoxy resin is not as good as that of the hydrophobic fumed silica, and the exposure of the hydrophobic particles in the coating after the abrasion of the coating surface improves the hydrophobic performance of the coating. When the abrasion cycle exceeds 15 times, the hydrophobic particles in the coating have been fully exposed, and further abrasion cycle will cause the hydrophobic particles to fall off from the coating, thereby causing the hydrophobic angle to decrease.

[0140] In summary, the super-durable energy storage luminescent anticorrosive coating provided by the present application has good luminescent performance, and also has good anticorrosive performance, water resistance and salt water permeability resistance. The preparation process is simple, the cost is low, and the present application can be used for the protection and emergency display of steel piles, lighthouses, warning signs, ships or metal facilities of offshore platforms, which can effectively reduce the corrosion of these metal facilities and the resulting failure, and play an emergency display role when the failure occurs, thereby solving the problem that the existing coating cannot provide anticorrosion and night recognition for metal at the same time in the marine environment.

[0141] The above merely illustrates the preferred embodiments of the present application, and is not used to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A superdurable energy storing light emitting anticorrosive coating characterized in that, By weight parts, including: energy storage light-emitting particles 30~65 parts, clay particles 10~35 parts, hydrophobic fumed silica 1~2 parts, resin 10~35 parts, curing agent 1~4 parts; The energy storage light-emitting particles are obtained by modifying treatment by the following two methods: The energy storage light-emitting particles are MeO·xAl2O3:Eu, wherein Me is selected from any one of Ca, Mg and Sr, and x=0.5~2.0; The energy storage light-emitting particles are modified by stearic acid, and the preparation is as follows: 2g of stearic acid and 10g of energy storage light-emitting particles are dissolved in 40mL of ethanol, and magnetic stirring is carried out at 60℃ for 6h, the solution is removed after the reaction is completed, and the reaction product is dried in an oven at 50℃ for 8h, and then ground and sieved to obtain the stearic acid modified energy storage light-emitting particles; or, The energy storage light-emitting particles are modified by octadecyl trimethoxysilane, and the preparation is as follows: 1mL of octadecyl trimethoxysilane and 10g of energy storage light-emitting particles are dissolved in 40mL of ethanol, and magnetic stirring is carried out at room temperature for 4h, the solution is removed after the reaction is completed, and the reaction product is dried in an oven at 50℃ for 8h, and then ground and sieved to obtain the silane modified energy storage light-emitting particles; The clay particles are modified by a hydrophobic modifier; the hydrophobic modifier for modifying the clay particles is selected from fatty acid type, coupling agent type and siloxane type hydrophobic modifiers; by weight parts, the clay particles:fatty acid type hydrophobic modifier=1:0.1~1, the clay particles:coupling agent type hydrophobic modifier=1:0.025~0.1, and the clay particles:siloxane type hydrophobic modifier=1:0.02~0.

1.

2. The superdurable, energy stored, light emitting, anticorrosive coating according to claim 1, characterized in that The particle size of the energy storage light-emitting particles is 5~20μm, the particle size of the clay particles modified by the hydrophobic modifier is less than 5μm, and the particle size of the hydrophobic fumed silica is 7~100nm.

3. The superdurable, energy stored, light emitting, anticorrosive coating according to claim 1, wherein, The resin is selected from epoxy resin and / or polydimethylsiloxane resin, and the curing agent is selected from polyamide curing agent and / or polydimethylsiloxane curing agent.

4. The superdurable energy storing and light emitting anticorrosive coating according to any one of claims 1-3, characterized in that, The clay particles are kaolin particles or sepiolite particles.

5. The method for preparing the ultra-durable energy-storing luminescent anti-corrosion coating as described in any one of claims 1 to 4, characterized in that, The method comprises the following steps: Step one: take the modified energy storage light-emitting particles, the clay particles modified by the hydrophobic modifier and the hydrophobic fumed silica in a proportion, add them to an excess of organic solvent, and ultrasonically oscillate for 1~2h to make them uniformly dispersed, to obtain a dispersion liquid; Step two: add the organic resin to the dispersion liquid obtained in step one, and fully stir to make them uniformly mixed, to obtain component A; Step three: add the curing agent to component A, fully stir to make them uniformly mixed, then coat on the surface of a substrate, and dry to obtain a super-durable energy storage light-emitting anticorrosive coating.

6. A process for the preparation of superdurable energy stored light emitting anticorrosive coating as claimed in claim 5 wherein, In step three, the substrate is metal, glass, wood board or paper board, and the coating method is spraying or brushing.

7. A process for the preparation of superdurable energy stored light emitting anticorrosive coating as claimed in claim 5 wherein, In step three, the coating thickness is 200μm~500μm.

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