阅读说明：本技术 一种耐磨防腐的石墨烯/二氧化硅/环氧树脂超滑移复合涂层的制备方法 (Preparation method of wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating ) 是由 杨进 张一凡 宋浩杰 贾晓华 李永 王思哲 于 2021-09-17 设计创作，主要内容包括：本发明公开了一种耐磨防腐的石墨烯/二氧化硅/环氧树脂超滑移复合涂层的制备方法,包括：1、将环氧树脂和固化剂混合后加入无水乙醇中,搅拌均匀,再加入气相二氧化硅,制得A组分；2、将环氧树脂加入无水乙醇中,搅拌均匀,再加入单缩水甘油醚封端聚二甲基硅氧烷和二缩水甘油醚封端聚二甲基硅氧烷,制得B组分；3、将固化剂加入无水乙醇中,搅拌均匀,加入石墨烯/聚多巴胺粉末,制得C组分；4、将A组分加入喷涂设备进行喷涂；将喷涂有A组分的涂层第一次固化；按质量比1：(0.6-1)将B、C组分混合均匀后加入喷涂设备并喷涂至静置后的A组分涂层上；第二次固化后,得到石墨烯/二氧化硅/环氧树脂超滑移复合涂层。具有良好的耐磨防腐性能。(The invention discloses a preparation method of a wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating, which comprises the following steps: 1. mixing epoxy resin and a curing agent, adding the mixture into absolute ethyl alcohol, uniformly stirring, and adding fumed silica to prepare a component A; 2. adding epoxy resin into absolute ethyl alcohol, uniformly stirring, and then adding mono-glycidyl ether end-capped polydimethylsiloxane and diglycidyl ether end-capped polydimethylsiloxane to prepare a component B; 3. adding a curing agent into absolute ethyl alcohol, uniformly stirring, and adding graphene/polydopamine powder to prepare a component C; 4. adding the component A into spraying equipment for spraying; curing the coating sprayed with the component A for the first time; according to the mass ratio of 1: (0.6-1) uniformly mixing the B, C components, adding the mixture into spraying equipment, and spraying the mixture onto the A component coating after standing; and (4) after the second curing, obtaining the graphene/silicon dioxide/epoxy resin ultra-slip composite coating. Has good wear-resisting and corrosion-resisting properties.)

1. A preparation method of a wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating is characterized by comprising the following steps:

step 1, preparing a component A:

mixing 55-65% of epoxy resin, 33-40% of curing agent and 2-5% of fumed silica according to the following sequence by mass percent: firstly, adding epoxy resin and a curing agent into absolute ethyl alcohol, stirring to uniformly disperse the epoxy resin and the curing agent, then adding fumed silica, and performing ultrasonic dispersion to obtain a component A;

step 2, preparing a component B:

mixing 90-94% of epoxy resin, 2-4% of mono-glycidyl ether end-capped polydimethylsiloxane and 4-6% of diglycidyl ether end-capped polydimethylsiloxane according to the following sequence by mass percent: firstly, adding epoxy resin into absolute ethyl alcohol, stirring to uniformly disperse the epoxy resin, then adding mono-glycidyl ether end-capped polydimethylsiloxane and di-glycidyl ether end-capped polydimethylsiloxane, and performing ultrasonic dispersion to obtain a component B;

step 3, preparing a component C:

mixing 88-90% of curing agent and 10-12% of graphene/polydopamine powder according to the following sequence by mass percent: firstly, adding a curing agent into absolute ethyl alcohol, stirring to uniformly disperse the curing agent, then adding graphene/polydopamine powder, and performing ultrasonic dispersion to obtain a component C;

the preparation method of the graphene/polydopamine powder comprises the following steps: adding 0.2g of graphene powder into a Tris buffer solution, performing ultrasonic dispersion, adding 0.2g of dopamine hydrochloride, uniformly stirring, performing centrifugal purification, and drying to obtain graphene/polydopamine powder;

step 4, preparing the graphene/silicon dioxide/epoxy resin super-slip composite coating:

firstly, adding the component A into spraying equipment for spraying; then, the coating is cured for the first time; and then, mixing the components in a mass ratio of 1: (0.6-1) mixing the component B and the component C, and stirring to uniformly disperse the components to obtain a mixture; then, adding the mixture into spraying equipment, and spraying the mixture onto the cured A component coating; and finally, curing the coating for the second time to obtain the graphene/silicon dioxide/epoxy resin ultra-slip composite coating.

2. The preparation method of the wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating according to claim 1, wherein graphene/polydopamine powder is added in the step 1, and the mass percent of the graphene/polydopamine powder in the A component is not higher than 3%.

3. The preparation method of the wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating according to claim 1, wherein the trimethyl siloxane end-capped polydimethylsiloxane is further added in the step 2, and the trimethyl siloxane end-capped polydimethylsiloxane accounts for not more than 4% of the component B by mass.

4. The preparation method of the wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating according to claim 1, wherein fumed silica is further added in the step 3, and the fumed silica accounts for not more than 4% of the C component by mass.

5. The method for preparing the abrasion-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating according to claim 1, wherein the first curing in the step 4 is curing at 120 ℃ for 10-15min or standing for two hours in a ventilated dust-free environment.

6. The method for preparing the wear-resistant and corrosion-resistant graphene/silica/epoxy resin ultra-slip composite coating according to claim 1, wherein the second curing in the step 4 is curing at 120 ℃ for two hours.

Technical Field

The invention belongs to the technical field of composite coating material preparation, and particularly relates to a preparation method of a wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating.

Background

The super-slip coating is a composite material which is researched on the basis of low adhesion and high sliding performance of the surface of an object to liquid such as water and the like in application, and is suitable for the fields of water collection and fog collection, self-cleaning, photo-thermal deicing and the like. The super-slip coating realizes the effect of' liquid repellent by the low surface energy and the smooth surface, and the low-cost fluoride lubricating liquid meeting the requirements is applied to the preparation of the super-slip coating, so that the prepared super-slip coating is environment-friendly and not durable, and is difficult to be practically applied.

The wear-resistant anticorrosive coating is an important protective material for ensuring stable use and operation of mechanical appliances, is suitable for the fields of components, ships, aerospace, civil engineering, medical instruments and the like, has quite large demand and continuously increased demand performance, and is new in the aspect of meeting high-grade requirements of various working conditions, wear resistance for a long time and corrosion resistance in various severe environments. However, according to the difference between the coating covering substrate and the application field, it is difficult to manufacture a wear-resistant and corrosion-resistant coating with strong universality, and a coating suitable for various working conditions and various complex environments is also in urgent need of research and development.

The epoxy resin is a high molecular polymer which is a polycondensation product of epichlorohydrin and bisphenol A or polyhydric alcohol. The bisphenol A epoxy resin has the largest yield and the most complete variety, and new modified varieties are continuously increased, and the quality is continuously improved. The bisphenol A epoxy resin has excellent physical mechanical and electrical insulation properties, adhesion properties with various materials, flexibility in use process, and good adhesion. Graphene as a novel two-dimensional nano material has excellent mechanical property and wear resistance, the intrinsic strength is as high as 130GPa, and the graphene has a unique two-dimensional plane structure, so that the shearing force between sheet layers is very small, the friction coefficient is extremely low, and the graphene has more stable antifriction and wear resistance than carbon materials such as fullerene, carbon nano tube and graphite. Fumed silica, commonly known as fumed silica, has many unique properties, such as: can improve the ageing resistance, the strength and the chemical resistance of other materials.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a preparation method of a wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating, which can improve the wear-resistant and corrosion-resistant performance of an epoxy resin-based ultra-slip coating.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a wear-resistant and corrosion-resistant graphene/silicon dioxide/epoxy resin ultra-slip composite coating comprises the following steps:

step 1, preparing a component A:

mixing 55-65% of epoxy resin, 33-40% of curing agent and 2-5% of fumed silica according to the following sequence by mass percent: firstly, adding epoxy resin and a curing agent into absolute ethyl alcohol, stirring to uniformly disperse the epoxy resin and the curing agent, then adding fumed silica, and performing ultrasonic dispersion to obtain a component A;

step 2, preparing a component B:

mixing 90-94% of epoxy resin, 2-4% of mono-glycidyl ether end-capped polydimethylsiloxane and 4-6% of diglycidyl ether end-capped polydimethylsiloxane according to the following sequence by mass percent: firstly, adding epoxy resin into absolute ethyl alcohol, stirring to uniformly disperse the epoxy resin, then adding mono-glycidyl ether end-capped polydimethylsiloxane and di-glycidyl ether end-capped polydimethylsiloxane, and performing ultrasonic dispersion to obtain a component B;

step 3, preparing a component C:

mixing 88-90% of curing agent and 10-12% of graphene/polydopamine powder according to the following sequence by mass percent: firstly, adding a curing agent into absolute ethyl alcohol, stirring to uniformly disperse the curing agent, and then adding graphene/polydopamine powder for ultrasonic dispersion to prepare a component C;

the preparation method of the graphene/polydopamine powder comprises the following steps: adding 0.2g of graphene powder into a Tris buffer solution, performing ultrasonic dispersion, adding 0.2g of dopamine hydrochloride, uniformly stirring, performing centrifugal purification, and drying to obtain graphene/polydopamine powder;

step 4, preparing the graphene/silicon dioxide/epoxy resin super-slip composite coating:

firstly, adding the component A into spraying equipment for spraying; then, the coating is cured for the first time; and then, mixing the components in a mass ratio of 1: (0.6-1) mixing the component B and the component C, and stirring to uniformly disperse the components to obtain a mixture; then, adding the mixture into spraying equipment, and spraying the mixture onto the cured A component coating; and finally, curing the coating for the second time to obtain the graphene/silicon dioxide/epoxy resin ultra-slip composite coating.

Further, graphene/polydopamine powder is added in the step 1, and accounts for not more than 3% of the component A in percentage by mass.

Further, the trimethyl siloxane end-capped polydimethylsiloxane is added in the step 2, and the trimethyl siloxane end-capped polydimethylsiloxane accounts for not more than 4% of the component B by mass.

Further, fumed silica is added in the step 3, and the fumed silica accounts for not more than 4% of the C component by mass.

Further, the first curing in the step 4 is curing at 120 ℃ for 10-15min or standing for two hours in a ventilated dust-free environment.

Further, the second curing in the step 4 is curing at 120 ℃ for two hours.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, by utilizing the excellent physical mechanical and electrical insulating properties and good adhesive force of the epoxy resin, and the ordered and compact connection of the mono-glycidyl ether end-capped polydimethylsiloxane, the di-glycidyl ether end-capped polydimethylsiloxane and the bisphenol A epoxy resin through ring-opening polymerization reaction, a compact polydimethylsiloxane chain brush can be formed on the surface of the coating to endow the coating with super-slip property, and meanwhile, the amino group on the graphene/poly-dopamine can play the same effect as an epoxy resin curing agent, so that the graphene is tightly combined with an epoxy resin matrix, and the strength, stability and wear resistance of the coating and the aging resistance, strength and chemical resistance of fumed silica are enhanced. Therefore, the prepared graphene/silicon dioxide/epoxy resin ultra-slip composite coating has good wear resistance, corrosion resistance and ultra-slip performance, and has good controllability.

Drawings

FIG. 1: the invention sprays the picture of graphene/silicon dioxide/epoxy resin ultra-slip composite coating on 1060 aluminum plate;

FIG. 2: scanning electron microscope images of the graphene/silicon dioxide/epoxy resin ultra-slip composite coating;

FIG. 3: in the embodiments 1 to 3 of the present invention, a dynamic friction coefficient map obtained by rubbing the graphene/silica/epoxy resin super-slip composite coating for 1 hour under a load of 10N by using a rotary rubbing machine is obtained;

FIG. 4: the graphene/silicon dioxide/epoxy resin super-slip composite coating is rubbed by a rotary rubbing machine for 1 hour under the load of 10N to obtain a light mirror image of a grinding mark;

FIG. 5: a macroscopic water sliding performance expression photo of the graphene/silicon dioxide/epoxy resin ultra-sliding composite coating;

FIG. 6: in the embodiments 1 to 3, the graphene/silica/epoxy resin ultra-slip composite coating based on the 1060 aluminum plate is subjected to electrochemical test in 3.5 wt% NaCl solution to obtain a potential kinetic polarization curve diagram;

FIG. 7: in the embodiments 1 to 3, the graphene/silica/epoxy resin ultra-slip composite coating using a 1060 aluminum plate as a substrate is subjected to an electrochemical test in a 3.5 wt% NaCl solution to obtain a Nyquist plot;

FIG. 8: in examples 1 to 3 of the present invention, the graphene/silica/epoxy resin ultra-slip composite coating based on 1060 aluminum plate was electrochemically tested in 3.5 wt% NaCl solution to obtain a phase angle.

FIG. 9: in the embodiments 1 to 3 of the present invention, the graphene/silica/epoxy resin ultra-slip composite coating layer using 1060 aluminum plate as the substrate is subjected to electrochemical test in 3.5 wt% NaCl solution to obtain a bode coefficient diagram.

Detailed Description

The present invention will be explained in further detail with reference to examples.

Example 1

Pretreatment of a matrix: the base material of the sample is 1060 aluminum plate, and the sample is sprayed immediately after being wiped by absolute ethyl alcohol;

step 1, preparing a component A:

adding 22g of DY-E44 type epoxy resin, 15g of DY-E6012 type curing agent and 400ml of absolute ethyl alcohol into a 1000ml beaker, stirring and dispersing for 40min on a magnetic stirrer at the rotating speed of 2000r/min, adding 2g of fumed silica and 1g of polydopamine powder, and performing ultrasonic dispersion for 25min to obtain a coating A component;

step 2, preparing a component B:

adding 30g of DY-E44 type epoxy resin and 300ml of absolute ethyl alcohol into a 1000ml beaker, stirring and dispersing for 40min on a magnetic stirrer at a rotating speed of 1500r/min, then adding 1g of mono-glycidyl ether terminated polydimethylsiloxane and 1.5g of diglycidyl ether terminated polydimethylsiloxane, and performing ultrasonic dispersion for 15min to obtain a coating B component;

step 3, preparing a component C:

adding 18g of DY-E6012 type curing agent and 200ml of absolute ethyl alcohol into a 500ml beaker, dispersing for 30min on a magnetic stirrer at the rotating speed of 1200r/min, adding 2g of graphene/polydopamine powder, and performing ultrasonic dispersion for 25min to obtain a coating C component;

the preparation method of the graphene/polydopamine powder comprises the following steps: adding 0.2g of graphene powder and 100mL of Tris buffer solution into a 250mL beaker, performing ultrasonic dispersion for 30min, adding 0.2g of dopamine hydrochloride, stirring for 18-24h, performing centrifugal purification, and drying at 60 ℃ for 4 hours to obtain graphene/polydopamine powder;

step 4, preparing the graphene/silicon dioxide/epoxy resin super-slip composite coating:

firstly, adding the component A into spraying equipment, and spraying at the pressure of 1200 Psi; then, standing the coating for two hours in a ventilated dust-free environment; and then, mixing the components in a mass ratio of 1: 1, mixing the component B and the component C, and dispersing for 45min at the rotating speed of 2000r/min on magnetic stirring to obtain a mixture; then, adding the mixture into spraying equipment, and spraying the mixture onto the A component coating after standing at the pressure of 1500 Psi; and finally, curing the coating at 120 ℃ for two hours to obtain the graphene/silicon dioxide/epoxy resin ultra-slip composite coating.

Example 2

The matrix was pretreated, the preparation of component a in step 1 and the preparation of component C in step 3 in the manner described in example 1;

step 2, preparing a component B:

adding 33g of DY-E44 type epoxy resin and 300ml of absolute ethyl alcohol into a 1000ml beaker, stirring and dispersing for 40min on a magnetic stirrer at a rotating speed of 1500r/min, then adding 1.2g of monoglycidyl ether terminated polydimethylsiloxane, 1.5g of diglycidyl ether terminated polydimethylsiloxane and 0.8g of trimethylsiloxane terminated polydimethylsiloxane, and ultrasonically dispersing for 18min to obtain a coating B component;

and 4, step 4: preparing a graphene/silicon dioxide/epoxy resin super-slip composite coating:

firstly, adding the component A into spraying equipment, and spraying at the pressure of 1300 Psi; then, standing the coating for two hours in a ventilated dust-free environment; and then, mixing the components in a mass ratio of 1: 0.6 mixing the component B and the component C, and stirring and dispersing for 50min at the rotating speed of 2000r/min on magnetic stirring to obtain a mixture; then, adding the mixture into spraying equipment, and spraying the mixture onto the A component coating after standing at the pressure of 1600 Psi; and finally, curing the coating at 120 ℃ for two hours to obtain the graphene/silicon dioxide/epoxy resin ultra-slip composite coating.

Example 3

The substrate was pre-treated, component a prepared in step 1, component B prepared in step 2 and graphene/polydopamine powder prepared in step 3 in the manner described in example 1;

step 3, preparing a component C:

adding 18g of DY-E6012 type curing agent and 200ml of absolute ethyl alcohol into a 500ml beaker, dispersing for 30min on a magnetic stirrer at the rotating speed of 1200r/min, adding 2.4g of graphene/polydopamine powder, and performing ultrasonic dispersion for 25min to obtain a coating C component;

step 4, preparing the graphene/silicon dioxide/epoxy resin super-slip composite coating:

firstly, adding the component A into spraying equipment, and spraying at the pressure of 1400 Psi; then, curing the coating sprayed with the component A at 120 ℃ for 10 min; and then, mixing the components in a mass ratio of 1: 0.8, mixing the component B and the component C, and stirring and dispersing for 60min at the rotating speed of 2000r/min on magnetic stirring to obtain a mixture; then, adding the mixture into a spraying device, and spraying the mixture onto the A component coating after standing at the pressure of 1700 Psi; and finally, curing the coating at 120 ℃ for two hours to obtain the graphene/silicon dioxide/epoxy resin ultra-slip composite coating.

From fig. 1, fig. 2 and fig. 5, it can be seen that the graphene/silicon dioxide/epoxy resin super-slip composite coating prepared by the invention is flat, smooth and lyophobic, and has good slip performance; as can be seen from fig. 4, the coating remained intact after 1 hour of rubbing under a load of 10N, leaving only a slight wear scar on the surface of the coating, with a higher wear resistance than most of the ultra-smooth coatings; from fig. 3, it can be seen that the dynamic friction coefficients of the coatings prepared in examples 1 to 3 are not significantly increased with time, the average friction coefficient is maintained between 0.12 and 0.15, and the friction coefficient of most of the current polymer-based ultra-smooth coatings under the same condition is generally about 0.18, which indicates that the graphene/silica/epoxy resin ultra-slip composite coating prepared by the invention has more excellent friction reduction performance; as can be seen from FIGS. 6 to 9, the coating prepared by the present invention has a good corrosion prevention effect on aluminum substrates, and the impedance measured in electrochemical experiments is 1 to 2 orders of magnitude higher than that of the polymer-based super-smooth coating on the market at present, showing excellent corrosion resistance.