CN119264759A - A wear-resistant and rust-proof Teflon coating and preparation method thereof - Google Patents
A wear-resistant and rust-proof Teflon coating and preparation method thereof Download PDFInfo
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Abstract
本发明提出了一种耐磨防锈特氟龙涂料及其制备方法，属于涂料技术领域。将聚四氟乙烯微粉经过辐照后与甲基丙烯酸缩水甘油酯接枝改性，然后与经过硅烷偶联剂改性和水解后的氧化硅包覆改性Zn/Fe沉积多孔氧化铝纳米球反应，加入特氟龙底涂料中，搅拌混合均匀，制得耐磨防锈特氟龙涂料。本发明制得的涂料固化成膜后涂层致密，具有良好的润滑条件和抗机械作用效果，优异的耐磨性、抗刮划性、耐介质性、耐高温等性能，可有效抵御滑动摩擦、撞击摩擦、汽蚀摩擦等高耐磨环境，既能弥补两接触面由于摩擦而造成的磨损缺陷，又能使两个相对运动面具有良好的润滑减摩作用，解决摩擦、磨损难题，长期保护底材。The present invention proposes a wear-resistant and rust-proof Teflon coating and a preparation method thereof, and belongs to the technical field of coatings. After irradiation, polytetrafluoroethylene micropowder is grafted with glycidyl methacrylate, and then reacted with silicon oxide-coated modified Zn/Fe deposited porous alumina nanospheres that have been modified with a silane coupling agent and hydrolyzed, and then added to a Teflon primer, stirred and mixed evenly, to obtain a wear-resistant and rust-proof Teflon coating. After the coating prepared by the present invention is cured into a film, the coating is dense, has good lubrication conditions and anti-mechanical effects, excellent wear resistance, scratch resistance, medium resistance, high temperature resistance and other properties, can effectively resist high wear-resistant environments such as sliding friction, impact friction, cavitation friction, etc., can not only make up for the wear defects of the two contact surfaces caused by friction, but also enable the two relatively moving surfaces to have good lubrication and friction reduction effects, solve the friction and wear problems, and protect the substrate for a long time.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a wear-resistant antirust Teflon coating and a preparation method thereof.
Background
Teflon coating is an industrial coating material based on Polytetrafluoroethylene (PTFE) and has various excellent characteristics such as non-tackiness, heat resistance, slidability, moisture resistance, abrasion resistance, corrosion resistance, so that it is widely used in many industries.
The wear-resistant coating has the characteristics of low friction coefficient of the surface of a coating, high bearing load, strong mechanical resistance and the like as a protective function coating, so that the friction between interfaces can be effectively reduced when the wear-resistant coating is subjected to external force, the wear strength and the wear resistance are reduced, the effects of protecting a base material and prolonging the service life of the base material are achieved, and the wear-resistant coating is widely applied to the fields of aerospace craft, vehicles, ships, instruments and meters, machine tool industries and the like. In recent years, with the increasing attention paid to renewable energy sources, the demand for abrasion-resistant coatings has been rapidly increased in the energy field, and particularly, the abrasion-resistant coatings have been widely used for wind power blades, nuclear reactor containment vessels, dam structures, turbines, and the like.
The existing domestic and foreign wear-resistant paint mainly realizes the wear-resistant effect by adding lubricants such as graphite, molybdenum disulfide, graphene and derivatives thereof into the paint to ensure that the paint has good lubrication conditions, and transferring friction pairs into internal friction of the lubricants during interface contact so as to reduce friction between contact surfaces and realize lubrication and antifriction, and secondly, adding wear-resistant aggregates such as aluminum oxide, silicon carbide and silicon dioxide into the paint to improve the strength of the paint and effectively resist frequent external wear, high-speed scouring, violent collision and the like.
In addition, the matrix resin plays a decisive role in the abrasion resistance of the coating.
The addition of hard particles to teflon coatings has become an effective method to resist abrasion, however, if the addition of hard particles is too large, it is difficult to spray uniformly and micro-cracks may be caused inside the coating, and if the particles are too small, the particles agglomerate due to the increase of surface energy, and cannot be mixed uniformly. Both greatly reduce the hydrophobic properties of the coating and the stability of wear, and at the same time, the existence of microscopic cracks also makes corrosive media more likely to invade, damage the coating structure and further damage the wear properties of the coating. Therefore, the dispersibility of the additive is improved, and the prevention of particle aggregation in the coating after spraying and crack generation near the additive become key factors for improving the wear resistance of the coating. Meanwhile, the prepared Teflon coating is required to have a good rust prevention function.
Disclosure of Invention
The invention aims to provide a wear-resistant rust-resistant Teflon coating and a preparation method thereof, which have good lubrication condition and mechanical action resistance, excellent wear resistance, scratch resistance, dielectric resistance, high temperature resistance and the like, can effectively resist high wear-resistant environments such as sliding friction, impact friction, cavitation friction and the like, can compensate wear defects of two contact surfaces caused by friction, can ensure that two opposite movement surfaces have good lubrication antifriction effect, solve friction and wear problems, and protect a substrate for a long time.
The technical scheme of the invention is realized as follows:
The invention provides a preparation method of a wear-resistant antirust Teflon coating, which comprises the following steps:
S1, preparing porous alumina nanospheres, namely adding aluminum sulfate and urea into water, adding a pore-forming agent, heating and stirring for reaction, adjusting the pH value of the solution, continuously stirring for reaction, centrifuging, washing, drying and calcining to obtain the porous alumina nanospheres, wherein the mass ratio of the aluminum sulfate to the urea to the pore-forming agent is 3-5:7-10:0.1-0.2;
S2, depositing ZnO/Fe 2O3, namely adding porous alumina nanospheres into water, adding zinc salt and ferric salt, stirring and mixing uniformly, adding citric acid, heating and stirring, centrifuging, washing, drying and calcining to obtain ZnO/Fe 2O3 deposited porous alumina nanospheres, wherein the mass ratio of the porous alumina nanospheres to the zinc salt to the ferric salt to the citric acid is 10:2-3:1-2:4-7;
S3, reducing, namely reducing the ZnO/Fe 2O3 deposited porous alumina nanospheres by hydrogen to obtain Zn/Fe deposited porous alumina nanospheres;
S4, modifying, namely adding Zn/Fe deposited porous alumina nanospheres into ethanol, adding a silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain modified Zn/Fe deposited porous alumina nanospheres, wherein the mass ratio of the Zn/Fe deposited porous alumina nanospheres to the silane coupling agent is 10:3-5;
S5, hydrolyzing, namely adding the modified Zn/Fe deposited porous alumina nanospheres into water, stirring and hydrolyzing to obtain the silica coated modified Zn/Fe deposited porous alumina nanospheres;
S6, grafting modification of Teflon, namely adding polytetrafluoroethylene micro powder into Augeo SL-191 solvent, adding glycidyl methacrylate, a polymerization inhibitor and a sensitizer under irradiation condition, introducing inert gas, heating and stirring for reaction, extracting with acetone after the reaction is finished, and drying to obtain modified Teflon powder, wherein the mass ratio of the polytetrafluoroethylene micro powder to the glycidyl methacrylate to the polymerization inhibitor to the sensitizer is 10:2-3:0.01-0.02:0.02-0.05;
S7, preparing the wear-resistant and rust-resistant Teflon coating, namely adding the modified Teflon powder and the silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres into the Teflon primer, and stirring for reaction to obtain the wear-resistant and rust-resistant Teflon coating, wherein the mass ratio of the modified Teflon powder to the silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres to the Teflon primer is 10:4-7:70-80.
As a further improvement of the invention, the pore-forming agent in the step S1 is at least one selected from cetyltrimethylammonium chloride, cetyldimethylbenzyl ammonium chloride and cetyltrimethylammonium bromide, the temperature of the heating and stirring reaction is 60-70 ℃ for 30-50min, the pH value of the solution is adjusted to 9-10, the time of the continuous stirring reaction is 90-120min, the temperature of the calcination is 600-700 ℃ and the time is 1-2h.
As a further improvement of the invention, the temperature of heating and stirring in the step S2 is 85-95 ℃, the time of heating and stirring is 1-3 hours, the temperature of calcining is 400-500 ℃, the time of calcining is 1-3 hours, the zinc salt is zinc chloride or zinc nitrate, and the ferric salt is at least one of ferric chloride, ferric nitrate and ferric sulfate.
As a further improvement of the invention, the hydrogen reduction in step S3 is carried out at a temperature of 1100-1200 ℃ for a time of 2-4 hours.
As a further improvement of the present invention, the silane coupling agent in step S4 is at least one of KH550, KH602, KH 792.
As a further improvement of the invention, the silane coupling agent is a mixture of KH602 and KH792, the mass ratio is 2-4:3-5, the temperature of the heating and stirring reaction is 40-50 ℃ and the time is 1-2h.
As a further improvement of the invention, the temperature of the stirring hydrolysis in the step S5 is 40-50 ℃ and the time is 7-10h.
As a further improvement of the invention, the temperature of the irradiation condition in the step S6 is 100-150 ℃, the total irradiation dose is 12-15kGy, the polymerization inhibitor is ferrous ammonium sulfate, the sensitizer is concentrated sulfuric acid, the temperature of the heating and stirring reaction is 60-70 ℃, and the time of the heating and stirring reaction is 3-5 hours.
As a further improvement of the invention, the stirring reaction time in the step S7 is 10-12h.
The invention further protects the wear-resistant and rust-resistant Teflon coating, which is prepared by the preparation method of the wear-resistant and rust-resistant Teflon coating.
The invention has the following beneficial effects:
The mesoporous alumina nanospheres prepared by the method have the advantages that the mesoporous structure forms a larger specific surface area, the surface deposition of ZnO and Fe 2O3 is promoted, then the ZnO and the Fe are reduced into Zn and Fe through hydrogen, a compact oxide layer is formed after the Zn and the Fe are oxidized, a substrate can be well protected from rust, meanwhile, the surface of the mesoporous alumina nanospheres is modified through the silane coupling agent with amino groups, the surface of the prepared modified Zn/Fe deposited porous alumina nanospheres is provided with amino groups, meanwhile, the silane structure is contained, a silicon oxide layer is formed under the hydrolysis action of water, the wear resistance and the mechanical property of the paint are further improved, and the high temperature resistance of the paint is also improved.
According to the invention, the C-C bond and C-F on the Teflon polytetrafluoroethylene chain are broken by electron beam or gamma ray irradiation to generate free radicals, and the free radicals are utilized to initiate a grafting reaction of the glycidyl methacrylate monomer on the surface of the Teflon polytetrafluoroethylene chain, so that the polarity of PTFE is improved, the compatibility and reactivity of the PTFE with other substances are further increased, the grafted modified Teflon powder can carry out a ring-opening reaction with the silica coated modified Zn/Fe deposited porous alumina nanospheres with amino groups on the surface, so that the silica coated modified Zn/Fe deposited porous alumina nanospheres can be uniformly dispersed in the Teflon coating, the compatibility of inorganic particles is improved, and the mechanical property, wear resistance, rust resistance, dielectric resistance and other characteristics of the coating are greatly improved.
Augeo SL-191 used in the invention is a novel hydrophilic and oleophilic environment-friendly solvent developed by Rhodia company, has high boiling point, is colorless and odorless, has lower volatilization rate and is nontoxic to human health and environment.
The coating prepared by the invention has compact coating after being cured into a film, has good lubricating condition and mechanical action resistance, excellent wear resistance, scratch resistance, dielectric resistance, high temperature resistance and the like, can effectively resist high wear-resistant environments such as sliding friction, impact friction, cavitation friction and the like, can compensate the wear defect of two contact surfaces caused by friction, can ensure that two opposite movement surfaces have good lubricating antifriction effect, solves the friction and wear problems, and protects a substrate for a long time.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The polytetrafluoroethylene micropowder has a water content of less than 0.05%, and is purchased from Shenyang Seamatsu technology Co., ltd., teflon primer 420G-703, purchased from Cormu, inc., augeo SL-191, purchased from Rhodia, inc.
Example 1
The embodiment provides a preparation method of a wear-resistant antirust Teflon coating, which comprises the following steps:
s1, preparing porous alumina nanospheres, namely adding 30g of aluminum sulfate and 70g of urea into 2L of water, adding 1g of hexadecyl dimethyl benzyl ammonium chloride, heating to 60 ℃, stirring and reacting for 30min, adjusting the pH value of the solution to 9, continuously stirring and reacting for 90min, centrifuging, washing, drying, and calcining at 600 ℃ for 1h to obtain the porous alumina nanospheres;
S2, depositing ZnO/Fe 2O3, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 2g of zinc chloride and 1g of ferric chloride, stirring and mixing uniformly, adding 4g of citric acid, heating to 85 ℃, stirring for 1h, centrifuging, washing, drying, calcining at 400 ℃ for 1h, and obtaining ZnO/Fe 2O3 deposited porous alumina nanospheres;
S3, reducing, namely heating the ZnO/Fe 2O3 deposited porous alumina nanospheres to 1100 ℃, and reducing for 2 hours by hydrogen to obtain the Zn/Fe deposited porous alumina nanospheres;
S4, modifying, namely adding 10g of Zn/Fe deposited porous alumina nanospheres into 200mL of ethanol, adding 3g of silane coupling agent, heating to 40 ℃, stirring and reacting for 1h, centrifuging, washing and drying to obtain modified Zn/Fe deposited porous alumina nanospheres;
the silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 2:3;
s5, hydrolyzing, namely adding 10g of modified Zn/Fe deposited porous alumina nanospheres into 100mL of water, stirring and hydrolyzing for 7 hours at 40 ℃ to prepare silica coated modified Zn/Fe deposited porous alumina nanospheres;
S6, grafting modification of Teflon, namely adding 10g of polytetrafluoroethylene micro powder into a 200mL Augeo SL-191 solvent, under the irradiation condition, the temperature is 100 ℃, the total irradiation dose is 12kGy, adding 2g of glycidyl methacrylate, 0.01g of ferrous ammonium sulfate and 0.02g of concentrated sulfuric acid, introducing nitrogen, heating to 60 ℃, stirring and reacting for 3 hours, extracting with acetone for 24 hours after the reaction is finished, and drying to obtain modified Teflon powder;
S7, preparing the wear-resistant and rust-resistant Teflon coating, namely adding 10g of modified Teflon powder and 4g of silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres into 70g of Teflon primer, and stirring and reacting for 10 hours to obtain the wear-resistant and rust-resistant Teflon coating.
Example 2
The embodiment provides a preparation method of a wear-resistant antirust Teflon coating, which comprises the following steps:
S1, preparing porous alumina nanospheres, namely adding 50g of aluminum sulfate and 100g of urea into 2L of water, adding 2g of cetyltrimethylammonium bromide, heating to 70 ℃, stirring and reacting for 50min, adjusting the pH value of the solution to 10, continuously stirring and reacting for 120min, centrifuging, washing, drying, and calcining at 700 ℃ for 2h to obtain the porous alumina nanospheres;
s2, depositing ZnO/Fe 2O3, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 3g of zinc chloride and 2g of ferric sulfate, stirring and mixing uniformly, adding 7g of citric acid, heating to 95 ℃, stirring for 3h, centrifuging, washing, drying, and calcining at 500 ℃ for 3h to prepare ZnO/Fe 2O3 deposited porous alumina nanospheres;
S3, reducing, namely heating the ZnO/Fe 2O3 deposited porous alumina nanospheres to 1200 ℃, and reducing for 4 hours by hydrogen to obtain the Zn/Fe deposited porous alumina nanospheres;
S4, modifying, namely adding 10g of Zn/Fe deposited porous alumina nanospheres into 200mL of ethanol, adding 5g of silane coupling agent, heating to 50 ℃, stirring and reacting for 2 hours, centrifuging, washing and drying to obtain modified Zn/Fe deposited porous alumina nanospheres;
The silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 4:5;
s5, hydrolyzing, namely adding 10g of modified Zn/Fe deposited porous alumina nanospheres into 100mL of water, stirring and hydrolyzing for 10 hours at 50 ℃ to prepare silica coated modified Zn/Fe deposited porous alumina nanospheres;
S6, grafting modification of Teflon, namely adding 10g of polytetrafluoroethylene micro powder into a 200mL Augeo SL-191 solvent, under the irradiation condition, the temperature is 150 ℃, the total irradiation dose is 15kGy, adding 3g of glycidyl methacrylate, 0.02g of ferrous ammonium sulfate and 0.05g of concentrated sulfuric acid, introducing nitrogen, heating to 70 ℃, stirring and reacting for 5 hours, extracting with acetone for 24 hours after the reaction is finished, and drying to obtain modified Teflon powder;
S7, preparing the wear-resistant and rust-resistant Teflon coating, namely adding 10g of modified Teflon powder and 7g of silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres into 80g of Teflon primer, and stirring and reacting for 12 hours to prepare the wear-resistant and rust-resistant Teflon coating.
Example 3
The embodiment provides a preparation method of a wear-resistant antirust Teflon coating, which comprises the following steps:
S1, preparing porous alumina nanospheres, namely adding 40g of aluminum sulfate and 80g of urea into 2L of water, adding 1.5g of cetyltrimethylammonium chloride, heating to 65 ℃, stirring and reacting for 40min, adjusting the pH value of the solution to 9.5, continuously stirring and reacting for 100min, centrifuging, washing, drying, and calcining at 650 ℃ for 1.5h to obtain the porous alumina nanospheres;
S2, depositing ZnO/Fe 2O3, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 2.5g of zinc nitrate and 1.5g of ferric nitrate, uniformly stirring and mixing, adding 5.5g of citric acid, heating to 90 ℃, stirring for 2 hours, centrifuging, washing, drying, and calcining at 450 ℃ for 2 hours to prepare ZnO/Fe 2O3 deposited porous alumina nanospheres;
s3, reducing, namely heating the ZnO/Fe 2O3 deposited porous alumina nanospheres to 1150 ℃, and reducing for 3 hours by hydrogen to obtain the Zn/Fe deposited porous alumina nanospheres;
S4, modifying, namely adding 10g of Zn/Fe deposited porous alumina nanospheres into 200mL of ethanol, adding 4g of silane coupling agent, heating to 45 ℃, stirring and reacting for 1.5h, centrifuging, washing and drying to obtain modified Zn/Fe deposited porous alumina nanospheres;
The silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 3:4;
S5, hydrolyzing, namely adding 10g of modified Zn/Fe deposited porous alumina nanospheres into 100mL of water, stirring and hydrolyzing for 8 hours at 45 ℃ to prepare silica coated modified Zn/Fe deposited porous alumina nanospheres;
S6, grafting modification of Teflon, namely adding 10g of polytetrafluoroethylene micro powder into a 200mL Augeo SL-191 solvent, under the irradiation condition, the temperature is 125 ℃, the total irradiation dose is 13kGy, adding 2.5g of glycidyl methacrylate, 0.015g of ferrous ammonium sulfate and 0.04g of concentrated sulfuric acid, introducing nitrogen, heating to 65 ℃, stirring and reacting for 4 hours, extracting with acetone for 24 hours after the reaction is finished, and drying to obtain modified Teflon powder;
S7, preparing the wear-resistant and rust-resistant Teflon coating, namely adding 10g of modified Teflon powder and 5g of silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres into 75g of Teflon primer, and stirring and reacting for 11h to obtain the wear-resistant and rust-resistant Teflon coating.
Example 4
The difference compared to example 3 is that the silane coupling agent is a single KH602.
Example 5
The difference compared to example 3 is that the silane coupling agent is a single KH792.
Comparative example 1
In comparison with example 3, the difference is that steps S4 and S5 are not performed.
The method comprises the following steps:
S1, preparing porous alumina nanospheres, namely adding 40g of aluminum sulfate and 80g of urea into 2L of water, adding 1.5g of cetyltrimethylammonium chloride, heating to 65 ℃, stirring and reacting for 40min, adjusting the pH value of the solution to 9.5, continuously stirring and reacting for 100min, centrifuging, washing, drying, and calcining at 650 ℃ for 1.5h to obtain the porous alumina nanospheres;
S2, depositing ZnO/Fe 2O3, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 2.5g of zinc nitrate and 1.5g of ferric nitrate, uniformly stirring and mixing, adding 5.5g of citric acid, heating to 90 ℃, stirring for 2 hours, centrifuging, washing, drying, and calcining at 450 ℃ for 2 hours to prepare ZnO/Fe 2O3 deposited porous alumina nanospheres;
s3, reducing, namely heating the ZnO/Fe 2O3 deposited porous alumina nanospheres to 1150 ℃, and reducing for 3 hours by hydrogen to obtain the Zn/Fe deposited porous alumina nanospheres;
S4, grafting modification of Teflon, namely adding 10g of polytetrafluoroethylene micro powder into a 200mL Augeo SL-191 solvent, under the irradiation condition, the temperature is 125 ℃, the total irradiation dose is 13kGy, adding 2.5g of glycidyl methacrylate, 0.015g of ferrous ammonium sulfate and 0.04g of concentrated sulfuric acid, introducing nitrogen, heating to 65 ℃, stirring and reacting for 4 hours, extracting with acetone for 24 hours after the reaction is finished, and drying to obtain modified Teflon powder;
S5, preparing the wear-resistant and rust-resistant Teflon coating, namely adding 10g of modified Teflon powder and 5gZn/Fe deposited porous alumina nanospheres into 75g of Teflon primer, and stirring and reacting for 11 hours to prepare the wear-resistant and rust-resistant Teflon coating.
Comparative example 2
The difference from example 3 is that zinc nitrate is not added in step S2.
The method comprises the following steps:
S2, depositing Fe 2O3, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 4g of ferric nitrate, stirring and uniformly mixing, adding 5.5g of citric acid, heating to 90 ℃, stirring for 2 hours, centrifuging, washing, drying, and calcining at 450 ℃ for 2 hours to obtain the Fe 2O3 deposited porous alumina nanospheres.
Comparative example 3
In comparison with example 3, the difference is that no ferric nitrate was added in step S2.
The method comprises the following steps:
s2, depositing ZnO, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 4g of zinc nitrate, stirring and mixing uniformly, adding 5.5g of citric acid, heating to 90 ℃, stirring for 2h, centrifuging, washing, drying and calcining at 450 ℃ for 2h to obtain the ZnO deposited porous alumina nanospheres.
Comparative example 4
In comparison with example 3, the difference is that steps S2 and S3 are not performed.
The method comprises the following steps:
S1, preparing porous alumina nanospheres, namely adding 40g of aluminum sulfate and 80g of urea into 2L of water, adding 1.5g of cetyltrimethylammonium chloride, heating to 65 ℃, stirring and reacting for 40min, adjusting the pH value of the solution to 9.5, continuously stirring and reacting for 100min, centrifuging, washing, drying, and calcining at 650 ℃ for 1.5h to obtain the porous alumina nanospheres;
S2, modifying, namely adding 10g of porous alumina nanospheres into 200mL of ethanol, adding 4g of silane coupling agent, heating to 45 ℃, stirring and reacting for 1.5h, centrifuging, washing and drying to obtain modified porous alumina nanospheres;
The silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 3:4;
S3, hydrolyzing, namely adding 10g of modified porous alumina nanospheres into 100mL of water, stirring and hydrolyzing for 8 hours at 45 ℃ to obtain silica coated modified porous alumina nanospheres;
S4, grafting modification of Teflon, namely adding 10g of polytetrafluoroethylene micro powder into a 200mL Augeo SL-191 solvent, under the irradiation condition, the temperature is 125 ℃, the total irradiation dose is 13kGy, adding 2.5g of glycidyl methacrylate, 0.015g of ferrous ammonium sulfate and 0.04g of concentrated sulfuric acid, introducing nitrogen, heating to 65 ℃, stirring and reacting for 4 hours, extracting with acetone for 24 hours after the reaction is finished, and drying to obtain modified Teflon powder;
S5, preparing the wear-resistant and rust-resistant Teflon coating, namely adding 10g of modified Teflon powder and 5g of silicon oxide coated modified porous alumina nanospheres into 75g of Teflon primer, and stirring and reacting for 11 hours to prepare the wear-resistant and rust-resistant Teflon coating.
Comparative example 5
The difference compared with example 3 is that the modified teflon powder in step S7 is replaced by an equal amount of polytetrafluoroethylene micropowder.
The method comprises the following steps:
S1, preparing porous alumina nanospheres, namely adding 40g of aluminum sulfate and 80g of urea into 2L of water, adding 1.5g of cetyltrimethylammonium chloride, heating to 65 ℃, stirring and reacting for 40min, adjusting the pH value of the solution to 9.5, continuously stirring and reacting for 100min, centrifuging, washing, drying, and calcining at 650 ℃ for 1.5h to obtain the porous alumina nanospheres;
S2, depositing ZnO/Fe 2O3, namely adding 10g of porous alumina nanospheres into 200mL of water, adding 2.5g of zinc nitrate and 1.5g of ferric nitrate, uniformly stirring and mixing, adding 5.5g of citric acid, heating to 90 ℃, stirring for 2 hours, centrifuging, washing, drying, and calcining at 450 ℃ for 2 hours to prepare ZnO/Fe 2O3 deposited porous alumina nanospheres;
s3, reducing, namely heating the ZnO/Fe 2O3 deposited porous alumina nanospheres to 1150 ℃, and reducing for 3 hours by hydrogen to obtain the Zn/Fe deposited porous alumina nanospheres;
S4, modifying, namely adding 10g of Zn/Fe deposited porous alumina nanospheres into 200mL of ethanol, adding 4g of silane coupling agent, heating to 45 ℃, stirring and reacting for 1.5h, centrifuging, washing and drying to obtain modified Zn/Fe deposited porous alumina nanospheres;
The silane coupling agent is a mixture of KH602 and KH792, and the mass ratio is 3:4;
S5, hydrolyzing, namely adding 10g of modified Zn/Fe deposited porous alumina nanospheres into 100mL of water, stirring and hydrolyzing for 8 hours at 45 ℃ to prepare silica coated modified Zn/Fe deposited porous alumina nanospheres;
S6, preparing the wear-resistant and rust-resistant Teflon coating, namely adding 10g of polytetrafluoroethylene micro powder and 5g of silica coated modified Zn/Fe deposited porous alumina nanospheres into 75g of Teflon primer, and stirring and reacting for 11 hours to prepare the wear-resistant and rust-resistant Teflon coating.
Test example 1
The abrasion-resistant rust-resistant teflon coatings prepared in examples 1 to 5 and comparative examples 1 to 5 were sprayed on the surface of stainless steel having a primer, with a thickness of about 20 μm. The abrasion resistance of the abrasion resistance testing device is tested by using GCr15 pellets with the diameter of 4.5mm as a counter-abrasion pair on a reciprocating type friction abrasion testing machine, the load is 8.2N, the testing time is 15min, and the abrasion rate of the abrasion resistance testing device is tested. Scratch resistance was tested as specified in GB/T92798-2008. The pencil hardness of the coating was measured according to GB/T6739-2006 specification. The paint film adhesion was measured according to GB/T9286-1998, the test piece was divided into 5X 5 cells by a blade, the test piece was adhered by a transparent adhesive tape, and the adhesive tape was peeled off to observe the integrity of the paint film. The results are shown in Table 1.
TABLE 1
| Group of | Wear Rate (. Times.10 -4mm3/N.m) | Hardness (H) | Scratch resistance (kg) | Adhesion (grade) |
| Example 1 | 1.2 | 4 | 13 | 0 |
| Example 2 | 1.0 | 4 | 13 | 0 |
| Example 3 | 0.9 | 4 | 15 | 0 |
| Example 4 | 3.5 | 3 | 11 | 1 |
| Example 5 | 4.1 | 3 | 12 | 1 |
| Comparative example 1 | 12.1 | 2 | 9 | 2 |
| Comparative example 2 | 6.4 | 3 | 11 | 1 |
| Comparative example 3 | 6.9 | 3 | 11 | 1 |
| Comparative example 4 | 8.5 | 3 | 10 | 1 |
| Comparative example 5 | 59.8 | 1 | 6 | 3 |
As can be seen from the above table, the coating prepared from the wear-resistant rust-resistant Teflon coating prepared in the examples 1-3 has good wear resistance and comprehensive properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. The preparation method of the wear-resistant rust-proof Teflon coating is characterized by comprising the following steps of:
S1, preparing porous alumina nanospheres, namely adding aluminum sulfate and urea into water, adding a pore-forming agent, heating and stirring for reaction, adjusting the pH value of the solution, continuously stirring for reaction, centrifuging, washing, drying and calcining to obtain the porous alumina nanospheres, wherein the mass ratio of the aluminum sulfate to the urea to the pore-forming agent is 3-5:7-10:0.1-0.2;
S2, depositing ZnO/Fe 2O3, namely adding porous alumina nanospheres into water, adding zinc salt and ferric salt, stirring and mixing uniformly, adding citric acid, heating and stirring, centrifuging, washing, drying and calcining to obtain ZnO/Fe 2O3 deposited porous alumina nanospheres, wherein the mass ratio of the porous alumina nanospheres to the zinc salt to the ferric salt to the citric acid is 10:2-3:1-2:4-7;
S3, reducing, namely reducing the ZnO/Fe 2O3 deposited porous alumina nanospheres by hydrogen to obtain Zn/Fe deposited porous alumina nanospheres;
S4, modifying, namely adding Zn/Fe deposited porous alumina nanospheres into ethanol, adding a silane coupling agent, heating, stirring, reacting, centrifuging, washing and drying to obtain modified Zn/Fe deposited porous alumina nanospheres, wherein the mass ratio of the Zn/Fe deposited porous alumina nanospheres to the silane coupling agent is 10:3-5;
S5, hydrolyzing, namely adding the modified Zn/Fe deposited porous alumina nanospheres into water, stirring and hydrolyzing to obtain the silica coated modified Zn/Fe deposited porous alumina nanospheres;
S6, grafting modification of Teflon, namely adding polytetrafluoroethylene micro powder into Augeo SL-191 solvent, adding glycidyl methacrylate, a polymerization inhibitor and a sensitizer under irradiation condition, introducing inert gas, heating and stirring for reaction, extracting with acetone after the reaction is finished, and drying to obtain modified Teflon powder, wherein the mass ratio of the polytetrafluoroethylene micro powder to the glycidyl methacrylate to the polymerization inhibitor to the sensitizer is 10:2-3:0.01-0.02:0.02-0.05;
S7, preparing the wear-resistant and rust-resistant Teflon coating, namely adding the modified Teflon powder and the silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres into the Teflon primer, and stirring for reaction to obtain the wear-resistant and rust-resistant Teflon coating, wherein the mass ratio of the modified Teflon powder to the silicon oxide coated modified Zn/Fe deposited porous alumina nanospheres to the Teflon primer is 10:4-7:70-80.
2. The preparation method according to claim 1, wherein the pore-forming agent in the step S1 is at least one selected from cetyltrimethylammonium chloride, cetyldimethylbenzyl ammonium chloride and cetyltrimethylammonium bromide, the temperature of the heating and stirring reaction is 60-70 ℃ for 30-50min, the pH value of the solution is adjusted to 9-10, the time of the continuous stirring reaction is 90-120min, the temperature of the calcination is 600-700 ℃ and the time is 1-2h.
3. The method according to claim 1, wherein the temperature of the heating and stirring in the step S2 is 85-95 ℃, the time of the heating and stirring is 1-3 hours, the temperature of the calcining is 400-500 ℃, the time of the calcining is 1-3 hours, the zinc salt is zinc chloride or zinc nitrate, and the iron salt is at least one of ferric chloride, ferric nitrate, and ferric sulfate.
4. The method according to claim 1, wherein the hydrogen reduction in step S3 is performed at a temperature of 1100-1200 ℃ for a time of 2-4 hours.
5. The method according to claim 1, wherein the silane coupling agent in step S4 is at least one of KH550, KH602, KH 792.
6. The preparation method according to claim 5, wherein the silane coupling agent is a mixture of KH602 and KH792 in a mass ratio of 2-4:3-5, and the temperature of the heating and stirring reaction is 40-50 ℃ for 1-2 hours.
7. The method according to claim 1, wherein the temperature of the stirring hydrolysis in step S5 is 40 to 50 ℃ for 7 to 10 hours.
8. The preparation method according to claim 1, wherein the temperature of the irradiation condition in the step S6 is 100-150 ℃, the total irradiation dose is 12-15kGy, the polymerization inhibitor is ferrous ammonium sulfate, the sensitizer is concentrated sulfuric acid, the temperature of the heating and stirring reaction is 60-70 ℃, and the time of the heating and stirring reaction is 3-5h.
9. The method according to claim 1, wherein the stirring reaction time in step S7 is 10 to 12 hours.
10. A wear-resistant and rust-resistant teflon coating, characterized in that it is produced by the method for producing a wear-resistant and rust-resistant teflon coating according to any one of claims 1 to 9.
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