CN115634822A - Application of super-hydrophobic coating based on modified nano-silica to metal - Google Patents
Application of super-hydrophobic coating based on modified nano-silica to metal Download PDFInfo
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Abstract
The invention belongs to the technical field of coating, and particularly relates to an application of a modified nano-silica-based super-hydrophobic coating on metal. The method comprises the following steps: preparing an epoxy resin adhesive; (2) preparing a low surface energy substance; (3) preparing a surface film substance; (4) application to metals: s1, taking a metal sheet with a clean surface, and brushing KH550; s2, brushing the liquid A; s3, uniformly covering the nitrile rubber powder on a metal sheet by using a micron-sized mesh screen, and drying; s4, spraying the liquid B to the metal sheet, and drying; and S5, uniformly spraying the solution C, and drying. The coating can obviously enhance the hydrophobicity and the wear resistance of metal when being applied to the metal, has relatively simple process and is easy for industrial production.
Description
Technical Field
The invention belongs to the technical field of coating, and particularly relates to an application of a modified nano-silica-based super-hydrophobic coating on metal.
Background
The initial inspiration of the super-hydrophobic surface is derived from the lotus leaf effect, the lotus leaf has self-cleaning capability and is derived from the micro-nano structure and wax crystal substances on the surface, so that the contact angle of the lotus leaf is larger when the lotus leaf is contacted with a water drop, and the lotus leaf is easy to roll off, and belongs to the bionic invention. The super-hydrophobicity refers to a super-hydrophobic state formed by that generally, a water drop is spherical on a solid surface, a contact angle is larger than 150 degrees, a rolling angle is smaller than 10 degrees, the lower the surface energy of a material is, the better the hydrophobicity is, and if a micro-rough structure exists, a layer of air film is formed between the water drop and the material. The application field of the super-hydrophobic material is quite wide nowadays, and the super-hydrophobic material has a very wide application prospect in fields such as corrosion prevention, pollution prevention, self-cleaning, adhesion prevention and drag reduction, microfluid control and the like. However, due to the limitation of the current technology and development cost, the superhydrophobic coating is mostly not good enough in hydrophobicity, is not wear-resistant and easy to age, is limited in application, and is not much in actual industrialization and commercialization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the application of the modified nano-silica-based super-hydrophobic coating on metal, the coating can obviously enhance the hydrophobicity and the wear resistance of the metal when being applied to the metal, the process is relatively simple, and the industrial production is easy to realize.
The application of the modified nano-silica-based super-hydrophobic coating on metal comprises the following steps:
(1) Formulating epoxy resin adhesives
Adding 2.0-2.4 parts by mass of epoxy resin into 7.6-8.0 parts by mass of ethyl acetate, stirring until the epoxy resin is dissolved, adding 1.5-2 parts by mass of addition type liquid silicone rubber, 8-8.5 parts by mass of ethyl acetate and 0.136-0.180 part by mass of tetraethylenepentamine, and adding the mixture into a reagent bottle for later use after the epoxy resin is dissolved to obtain solution A;
(2) Formulating low surface energy materials
Stirring silicone oil, epoxy resin, tetraethylenepentamine, ethyl acetate and absolute ethyl alcohol until the silicone oil, the epoxy resin, the tetraethylenepentamine, the ethyl acetate and the absolute ethyl alcohol are dissolved, then adding fluorine modified nano silicon dioxide, and dispersing the fluorine modified nano silicon dioxide into the solution by ultrasonic waves to obtain solution B;
(3) Preparing surface film material
Adding epoxy resin and tetraethylenepentamine into ethyl acetate for dissolving, and filling into a reagent bottle for later use to obtain solution C;
(4) Application to metal
S1, taking a metal sheet with a clean surface, and brushing KH550;
s2, brushing the liquid A;
s3, uniformly covering the nitrile rubber powder on a metal sheet by using a micron-sized mesh screen, and drying;
s4, spraying the liquid B to the metal sheet, and drying;
and S5, uniformly spraying the solution C, and drying.
Wherein:
preferably, in step (1), the epoxy resin adhesive is 22% epoxy resin adhesive, and the preparation method is as follows: weighing 2.2 parts by mass of epoxy resin, adding the epoxy resin into 7.8 parts by mass of ethyl acetate, stirring to dissolve the epoxy resin, adding 1.75 parts by mass of addition type liquid silicone rubber, 8.25 parts by mass of ethyl acetate and 0.159 part by mass of tetraethylenepentamine, and adding the mixture into a reagent bottle after the mixture is completely dissolved to obtain solution A.
In the step (2), the preparation of the low surface energy substance is specifically as follows: adding 1-1.4 parts by mass of silicone oil, 1.8-2.2 parts by mass of epoxy resin, 0.090-0.127 part by mass of tetraethylenepentamine, 7.2725-8.95 parts by mass of ethyl acetate and 7.2725-9.28 parts by mass of absolute ethyl alcohol, stirring until completely dissolving, adding 0.8-1.2 parts by mass of fluorine modified nano silicon dioxide, and performing ultrasonic dispersion to the solution until completely dispersing to obtain solution B.
Preferably, in step (2), the low surface energy material is specifically formulated as: adding 1.2 parts by mass of silicone oil, 2 parts by mass of epoxy resin, 0.109 part by mass of tetraethylenepentamine, 7.2725 parts by mass of ethyl acetate and 7.2725 parts by mass of absolute ethyl alcohol, stirring until complete dissolution, and adding fluorine modified nano silicon dioxide for ultrasonic dispersion to obtain solution B.
In the step (2), the mass ratio of the silicone oil to the tetraethylenepentamine is 10-12; the mass ratio of the fluorine modified nano silicon dioxide to the silicone oil is 0.57-1.2. The mass ratio of the ethyl acetate to the absolute ethyl alcohol is 0.8-1.2. The mass ratio of the epoxy resin to the silicone oil is 1.29-2.2.
In the step (3), 2-4 parts by mass of epoxy resin and 0.181-0.33 part by mass of tetraethylenepentamine are added into 95.67-97.819 parts by mass of ethyl acetate, stirred until dissolved, and filled into a reagent bottle for later use to obtain solution C.
Preferably, in step (3), 3 parts by mass of epoxy resin and 0.27 part by mass of tetraethylenepentamine are added and dissolved in 96.73 parts by mass of ethyl acetate, and the solution is filled into a reagent bottle for standby as solution C.
In the step S1, the thickness of the brush coating KH550 is 0.1-0.2mm.
In step S2, the thickness of the brushing liquid A is 0.1-0.2mm.
In step S3, the covering thickness of the nitrile rubber powder is 0.2-0.4mm.
In step S4, the thickness of the spraying liquid B is 0.2-0.4mm.
In step S5, the thickness of the spraying C liquid is 0.08-0.12mm.
In steps S3-S5, the drying conditions are as follows: 50-60 ℃ for 2-3 hours.
The metal of the present invention is exemplified by a carbon-iron alloy.
The invention is mainly applied to daily metal base materials, has good wear resistance and hydrophobicity, the optimal contact angle of the finished product can reach more than 160 degrees, and the good hydrophobicity can be still maintained even when 4500g of shakeout is subjected to standard shakeout experiments.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, a low-surface-energy substance is manufactured through the synergistic effect of fluorine-silicon modification, and a micro-nano structure is constructed by applying the mutual adhesion of nitrile rubber powder and modified nano-silica, so that the hydrophobic capacity is greatly enhanced and is far beyond that of domestic similar coating products.
2. The invention effectively solves the problems of weak adhesion, easy shedding and the like of the metal surface by covering a layer of nitrile rubber on the metal surface by using the adhesion effect of the epoxy resin and the liquid silicone rubber, and can be applied to the metal surface.
3. The invention uses wear-resistant and hydrophobic nitrile rubber as a substrate, which can effectively improve the wear resistance of the coating and prolong the service life of the coating.
4. The invention has relatively simple process and is easy for industrialized production.
Drawings
FIG. 1-1 is a graph of the contact angle shown for an unground sample prepared according to example 1;
FIGS. 1-2 are photographs showing the contact angle after passing 4500g shakeout experiments on samples formulated in example 1;
FIG. 2-1 is a graph of the contact angle shown for an ungrased sample prepared according to example 2;
FIG. 2-2 is a photograph showing the contact angle after passing through a 4500g shakeout test, of a sample prepared according to example 2;
FIG. 3-1 is a photograph of an unground sample prepared according to example 3 showing contact angles;
FIG. 3-2 is a photograph showing the contact angle after passing through a 4500g shakeout test for the sample formulated in example 3;
FIG. 4-1 is a photograph of an unground sample obtained by the method of comparative example 1 showing the contact angle;
FIG. 4-2 is a picture of the contact angle shown after passing 4500g of the shakeout test for the sample resulting from the method of comparative example 1;
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings.
The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby. The procedures, conditions, reagents, test methods and the like for carrying out the present invention are general knowledge and common general knowledge in the art except for the contents specifically mentioned below, and the present invention is not particularly limited. The data given in the examples below include specific operating and reaction conditions and products.
The epoxy resin used in the examples was E-44.
The fluorine-modified nanosilica used in the examples is a product marketed by Weifang-Heng scintillating nanomaterials Ltd.
In the embodiment, the iron sheet is made of carbon-iron alloy.
Example 1
(1) Preparing 20% of epoxy resin: adding 2.0 parts by mass of epoxy resin into 8 parts by mass of ethyl acetate, stirring until the epoxy resin is dissolved, adding 1.75 parts by mass of addition type liquid silicone rubber, 8.25 parts by mass of ethyl acetate and 0.175 part by mass of tetraethylenepentamine, dissolving, and adding into a reagent bottle for later use to obtain solution A;
(2) Coating KH550 on an iron sheet with a thickness of 0.1mm, coating 20% epoxy resin with a thickness of 0.1mm, uniformly dispersing nitrile butadiene rubber powder on the iron sheet with a micron-sized screen with a thickness of 0.2mm, and drying in a drying oven at 50 ℃ for 2 hours;
(3) Preparing a low surface energy substance: adding 1.4 parts by mass of silicone oil, 1.8 parts by mass of epoxy resin, 0.140 part by mass of tetraethylenepentamine, 7.42 parts by mass of ethyl acetate and 9.28 parts by mass of absolute ethyl alcohol, stirring until the materials are completely dissolved, and then adding 0.8 part by mass of fluorine modified nano-silica into the solution to be dispersed completely to obtain solution B;
(4) Taking out the iron sheet, uniformly spraying the solution B by a spraying method, wherein the thickness is 0.2mm, and then placing the iron sheet in a drying oven for drying for 2 hours at a constant temperature of 50 ℃;
(5) Preparing 2% of epoxy resin of a surface film substance: adding 2 parts by mass of epoxy resin and 0.181 parts by mass of tetraethylenepentamine into 97.819 parts by mass of ethyl acetate for dissolving, and filling into a reagent bottle for later use to obtain solution C;
(6) Taking out the iron sheet, spraying a thin layer of 0.08mm on the surface of the solution C by a spraying method, and drying for 2 hours at a constant temperature of 50 ℃;
the contact angle of the hydrophobic surface obtained by the operation is 155.63 degrees;
after 4500g shakeout test, the contact angle is 152.36 degrees.
Example 2
(1) Preparing 22% of epoxy resin: adding 2.2 parts by mass of epoxy resin into 7.8 parts by mass of ethyl acetate, stirring until the epoxy resin is dissolved, adding 1.75 parts by mass of addition type liquid silicone rubber, 8.25 parts by mass of ethyl acetate and 0.159 part by mass of tetraethylenepentamine, and adding the mixture into a reagent bottle for later use after the epoxy resin is dissolved to obtain solution A;
(2) Coating KH550 on the iron sheet with a thickness of 0.15mm, coating 22% epoxy resin with a thickness of 0.15mm, uniformly dispersing nitrile rubber powder on the iron sheet with a micron-sized screen with a thickness of 0.3mm, and drying in a drying oven at 55 ℃ for 2.5 hours;
(3) Preparing a low surface energy substance: adding 1.2 parts by mass of silicone oil, 1.6 parts by mass of epoxy resin, 0.109 part by mass of tetraethylenepentamine, 7.2725 parts by mass of ethyl acetate and 7.2725 parts by mass of absolute ethyl alcohol, stirring until complete dissolution, and then adding 1.0 part by mass of fluorine modified nano-silica to the solution for complete dispersion to obtain solution B;
(4) Taking out the iron sheet, uniformly spraying the solution B by a spraying method, wherein the thickness is 0.3mm, and then placing the iron sheet in a drying oven for drying for 2.5 hours at the constant temperature of 55 ℃;
(5) Preparing a surface film substance 3% of epoxy resin: adding 3 parts by mass of epoxy resin and 0.27 part by mass of tetraethylenepentamine into 96.73 parts by mass of ethyl acetate for dissolving, and filling into a reagent bottle for later use to obtain solution C;
(6) Taking out the iron sheet, spraying a thin layer of 0.1mm on the surface of the solution C by a spraying method, and drying for 2.5 hours at the constant temperature of 55 ℃;
the contact angle of the hydrophobic surface obtained by the operation is 160.63 degrees;
after 4500g shakeout test, the contact angle was 157.33 °.
Example 3
(1) Preparing 24% epoxy resin: adding 2.4 parts by mass of epoxy resin into 7.6 parts by mass of ethyl acetate, stirring until the epoxy resin is dissolved, adding 1.75 parts by mass of addition type liquid silicone rubber, 8.25 parts by mass of ethyl acetate and 0.2 part by mass of tetraethylenepentamine, and adding the mixture into a reagent bottle for later use after the epoxy resin is dissolved to obtain solution A;
(2) Coating KH550 on the iron sheet with a thickness of 0.2mm, coating 24% epoxy resin with a thickness of 0.2mm, uniformly dispersing nitrile rubber powder on the iron sheet with a micron-sized screen with a thickness of 0.4mm, and drying in a drying oven at 60 deg.C for 3 hours;
(3) Preparing a low surface energy substance: adding 1 part by mass of silicone oil, 2.2 parts by mass of epoxy resin, 0.083 part by mass of tetraethylenepentamine, 8.95 parts by mass of ethyl acetate and 7.465 parts by mass of absolute ethyl alcohol, stirring until complete dissolution, and then adding 1.2 parts by mass of fluorine modified nano-silica into the solution to be dispersed completely to obtain solution B;
(4) Taking out the iron sheet, uniformly spraying the solution B by a spraying method, wherein the thickness is 0.4mm, and then placing the iron sheet in a drying oven to dry for 3 hours at the constant temperature of 60 ℃;
(5) Preparing 4% epoxy resin of a surface film substance, adding 4 parts by mass of epoxy resin and 0.33 part by mass of tetraethylenepentamine to 95.67 parts by mass of ethyl acetate for dissolving, and filling into a reagent bottle for later use to obtain solution C;
(6) Taking out the iron sheet, spraying a thin layer of 0.12mm on the surface of the solution C by a spraying method, and drying for 3 hours at a constant temperature of 60 ℃;
the contact angle of the hydrophobic surface obtained by the operation is 153.43 degrees;
after 4500g shakeout test, the contact angle was 151.33 °.
Comparative example 1
(1) Preparation of 20% epoxy adhesive: weighing 2 parts by mass of epoxy resin, weighing 8 parts by mass of ethyl acetate solution, adding magnetons, violently stirring until the solution is completely dissolved, weighing 2 parts by mass of addition type liquid silicone rubber, 8 parts by mass of ethyl acetate, weighing 0.18 part by mass of tetraethylenepentamine, adding the mixture into a beaker filled with the epoxy resin, starting a magnetic stirrer, violently stirring, and completely dissolving;
(2) Coating KH550 on the iron sheet with a thickness of 0.2mm, coating 20% epoxy resin adhesive with a thickness of 0.2mm, uniformly covering rubber powder on the iron sheet with a micron-sized screen with a thickness of 0.2mm, and heating in a drying oven at a constant temperature of 60 deg.C for 4 hours;
(3) Preparing 3% epoxy resin adhesive: weighing 3 parts by mass of epoxy resin, adding 0.273 part by mass of tetraethylenepentamine, weighing 97 parts by mass of ethyl acetate, and stirring until the epoxy resin is completely dissolved;
(4) Taking out the iron sheet, coating 3% of adhesive on the iron sheet with the thickness of 0.1mm, and drying the iron sheet in a drying oven at the constant temperature of 60 ℃ for 4 hours;
(5) Taking 3 parts by mass of Poss and 2 parts by mass of addition type liquid silicone rubber, adding 20 parts of ethyl acetate and 0.18 part of curing agent tetraethylenepentamine, fully dissolving, soaking the dried iron sheet in Poss/organic silicon solution for 15 minutes, taking out, and heating and curing at the constant temperature of 50 ℃ for 4 hours;
(6) Taking out the iron sheet, washing the iron sheet for 50 minutes by using ethyl acetate, and then drying the iron sheet for 4 hours at the constant temperature of 50 ℃;
(7) Obtaining the super-hydrophobic iron sheet with excellent performance, wherein the contact angle of the super-hydrophobic iron sheet is 150.36 degrees;
(8) The contact angle of the iron piece after treatment with 4500g of shakeout was 45.23 °.
The comparison shows that when Poss/organic silicon is applied to the iron sheet, the abrasion resistance of the Poss/organic silicon is poor, and the Poss/organic silicon is not suitable for being applied to the iron sheet.
Claims (10)
1. The application of the super-hydrophobic coating based on the modified nano-silica on the metal is characterized in that: the method comprises the following steps:
(1) Formulating epoxy resin adhesives
Adding 2.0-2.4 parts by mass of epoxy resin into 7.6-8.0 parts by mass of ethyl acetate, stirring until the epoxy resin is dissolved, adding 1.5-2 parts by mass of addition type liquid silicone rubber, 8-8.5 parts by mass of ethyl acetate and 0.136-0.180 part by mass of tetraethylenepentamine, and adding the mixture into a reagent bottle for later use after the epoxy resin is dissolved to obtain solution A;
(2) Formulating low surface energy materials
Stirring silicone oil, epoxy resin, tetraethylenepentamine, ethyl acetate and absolute ethyl alcohol until the silicone oil, the epoxy resin, the tetraethylenepentamine, the ethyl acetate and the absolute ethyl alcohol are dissolved, then adding fluorine modified nano silicon dioxide, and dispersing the fluorine modified nano silicon dioxide into the solution by ultrasonic waves to obtain solution B;
(3) Preparing surface film material
Adding epoxy resin and tetraethylenepentamine into ethyl acetate for dissolving, and filling into a reagent bottle for later use to obtain solution C;
(4) Application to metal
S1, taking a metal sheet with a clean surface, and brushing KH550;
s2, brushing the solution A;
s3, uniformly covering the nitrile rubber powder on a metal sheet by using a micron-sized mesh screen, and drying;
s4, spraying the liquid B to the metal sheet, and drying;
and S5, uniformly spraying the solution C, and drying.
2. The use of the modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step (2), the mass ratio of the silicone oil to the tetraethylenepentamine is 10-12; the mass ratio of the fluorine modified nano silicon dioxide to the silicone oil is 0.57-1.2.
3. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step (2), the mass ratio of the ethyl acetate to the absolute ethyl alcohol is 0.8-1.2.
4. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step (2), the mass ratio of the epoxy resin to the silicone oil is 1.29-2.2.
5. The use of the modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step (3), 2-4 parts by mass of epoxy resin and 0.181-0.33 part by mass of tetraethylenepentamine are added into 95.67-97.819 parts by mass of ethyl acetate, stirred until dissolved, and filled into a reagent bottle for later use to obtain solution C.
6. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step S1, the thickness of the brush coating KH550 is 0.1-0.2mm.
7. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step S2, the thickness of the brushing liquid A is 0.1-0.2mm.
8. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in the step S3, the covering thickness of the nitrile rubber powder is 0.2-0.4mm; in step S4, the thickness of the spraying liquid B is 0.2-0.4mm.
9. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in step S5, the thickness of the spraying C liquid is 0.08-0.12mm.
10. Use of a modified nanosilica-based superhydrophobic coating on a metal according to claim 1, wherein: in steps S3-S5, the drying conditions are as follows: 50-60 ℃ for 2-3 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731586A (en) * | 2023-06-19 | 2023-09-12 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Multifunctional bionic structure surface and preparation method thereof |
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| CN111019485A (en) * | 2019-12-25 | 2020-04-17 | 三峡大学 | Preparation method of friction-resistant anti-icing coating |
| CN113019852A (en) * | 2021-02-03 | 2021-06-25 | 山东理工大学 | Preparation method of micro-nano structure super-hydrophobic coating constructed based on nitrile butadiene rubber powder |
| CN114369403A (en) * | 2021-12-30 | 2022-04-19 | 山东理工大学 | Application of high-wear-resistance super-hydrophobic coating based on Poss hybrid molecule/organic silicon on glass |
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Patent Citations (3)
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| CN111019485A (en) * | 2019-12-25 | 2020-04-17 | 三峡大学 | Preparation method of friction-resistant anti-icing coating |
| CN113019852A (en) * | 2021-02-03 | 2021-06-25 | 山东理工大学 | Preparation method of micro-nano structure super-hydrophobic coating constructed based on nitrile butadiene rubber powder |
| CN114369403A (en) * | 2021-12-30 | 2022-04-19 | 山东理工大学 | Application of high-wear-resistance super-hydrophobic coating based on Poss hybrid molecule/organic silicon on glass |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116731586A (en) * | 2023-06-19 | 2023-09-12 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Multifunctional bionic structure surface and preparation method thereof |
| CN116731586B (en) * | 2023-06-19 | 2024-04-12 | 洛阳船舶材料研究所(中国船舶集团有限公司第七二五研究所) | Multifunctional bionic structure surface and preparation method thereof |
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