CN112359361A - Super-hydrophobic surface treating agent and preparation method and application thereof - Google Patents

Super-hydrophobic surface treating agent and preparation method and application thereof Download PDF

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Publication number
CN112359361A
CN112359361A CN202011103301.9A CN202011103301A CN112359361A CN 112359361 A CN112359361 A CN 112359361A CN 202011103301 A CN202011103301 A CN 202011103301A CN 112359361 A CN112359361 A CN 112359361A
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China
Prior art keywords
treating agent
surface treating
silica sol
super
nano silica
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Pending
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CN202011103301.9A
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Chinese (zh)
Inventor
李智锋
胡建祥
萧展锋
王宗军
潘叶江
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Vatti Co Ltd
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Vatti Co Ltd
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Publication date
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Priority to CN202011103301.9A priority Critical patent/CN112359361A/en
Publication of CN112359361A publication Critical patent/CN112359361A/en
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F14/00Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
    • C23F14/02Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means

Abstract

The invention discloses a super-hydrophobic surface treating agent and a preparation method thereof, wherein the super-hydrophilic surface treating agent comprises the following components in percentage by mass: 5.0-8.0% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water. The hydrophobic surface treating agent provided by the invention is reasonable in components, safe and effective, can be used for a long time, has the density of 0.93-1.00 relative to water and the pH of 3-4, and thus lays a solid foundation for a process for treating a metal surface by selecting the hydrophobic surface treating agent; in addition, the surface treating agent provided by the invention is simple in preparation process, easy in raw material obtaining, excellent in easy-to-clean property and worthy of great popularization and application.

Description

Super-hydrophobic surface treating agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of metal surface processing, and particularly relates to a super-hydrophobic surface treating agent, and a preparation method and application thereof.
Background
The steam generating device of the steam box and the steam baking all-in-one machine can heat water to convert the water into high-temperature steam, and the surface of the steam generating device can be scaled after the steam generating device is used for a long time, so that the heating efficiency of the steam generating device can be reduced, and the temperature control precision can be influenced; part of the massive scale can fall off in a massive mode, and the fallen scale can block a pipeline, so that the machine cannot be normally used.
In order to solve the problems, the scale removal method of the products on the market at present adopts a scale remover such as citric acid and the like for cleaning, but the frequent use can affect the health of the human body; the water pump is additionally arranged for cleaning, but the scale cleaning effect is not ideal because the scale is adhered to the surface of the evaporator; therefore, the research on new surface treatment agents capable of solving the problem of easy scaling of metal surfaces is still a major challenge at the present stage.
Disclosure of Invention
In view of the above, the main object of the present invention is to provide a super-hydrophobic surface treatment agent, which enables a metal surface to be in a super-hydrophobic state after the metal surface is treated by the surface treatment agent, thereby solving the problem that the metal surface is easy to scale after long-term use.
The invention also aims to provide a preparation method of the super-hydrophobic surface treating agent;
the invention also aims to provide application of the super-hydrophobic surface treating agent.
In order to achieve the purpose, the technical scheme of the invention is realized as follows: the super-hydrophobic surface treatment agent comprises the following components in percentage by weight:
preferably, 5-8% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water.
Preferably, the modified nano silica sol is hydrophobic nano silica sol.
Preferably, the stabilizer is at least one of ethylene glycol ethyl ether, dimethyl siloxane, ethylene glycol butyl ether and diethylene glycol butyl ether.
Preferably, the relative density of the super-hydrophobic surface treatment agent is 0.93-1.00; the pH value is 3-4.
The second technical scheme of the invention is realized as follows: the preparation method of the super-hydrophobic surface treating agent is realized by the following steps:
s1, respectively weighing the following components in percentage by weight: 5-8% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water;
s2, heating the water in the S1 to 45-55 ℃, adding the modified nano silica sol into the water, keeping the temperature of 45-55 ℃, stirring for at least 10min, and cooling to room temperature to obtain a first intermediate mixed solution;
s3, adding the stabilizer obtained in the S1 into the first intermediate mixed solution obtained in the S2, and stirring for at least 30min to obtain a second intermediate mixed solution;
s4, adding the fluosilicic acid obtained in the step S1 into the second intermediate mixed solution obtained in the step S3, and adjusting the pH value to 3-4 to obtain a crude surface treating agent solution;
s5, filtering the crude surface treating agent solution obtained in the step S4 to obtain the colorless transparent liquid super-hydrophobic surface treating agent.
Preferably, in the step S2, the stirring time is 10-20 min;
preferably, in the step S3, the stirring time is 30-40 min.
Preferably, in S5, a 400-450 mesh screen is used for filtering.
Compared with the prior art, the hydrophobic surface treating agent provided by the invention is reasonable in components, safe and effective, can be used for a long time, has the density of 0.93-1.00 relative to water and the pH of 3-4, and thus lays a solid foundation for the process of treating the metal surface by selecting the hydrophobic surface treating agent; in addition, the surface treating agent provided by the invention is simple in preparation process, easy in raw material obtaining, excellent in easy-to-clean property and worthy of great popularization and application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
It should be noted that: the raw material components used in the examples of the present invention may be prepared by themselves or purchased.
The super-hydrophobic surface treating agent provided by the embodiment of the invention comprises the following components in percentage by weight:
5-8% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water.
Wherein the modified nano silica sol is hydrophobic nano silica sol; the stabilizer is at least one of ethylene glycol ethyl ether, dimethyl siloxane, ethylene glycol butyl ether and diethylene glycol butyl ether.
Furthermore, the method is simple. The relative density of the super-hydrophobic surface treatment agent is 0.93-1.00; the pH value is 3-4.
The embodiment of the invention also provides a preparation method of the super-hydrophobic surface treating agent, which is realized by the following steps:
s1, respectively weighing the following components in percentage by weight: 5-8% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water;
s2, heating the water in the S1 to 45-55 ℃, adding the modified nano silica sol into the water, keeping the temperature of 45-55 ℃, stirring for at least 10min, preferably 10-20 min, and cooling to room temperature to obtain a first intermediate mixed solution;
s3, adding the stabilizer obtained in the S1 into the first intermediate mixed solution obtained in the S2, and stirring for at least 30min, preferably 30-40 min to obtain a second intermediate mixed solution;
s4, adding the fluosilicic acid obtained in the step S1 into the second intermediate mixed solution obtained in the step S3, and adjusting the pH value to 3-4 to obtain a crude surface treating agent solution;
and S5, filtering the crude surface treating agent solution obtained in the step S4 by using a 400-450-mesh filter screen to obtain a colorless transparent liquid super-hydrophobic surface treating agent.
The following are specific examples
Example 1
The hydrophobic surface treating agent provided by the embodiment 1 of the invention comprises the following components in percentage by weight:
6.5 percent of hydrophobic nano silica sol, 0.3 percent of ethylene glycol ethyl ether, 1.0 percent of fluosilicic acid and the balance of pure water.
The hydrophobic surface treating agent provided by the embodiment 1 of the invention is obtained by the following steps:
s1, respectively weighing the following components in percentage by weight: 6.5 percent of hydrophobic nano silica sol, 0.3 percent of ethylene glycol ethyl ether, 1.0 percent of fluosilicic acid and the balance of pure water;
s2, heating the water in the S1 to 50 ℃, adding the hydrophobic nano silica sol into the water, keeping the temperature of 50 ℃, stirring for 15min, and cooling to room temperature to obtain a first intermediate mixed solution;
s3, adding the ethylene glycol ethyl ether obtained in the S1 into the first intermediate mixed solution obtained in the S2, and stirring for 35min to obtain a second intermediate mixed solution;
s4, adding the fluosilicic acid obtained in the step S1 into the second intermediate mixed solution obtained in the step S3, and adjusting the pH value to 3-4 to obtain a crude surface treating agent solution;
and S5, filtering the crude surface treating agent solution obtained in the step S4 by using a 400-450-mesh filter screen to obtain a colorless transparent liquid super-hydrophobic surface treating agent.
Example 2
The hydrophobic surface treating agent provided by the embodiment 2 of the invention comprises the following components in percentage by weight:
5.0 percent of hydrophobic nano silica sol, 0.1 percent of ethylene glycol ethyl ether, 0.5 percent of fluosilicic acid and the balance of pure water.
The hydrophobic surface treating agent provided by the embodiment 2 of the invention is obtained by the following steps:
s1, respectively weighing the following components in percentage by weight: 5.0 percent of hydrophobic nano silica sol, 0.1 percent of ethylene glycol ethyl ether, 0.5 percent of fluosilicic acid and the balance of pure water;
s2, heating the water in the S1 to 50 ℃, adding the hydrophobic nano silica sol into the water, keeping the temperature at 45 ℃, stirring for 10min, and cooling to room temperature to obtain a first intermediate mixed solution;
s3, adding the ethylene glycol ethyl ether obtained in the S1 into the first intermediate mixed solution obtained in the S2, and stirring for 30min to obtain a second intermediate mixed solution;
s4, adding the fluosilicic acid obtained in the step S1 into the second intermediate mixed solution obtained in the step S3, and adjusting the pH value to 3-4 to obtain a crude surface treating agent solution;
and S5, filtering the crude surface treating agent solution obtained in the step S4 by using a 400-450-mesh filter screen to obtain a colorless transparent liquid super-hydrophobic surface treating agent.
Example 3
The hydrophobic surface treating agent provided by the embodiment 3 of the invention comprises the following components in percentage by weight:
8.0 percent of hydrophobic nano silica sol, 0.5 percent of ethylene glycol ethyl ether, 1.5 percent of fluosilicic acid and the balance of pure water.
The hydrophobic surface treating agent provided by the embodiment 3 of the invention is obtained by the following steps:
s1, respectively weighing the following components in percentage by weight: 8.0 percent of hydrophobic nano silica sol, 0.5 percent of ethylene glycol ethyl ether, 1.5 percent of fluosilicic acid and the balance of pure water;
s2, heating the water in the S1 to 55 ℃, adding the hydrophobic nano silica sol into the water, keeping the temperature of 55 ℃, stirring for 20min, and cooling to room temperature to obtain a first intermediate mixed solution;
s3, adding the ethylene glycol ethyl ether obtained in the S1 into the first intermediate mixed solution obtained in the S2, and stirring for 40min to obtain a second intermediate mixed solution;
s4, adding the fluosilicic acid obtained in the step S1 into the second intermediate mixed solution obtained in the step S3, and adjusting the pH value to 3-4 to obtain a crude surface treating agent solution;
and S5, filtering the crude surface treating agent solution obtained in the step S4 by using a 400-450-mesh filter screen to obtain a colorless transparent liquid super-hydrophobic surface treating agent.
Example 4
The hydrophobic surface treating agent provided by the embodiment 4 of the invention comprises the following components in percentage by weight:
5.0 percent of hydrophobic nano-silica sol, 0.5 percent of dimethyl siloxane, 0.5 percent of fluosilicic acid and the balance of pure water.
The preparation method of the hydrophobic surface treating agent provided by the embodiment 4 of the invention is the same as that of the embodiment 1.
Example 5
The hydrophobic surface treating agent provided by the embodiment 5 of the invention comprises the following components in percentage by weight:
8.0 percent of hydrophobic nano silica sol, 0.1 percent of diethylene glycol monobutyl ether, 1.5 percent of fluosilicic acid and the balance of pure water.
The preparation method of the hydrophobic surface treating agent provided by the embodiment 5 of the invention is the same as that of the embodiment 1.
Comparative example 1
The components and content of a surface treatment agent provided in comparative example 1 of the present invention are substantially the same as those of the surface treatment agent of example 1, except that comparative example 1 does not contain a modified nano silica sol.
In addition, comparative example 1 of the present invention provides a surface treating agent prepared by the same method as example 1.
Comparative example 2
The components and content of the surface treating agent provided by comparative example 2 of the invention are basically the same as those of the surface treating agent in example 1, except that the modified nano silica sol in comparative example 2 is 4.0%.
In addition, comparative example 2 of the present invention provides a surface treating agent prepared by the same method as example 1.
Comparative example 3
The components and content of the surface treating agent provided by comparative example 3 of the present invention are substantially the same as those of the surface treating agent of example 1, except that the modified nano silica sol of comparative example 3 is 9.0%.
In addition, comparative example 3 of the present invention provides a surface treating agent prepared by the same method as example 1.
Comparative example 4
Comparative example 4 of the present invention provides a surface treatment agent having the same composition and content as those of the surface treatment agent of example 1, but the preparation method of the surface treatment agent of comparative example 4 is different from that of example 1 in that: heating the water in S1 to 40 ℃, adding the modified nano-silica sol into the water, keeping the temperature of 40 ℃, stirring for at least 10min, and cooling to room temperature to obtain a first intermediate mixed solution.
Comparative example 5
Comparative example 5 of the present invention provides a surface treatment agent having the same composition and content as those of the surface treatment agent composition of example 1, but the preparation method of the surface treatment agent of comparative example 5 is different from that of example 1 in that: heating the water in S1 to 60 ℃, adding the modified nano-silica sol into the water, keeping the temperature of 60 ℃, stirring for at least 10min, and cooling to room temperature to obtain a first intermediate mixed solution.
In order to verify the density of the phase and the pH of the surface treatment agents obtained in examples 1 to 5 and comparative examples 1 to 5 of the present invention, the density of the phase and the pH of the surface treatment agents obtained in examples 1 to 5 and comparative examples 1 to 5 were measured, and the results were as follows:
TABLE 1 results of examining the properties of the surface-treating agents obtained in examples 1 to 5 and comparative examples 1 to 5
Density of phase density pH value
Example 1 1.00 3~4
Example 2 0.98 3~4
Example 3 0.95 3~4
Example 4 0.93 3~4
Example 5 0.94 3~4
Comparative example 1 0.70 2~2.5
Comparative example 2 0.80 2~2.5
Comparative example 3 0.85 2~2.5
Comparative example 4 0.84 3.5~4
Comparative example 5 0.81 3.5~4
According to the specific contents of the examples 1 to 5 and the comparative examples 1 to 5 and by combining the data in the table 1, when any one of the selected modified nano silica sol, the stabilizer and the fluosilicic acid and the content of each component are not in the content range set by the scheme of the application, or the modified nano silica sol is not contained, the relative density of the obtained surface treating agent is not in the range of 0.93-1.00, and the pH value is not in the range of 3-4; in addition, according to the specific contents of example 1 and comparative examples 4 and 5 and the data in table 1, in the process of preparing the surface treating agent, when the heating temperature of water is not in the temperature range set by the scheme of the application, the relative density of the obtained surface treating agent is not in the range of 0.93-1.00, and the pH value is not in the range of 3-4; therefore, in order to obtain a surface treatment agent having a relative density of 0.93 to 1.00 and a pH of 3 to 4, the components and the content ranges of the components set in the present embodiment should be satisfied, and the process parameters for preparing the surface treatment agent should be within the ranges set in the present embodiment.
In conclusion, the surface treating agent provided by the invention is reasonable in components, safe and effective, can be used for a long time, has the density of 0.93-1.00 relative to water and the pH value of 3-4, and lays a solid foundation for the process for treating the metal surface by selecting the surface treating agent; in addition, the surface treating agent provided by the invention is simple in preparation process, easy in raw material obtaining, excellent in easy-to-clean property and worthy of great popularization and application.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (8)

1. The super-hydrophobic surface treatment agent is characterized by comprising the following components in percentage by weight:
5.0-8.0% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water.
2. The super-hydrophobic surface treating agent according to claim 1, wherein the modified nano silica sol is a hydrophobic nano silica sol.
3. The superhydrophobic surface treatment according to claim 1, wherein the stabilizer is at least one of ethylene glycol ethyl ether, dimethyl siloxane, ethylene glycol butyl ether, and diethylene glycol butyl ether.
4. The superhydrophobic surface treatment agent according to any one of claims 1-3, wherein the relative density of the superhydrophobic surface treatment agent is 0.93-1.00; the pH value is 3-4.
5. A method for preparing the superhydrophobic surface treatment agent according to any one of claims 1-4, wherein the method is realized by the following steps:
s1, respectively weighing the following components in percentage by weight: 5-8% of modified nano silica sol, 0.1-0.5% of stabilizer, 0.5-1.5% of fluosilicic acid and the balance of pure water;
s2, heating the water in the S1 to 45-55 ℃, adding the modified nano silica sol into the water, keeping the temperature of 45-55 ℃, stirring for at least 10min, and cooling to room temperature to obtain a first intermediate mixed solution;
s3, adding the stabilizer obtained in the S1 into the first intermediate mixed solution obtained in the S2, and stirring for at least 30min to obtain a second intermediate mixed solution;
s4, adding the fluosilicic acid obtained in the step S1 into the second intermediate mixed solution obtained in the step S3, and adjusting the pH value to 3-4 to obtain a crude surface treating agent solution;
s5, filtering the crude surface treating agent solution obtained in the step S4 to obtain the colorless transparent liquid super-hydrophobic surface treating agent.
6. The method of claim 5, wherein the stirring time in S2 is 10-20 min.
7. The method of claim 6, wherein the stirring time in S3 is 30-40 min.
8. The method according to claim 7, wherein in S5, a 400-450 mesh screen is used for filtering.
CN202011103301.9A 2020-10-15 2020-10-15 Super-hydrophobic surface treating agent and preparation method and application thereof Pending CN112359361A (en)

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Application Number Priority Date Filing Date Title
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102220036A (en) * 2011-06-02 2011-10-19 北京化工大学 Method for preparing white carbon black modified by silane coupling agent
CN104854203A (en) * 2012-12-21 2015-08-19 荷兰联合利华有限公司 Composition for hydrophobic coating
CN105350317A (en) * 2015-10-14 2016-02-24 安徽中恩化工有限公司 Environment-friendly super-hydrophobic oil-resistant surface treating agent for textile, and synthetic method and application thereof
CN106862039A (en) * 2017-01-18 2017-06-20 华南理工大学 A kind of hydrophilic super-hydrophobic bipolar self-cleaning composite membrane of durability and preparation method thereof
CN108102538A (en) * 2017-12-21 2018-06-01 天津城建道桥工程有限公司 A kind of preparation method of hydrophobic coating and its application in cable-stayed bridge metal component
CN108165058A (en) * 2017-12-30 2018-06-15 浙江工业大学 A kind of preparation method of the micro-nano secondary structure super hydrophobic surface of silicon substrate
WO2018164339A1 (en) * 2017-03-08 2018-09-13 인하대학교 산학협력단 Anthracene-perfluoropolyether-based superhydrophobic surface treatment agent and method for superhydrophobic surface treatment of pet fiber using same
CN111748227A (en) * 2020-05-29 2020-10-09 华帝股份有限公司 Hydrophobic coating and cooking equipment with same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102220036A (en) * 2011-06-02 2011-10-19 北京化工大学 Method for preparing white carbon black modified by silane coupling agent
CN104854203A (en) * 2012-12-21 2015-08-19 荷兰联合利华有限公司 Composition for hydrophobic coating
CN105350317A (en) * 2015-10-14 2016-02-24 安徽中恩化工有限公司 Environment-friendly super-hydrophobic oil-resistant surface treating agent for textile, and synthetic method and application thereof
CN106862039A (en) * 2017-01-18 2017-06-20 华南理工大学 A kind of hydrophilic super-hydrophobic bipolar self-cleaning composite membrane of durability and preparation method thereof
WO2018164339A1 (en) * 2017-03-08 2018-09-13 인하대학교 산학협력단 Anthracene-perfluoropolyether-based superhydrophobic surface treatment agent and method for superhydrophobic surface treatment of pet fiber using same
CN108102538A (en) * 2017-12-21 2018-06-01 天津城建道桥工程有限公司 A kind of preparation method of hydrophobic coating and its application in cable-stayed bridge metal component
CN108165058A (en) * 2017-12-30 2018-06-15 浙江工业大学 A kind of preparation method of the micro-nano secondary structure super hydrophobic surface of silicon substrate
CN111748227A (en) * 2020-05-29 2020-10-09 华帝股份有限公司 Hydrophobic coating and cooking equipment with same

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Application publication date: 20210212