CN112979178B - Preparation method of processable ceramic surface hydrophobic film - Google Patents

Preparation method of processable ceramic surface hydrophobic film Download PDF

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CN112979178B
CN112979178B CN202110158346.4A CN202110158346A CN112979178B CN 112979178 B CN112979178 B CN 112979178B CN 202110158346 A CN202110158346 A CN 202110158346A CN 112979178 B CN112979178 B CN 112979178B
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ceramic
coupling agent
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processable ceramic
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CN112979178A (en
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李彦博
崔庆龙
康军
李宁
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Beijign Institute of Aerospace Control Devices
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

The invention relates to a method for preparing a hydrophobic membrane on the surface of machinable ceramics, (1) cleaning the surface of the machinable ceramics; (2) Carrying out coupling agent treatment on the surface of the machinable ceramic to obtain the machinable ceramic modified by the coupling agent; (3) Uniformly spraying amine solution on the surface of the machinable ceramic modified by the coupling agent for reaction, then placing the machinable ceramic in a forced air drying oven, drying the machinable ceramic for 1 hour at 120 ℃, and cooling the machinable ceramic to room temperature to obtain a hydrophobic membrane on the surface of the machinable ceramic; the amine solution is ethanol solution of alcohol amine reagent, and the mass concentration of the alcohol amine reagent is 0.5-2%. The machinable ceramic hydrophobic membrane layer prepared by the invention can isolate the infiltration of water vapor to machinable ceramic under a high-humidity environment, and also can ensure better bonding performance with epoxy glue.

Description

Preparation method of processable ceramic surface hydrophobic film
Technical Field
The invention belongs to the field of surface engineering and application, and relates to a preparation method of a processable ceramic surface hydrophobic membrane.
Background
The machinable ceramic is a composite polycrystalline material consisting of fluorophlogopite microcrystal and glass, has the characteristics of excellent insulating property, high and low temperature resistance, thermal shock resistance, no gas release and the like, can achieve very high machining precision after mechanical processing such as turning, milling, planing, grinding, drilling, cutting, tapping and the like, and is commonly used as a framework material of precision parts. However, the material has poor moisture resistance, and the insulation quality of the electrical material prepared from the material is very easy to be reduced in an environment with the relative humidity of more than 75%, so that faults such as power transmission errors, feedback signal abnormity and the like are caused in serious conditions.
A layer of hydrophobic film is constructed on the surface of the material, so that the insulating property of the material in a humid environment can be improved. Patent (201810487037. X) prepares a super-hydrophobic high self-cleaning antifouling coating by using a fluorine-containing silane reagent, but the price of the fluorine-containing silane is higher. In the patent (201910335154.9), a layer of hydrophobic film is plated by using a multi-carbon long-chain alkyl under the action of plasma enhanced chemical vapor deposition, and no fluorine-containing waste gas is generated in the film plating process, so that the method is environment-friendly. However, the hydrophobic film prepared by these methods has better hydrophobic effect, and the film layer has poorer adhesive effect with epoxy resin, which is very disadvantageous particularly for the later process requiring adhesive assembly. Therefore, a process method which can improve the hydrophobic effect of the processable ceramic material and does not influence the later bonding property needs to be found.
Disclosure of Invention
The invention solves the technical problems that: the method overcomes the defects of the prior art and provides a method for preparing a hydrophobic film on the surface of processable ceramic, so that the processable ceramic has hydrophobicity without reducing the bonding performance between the surface of the processable ceramic and epoxy glue.
The technical scheme of the invention is as follows:
a method for preparing a processable ceramic surface hydrophobic film comprises the following steps:
step (1), cleaning the surface of the machinable ceramic;
step (2), carrying out coupling agent treatment on the surface of the machinable ceramic to obtain coupling agent modified machinable ceramic; the coupling agent is a silane coupling agent with an epoxy group at the end of a molecule;
step (3) uniformly spraying amine solution on the surface of the processable ceramic modified by the coupling agent obtained in the step (2) for reaction, then placing the processable ceramic surface in a forced air drying oven, drying the processable ceramic surface for 1h at 120 ℃, and cooling the processable ceramic surface to room temperature to obtain a hydrophobic film on the processable ceramic surface; the amine solution is an ethanol solution of an alcohol amine reagent, and the mass concentration of the alcohol amine reagent is 0.5-2%.
And (2) cleaning the surface of the machinable ceramic by using plasma in the step (1).
The plasma cleaning power is 140W-200W, and the cleaning time is 2-5 min.
In the step (2), the coupling agent treatment is carried out on the machinable ceramic surface by the following steps:
adding a coupling agent into an ethanol aqueous solution for hydrolysis, adjusting the pH value to 3-4 by using acetic acid, and carrying out reflux reaction for 0.5-2 h under the stirring condition, wherein the mass ratio of the coupling agent to water to ethanol in the coupling agent ethanol solution is 1;
soaking the cleaned processable ceramic into an ethanol solution of the coupling agent after the reflux reaction for 5-20 min;
and taking out the soaked processable ceramic, placing the processable ceramic in a forced air drying oven, drying for 1h at 100 ℃, and taking out the processable ceramic to obtain the processable ceramic treated by the surface coupling agent.
The reflux reaction temperature is 80-90 ℃.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the processable ceramic surface hydrophobic membrane provided by the invention, the processable ceramic after plasma cleaning is treated by using the silane coupling agent, and then the surface of the processable ceramic is subjected to high-temperature reaction treatment by using the amine reagent, so that the processable ceramic membrane which has a hydrophobic effect and a good bonding property with epoxy glue is obtained.
Compared with the machinable ceramic without hydrophobic treatment, the machinable ceramic hydrophobic membrane layer prepared by the invention isolates the infiltration of water vapor to the machinable ceramic under high-humidity environment and ensures better bonding performance with epoxy glue.
The method for preparing the processable ceramic surface hydrophobic film is particularly suitable for the fields of electrical insulation, bonding and the like.
Drawings
FIG. 1 is a flow chart of the present invention;
FIG. 2 is a SEM of a hydrophobic membrane of a machinable ceramic surface according to an embodiment of the present invention, wherein a is the machinable ceramic surface and b is the machinable ceramic surface with the hydrophobic membrane attached;
fig. 3 is a comparison of contact angle measurements provided by examples of the present invention, where a is processable ceramic and b is processable ceramic with a hydrophobic film attached.
Detailed Description
The invention is further illustrated by the following examples.
As shown in figure 1, the invention provides a method for preparing a hydrophobic membrane on the surface of a processable ceramic, which comprises the following steps:
and (1) cleaning the surface of the machinable ceramic.
The cleaning of the surface of the machinable ceramic comprises: and placing the machinable ceramic in a plasma cleaning machine, setting the power to be 70-100%, and cleaning for 2-5 min to obtain the machinable ceramic with the cleaned surface.
And (2) treating the surface of the processable ceramic with a coupling agent to obtain the coupling agent modified processable ceramic.
A processable ceramic surface coupling agent treatment comprising:
adding a coupling agent into an ethanol aqueous solution for hydrolysis, adjusting the pH value to 3-4 by using acetic acid, and carrying out reflux reaction for 1h under the stirring condition; the ratio of the coupling agent, water and ethanol in the ethanol solution of the coupling agent is 1. The coupling agent is a silane coupling agent containing an epoxy group at the molecular end. The reflux reaction temperature is 80-90 ℃.
And soaking the cleaned processable ceramic into an ethanol solution of the coupling agent after the reflux reaction for 5-20 min.
And taking out the soaked processable ceramic, placing the processable ceramic in a forced air drying oven, drying the processable ceramic for 1h at 100 ℃, and taking out the processable ceramic to obtain the processable ceramic treated by the surface coupling agent.
And (3) spraying amine solution on the surface of the processable ceramic modified by the coupling agent obtained in the step (2) for reaction to obtain the hydrophobic film on the surface of the processable ceramic.
And (3) uniformly spraying the amine solution on the surface of the processable ceramic treated by the surface coupling agent, placing the processable ceramic in a forced air drying oven, drying at 120 ℃ for 1h, and cooling to room temperature to obtain the processable ceramic with the hydrophobic film.
The amine solution is ethanol solution of alcohol amine reagent. The mass concentration of the alcamines reagent in the amine solution is 0.5-2%.
The method for preparing the hydrophobic membrane on the surface of the machinable ceramic provided by the invention comprises the steps of carrying out coupling agent treatment on the machinable ceramic subjected to surface plasma cleaning, and then carrying out high-temperature reaction on the surface of the machinable ceramic by using an amine solvent to finally obtain the hydrophobic membrane.
Compared with the machinable ceramic without hydrophobic treatment, the machinable ceramic hydrophobic membrane layer prepared by the invention can isolate the infiltration of water vapor to the machinable ceramic under a high-humidity environment and ensure better bonding performance with epoxy glue.
The method for preparing the hydrophobic membrane on the surface of the machinable ceramic is particularly suitable for the fields of electrical insulation, bonding and the like.
Example 1
1. The embodiment of the invention provides a processable ceramic with a hydrophobic film attached to the surface, and the specific preparation method comprises the following steps:
and placing the machinable ceramic material in a plasma cleaning cabin, setting the power of a plasma cleaner to be 70% and the cleaning time to be 3min, and performing plasma cleaning on the machinable ceramic material.
10.0g of deionized water, 10.0g of organosilane KH-560 and 180.0g of absolute ethyl alcohol are respectively weighed in a flask by using an analytical balance, stirred uniformly, added with a proper amount of acetic acid to adjust the pH value to 3-4, and refluxed and reacted for 1 hour at 80 ℃ under the stirring condition.
And putting the processable ceramic cleaned by the plasma into an organosilane solution to ensure that the surface of the processable ceramic is completely soaked, keeping for 10min, taking out the processable ceramic, putting the processable ceramic into a 100 ℃ blast drying oven for 1h, and cooling to obtain the processable ceramic treated by the surface coupling agent.
And uniformly spraying an ethanol solution of triethanolamine with the mass fraction of 1% on the surface of the machinable ceramic treated by the surface coupling agent, then placing the machinable ceramic in a 120 ℃ forced air drying oven for 1h, and cooling to obtain the machinable ceramic with the hydrophobic membrane attached to the surface.
2. The workable ceramic with the hydrophobic film attached on the surface provided by the invention is subjected to performance characterization, and the result is as follows:
the surface appearance (shown in figure 2) of the machinable ceramic subjected to surface hydrophobic treatment is smooth, and energy spectrum data show that the content of C element is increased to more than 46%, and F element is not detected on the surface, which indicates that the surface of the machinable ceramic is covered by a layer of organic silane film. Table 1 shows the surface energy spectrum analysis data of the machinable ceramics.
TABLE 1 processable ceramic surface Spectroscopy data
Figure BDA0002934706010000051
The contact angle of the machinable ceramic subjected to surface hydrophobic treatment (as shown in figure 3) is increased from the untreated 9.2 degrees to over 42.8 degrees, and the hydrophobic property is enhanced. Under a humid environment, the moisture absorption rate of the processable ceramic is reduced to 0.015% from 0.036% before treatment due to the existence of the hydrophobic film. Table 2 shows the effect of the hydrophobic film on the moisture absorption rate of the processable ceramics.
TABLE 2 Effect of hydrophobic films on moisture absorption Rate of processable ceramics
Figure BDA0002934706010000052
The workable ceramics having the hydrophobic film attached to the surface thereof were subjected to a test for adhesive strength, and the test results (as shown in Table 3) showed that the adhesive strength was not lowered and the failure form was not changed.
TABLE 3 comparison of adhesion Properties
Figure BDA0002934706010000061
Comparative example 1
And placing the machinable ceramic material in a plasma cleaning cabin, setting the power of a plasma cleaner to be 70% and the cleaning time to be 3min, and performing plasma cleaning on the machinable ceramic material.
Respectively weighing 10.0g of deionized water, 10.0g of organosilane KH-570 and 180.0g of absolute ethyl alcohol into a flask by using an analytical balance, uniformly stirring, adding a proper amount of acetic acid to adjust the pH value to 3-4, and carrying out reflux reaction for 1h at 80 ℃ under the stirring condition.
And putting the processable ceramic cleaned by the plasma into an organosilane solution to ensure that the surface of the processable ceramic is completely soaked, keeping for 10min, taking out the processable ceramic, putting the processable ceramic into a forced air drying oven at 100 ℃ for 1h, and cooling to obtain the processable ceramic treated by the surface coupling agent KH-570.
As a result of the performance test, the processable ceramics treated in this manner had a contact angle as high as 79 ℃ and a moisture absorption as low as 0.014%, but had a bond strength as low as 0.617kN.
Comparative example 2
According to the weight ratio of absolute ethyl alcohol: perfluorodecyl triethoxysilane =2000:1 (mass ratio), immersing the machinable ceramic materials subjected to ultrasonic cleaning and plasma cleaning into the mixed solution at room temperature, taking out after soaking for 24h, washing with absolute ethyl alcohol, and heating in a blast drying oven at 100 ℃ for 6h; repeating the soaking and drying processes for 2 times to obtain the machinable ceramic material treated by the perfluorodecyl triethoxysilane.
The performance test result shows that the processable ceramic treated by the method has a contact angle of 82.3 degrees, but the moisture absorption rate of 0.021 percent, and the bonding strength is reduced to 5.6kN.
Therefore, compared with the machinable ceramic which is not subjected to hydrophobic treatment, the machinable ceramic hydrophobic membrane layer prepared by the invention isolates the infiltration of water vapor to the machinable ceramic under the high-humidity environment and ensures better bonding performance with epoxy glue.
The invention has not been described in detail in part of the common general knowledge of those skilled in the art. The specific embodiments described are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (4)

1. A method for preparing a machinable ceramic surface hydrophobic membrane is characterized by comprising the following steps:
step (1), cleaning the surface of the machinable ceramic;
step (2), carrying out coupling agent treatment on the surface of the machinable ceramic to obtain coupling agent modified machinable ceramic; the coupling agent is a silane coupling agent with an epoxy group at the end of a molecule;
the coupling agent treatment of the machinable ceramic surface comprises the following steps:
adding a coupling agent into an ethanol aqueous solution for hydrolysis, adjusting the pH value to 3-4 by using acetic acid, and carrying out reflux reaction for 0.5-2 h under the stirring condition, wherein the mass ratio of the coupling agent to water to ethanol in the coupling agent ethanol solution is 1;
soaking the cleaned processable ceramic into an ethanol solution of the coupling agent after the reflux reaction for 5-20 min;
taking out the soaked processable ceramic, placing the processable ceramic in a forced air drying oven, drying for 1h at 100 ℃, and taking out the processable ceramic to obtain processable ceramic treated by the surface coupling agent;
step (3) uniformly spraying amine solution on the surface of the processable ceramic modified by the coupling agent obtained in the step (2) for reaction, then placing the processable ceramic surface in a forced air drying oven, drying the processable ceramic surface for 1h at 120 ℃, and cooling the processable ceramic surface to room temperature to obtain a hydrophobic membrane of the processable ceramic surface; the amine solution is an ethanol solution of an alcohol amine reagent, and the mass concentration of the alcohol amine reagent is 0.5-2%.
2. A method of preparing a hydrophobic membrane of a processable ceramic surface according to claim 1, wherein the plasma is used to clean the processable ceramic surface in step (1).
3. The method for preparing the hydrophobic membrane on the workable ceramic surface of claim 2, wherein the plasma cleaning power is 140W-200W and the cleaning time is 2-5 min.
4. The method for preparing the hydrophobic membrane on the workable ceramic surface of claim 1, wherein the reflux reaction temperature is 80-90 ℃.
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US6020028A (en) * 1998-06-05 2000-02-01 Kinneberg; Bruce I. Silane adhesion catalysts
US20110281121A1 (en) * 2010-05-17 2011-11-17 Mingqian He Surface Treatment and Article
CN104016716B (en) * 2013-03-01 2016-03-23 安徽格丰环保科技有限公司 A kind of preparation technology of porous ceramics functional materials
CN105622166B (en) * 2016-01-12 2018-09-11 武汉理工大学 A kind of processing method on silane coupler modified titanium boride ceramics surface
TWI614228B (en) * 2016-11-29 2018-02-11 財團法人金屬工業研究發展中心 Surface treatment method for ceramic
CN107555808A (en) * 2017-09-06 2018-01-09 安徽凯盛基础材料科技有限公司 A kind of method of hollow glass micropearl surface hydrophobic processing

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