CN111155089A - Preparation method of durable anti-ice super-hydrophobic stainless steel coating - Google Patents
Preparation method of durable anti-ice super-hydrophobic stainless steel coating Download PDFInfo
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- CN111155089A CN111155089A CN202010063123.5A CN202010063123A CN111155089A CN 111155089 A CN111155089 A CN 111155089A CN 202010063123 A CN202010063123 A CN 202010063123A CN 111155089 A CN111155089 A CN 111155089A
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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Abstract
The invention discloses a preparation method of a durable anti-icing super-hydrophobic stainless steel coating. The surface of the stainless steel coating is treated by a low surface energy substance to show good hydrophobic property and long anti-icing time. The ZnO coating is prepared by adopting an electrodeposition method and a hydrothermal method, firstly, a ZnO seed layer is prepared on the surface of the stainless steel by adopting electrodeposition, and then, the ZnO seed layer is grown by adopting the hydrothermal method; then calcining at a certain temperature and for a certain time, and then treating with a low-surface-energy substance dodecyl mercaptan ethanol solution to obtain the super-hydrophobic ZnO coating; and finally irradiating the super-hydrophobic ZnO coating for different time under ultraviolet rays to obtain the hydrophobic ZnO coating and the hydrophilic ZnO coating. The invention has the advantages of simplicity, high efficiency, cheap and available raw materials and wide application range, the contact angle between the surface of the obtained super-hydrophobic coating and water is more than 150 degrees, the rolling angle is less than 5 degrees, the ice resistance of the super-hydrophobic coating is excellent, and the super-hydrophobic coating is easy to produce and apply on a large scale.
Description
Technical Field
The invention relates to the technical field of stainless steel materials, in particular to a preparation method of a durable anti-icing super-hydrophobic stainless steel coating.
Background
The special surface wetting behavior (superhydrophobic surfaces) has been a focus of attention in the field of materials research. The lotus flower type intelligent touch screen is from lotus flowers, due to the micro-nano structure and low surface energy of the surface of the lotus flower, the contact angle between the surface of the lotus flower type intelligent touch screen and water is larger than 150 degrees, the rolling angle is smaller than 10 degrees, liquid drops keep spherical shapes on the lotus flower type intelligent touch screen and can roll easily, the lotus flower type intelligent touch screen is considered as a lotus flower effect, and the lotus flower type intelligent touch screen has great interest in wide application in the aspects of self-cleaning, corrosion prevention, oil-water separation. The use of superhydrophobic surfaces to prevent or delay the icing process has been a focus of research. The ice resistance of the superhydrophobic surface can be attributed to the following reasons: one is that water can be removed before freezing and the other is that crystallization delays caused by lower freezing points or heat transfer barriers. Therefore, it is important to prepare a super-hydrophobic coating with good ice resistance.
Stainless steel is one of the most important engineering materials and has been widely used in the construction and mechanical engineering fields. Therefore, the preparation of the super-hydrophobic stainless steel surface coating with good ice resistance is of great significance.
Disclosure of Invention
The invention aims to solve the problems that: the preparation method of the durable anti-ice super-hydrophobic stainless steel coating is simple and efficient, the raw materials are cheap and available, and the application range is wide.
The technical scheme provided by the invention for solving the problems is as follows: a method for preparing a durable anti-icing super-hydrophobic stainless steel coating comprises the following steps,
firstly, polishing a stainless steel sheet by using sand paper, and then ultrasonically cleaning the stainless steel sheet by using acetone;
secondly, preparing 0.01-0.1 mol/L Zn (NO)3)2·6H2Placing the O solution in a constant-temperature water bath kettle for 1-3 h;
thirdly, controlling the voltage to be 1-3V by using a direct current stabilized voltage supply, and controlling the electrodeposition time to be 1-10 min;
fourthly, preparing Zn (NO) with the concentration of 0.05 to 0.5mol/L3)2·6H2Dropwise adding ammonia water into the O solution until the measured value of a PH meter is 9-12;
fifthly, placing the stainless steel sheet with the surface deposited with the ZnO into a reaction kettle, pouring the solution prepared in the fourth step, and placing the reaction kettle into a vacuum drying oven at 80-120 ℃ for 3-6 hours;
sixthly, putting the preserved sample into a vacuum sintering furnace for sintering;
seventhly, placing the sintered sample in a dodecanethiol ethanol solution with the preparation ratio of 1: 500-1000, soaking for 1-10 min, preparing a super-hydrophobic ZnO sample, and dividing the super-hydrophobic ZnO sample into three batches;
eighthly, measuring contact angles and rolling angles of the first batch of samples, wherein the surface contact angle is 155-165 degrees, and the rolling angle is 3-6 degrees;
ninth, irradiating the second batch of samples with ultraviolet light for 10-20 hours to prepare a hydrophobic ZnO sample;
tenthly, irradiating the third batch of samples by using ultraviolet light for 20-30 h to prepare a hydrophilic ZnO sample;
eleven, placing the three samples on a refrigeration table, adjusting the temperature of the refrigeration table to be 0-15 ℃, respectively dripping 2-5 mu L of water drops on the three samples, and recording the time for freezing the water drops.
Preferably, the ultrasonic cleaning time of the acetone in the step one is 10-20 min.
Preferably, in the sixth step, the sintering temperature is 180-250 ℃, and the calcining time is 3-6 h.
Compared with the prior art, the invention has the advantages that: the preparation method is simple and efficient, the raw materials are cheap and available, the application range is wide, the contact angle between the surface of the obtained super-hydrophobic coating and water is more than 150 degrees, the rolling angle is less than 5 degrees, the ice resistance of the super-hydrophobic coating is excellent, and the super-hydrophobic coating is easy to produce and apply on a large scale.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an SEM image of ZnO as a stainless steel substrate according to the present invention;
FIG. 2 is an XRD pattern of ZnO on a stainless steel substrate according to the present invention;
FIG. 3 is a graph of a contact angle measurement of a ZnO coating on a stainless steel substrate modified with dodecanethiol ethanol according to the present invention;
fig. 4 is a histogram comparing the freezing time of three ZnO coatings on a stainless steel substrate according to the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be provided with reference to the accompanying drawings and examples, so that how to implement the embodiments of the present invention by using technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
The first embodiment is as follows: polishing a stainless steel sheet by using sand paper, and then ultrasonically cleaning the stainless steel sheet for 20min by using acetone; 0.01mol/L Zn (NO) is prepared3)2·6H2Putting the O solution into a water bath kettle with the constant temperature of 65 ℃ for 2 h; controlling the voltage to be 1.8V by adopting a direct current stabilized voltage supply, and depositing for 10min to deposit a ZnO seed layer on the stainless steel sheet; zn (NO) with the concentration of 0.1mol/L is prepared3)2·6H2Adding ammonia water dropwise into the O solution, adjusting the pH to 8, and incompletely dissolving the precipitate generated by the reaction; putting the stainless steel sheet with the surface deposited with ZnO into a reaction kettle, and pouring prepared Zn (NO)3)2Putting the reaction kettle into a vacuum drying oven at 120 ℃ for drying for 4 hours, cooling to room temperature, taking out a sample, washing and drying; putting the preserved sample into a vacuum sintering furnace for sintering, wherein the sintering temperature is 200 ℃, the sintering time is 4 hours, and the sample is cooled to room temperature along with the furnace after sintering; preparation 1: ten of 1000Placing the sintered sample in a prepared solution to be soaked for 10min, taking out and drying to obtain a super-hydrophobic ZnO sample, and dividing the sample into three batches; measuring the contact angle of the ZnO surface of the first batch of samples by using a contact angle measuring instrument to obtain the surface contact angle of 159.47 degrees and the rolling angle of 6 degrees; respectively irradiating the second batch of samples and the third batch of samples for 12h and 24h by using ultraviolet light to obtain a hydrophobic ZnO sample and a hydrophilic ZnO sample; the three samples were placed on a refrigeration table and 4. mu.L of water droplets were dropped below the three samples, respectively, and the freezing times of the water droplets at-5 ℃, -10 ℃, -15 ℃ were recorded, respectively.
The second embodiment is as follows: polishing a stainless steel sheet by using sand paper, and then ultrasonically cleaning the stainless steel sheet for 20min by using acetone; 0.01mol/L Zn (NO) is prepared3)2·6H2Putting the O solution into a water bath kettle with the constant temperature of 65 ℃ for 2 h; controlling the voltage to be 1.8V by adopting a direct current stabilized voltage supply, and depositing for 10min to deposit a ZnO seed layer on the stainless steel sheet; zn (NO) with the concentration of 0.1mol/L is prepared3)2·6H2Dropwise adding ammonia water into the O solution, adjusting the pH to 10, and still precipitating a small part of the O solution; putting the stainless steel sheet with the surface deposited with ZnO into a reaction kettle, and pouring prepared Zn (NO)3)2Putting the reaction kettle into a vacuum drying oven at 120 ℃ for drying for 4 hours, cooling to room temperature, taking out a sample, washing and drying; putting the preserved sample into a vacuum sintering furnace for constant temperature sintering, wherein the sintering temperature is 200 ℃, the sintering time is 4 hours, and the sample is cooled to room temperature along with the furnace after sintering; preparation 1: 1000, soaking the sintered sample in a prepared solution for 10min, taking out and drying to obtain a super-hydrophobic ZnO sample, and dividing the sample into three batches; measuring the contact angle of the ZnO surface of the first batch of samples by using a contact angle measuring instrument to obtain the surface contact angle of 161.22 degrees and the rolling angle of 5.2 degrees; respectively irradiating the second batch of samples and the third batch of samples for 12h and 24h by using ultraviolet light to obtain a hydrophobic ZnO sample and a hydrophilic ZnO sample; the three samples were placed on a refrigeration table and 4. mu.L of water droplets were dropped below the three samples, respectively, and the freezing times of the water droplets at-5 ℃, -10 ℃, -15 ℃ were recorded, respectively.
The third concrete implementation mode: stainless steelPolishing the sheet with sand paper, and ultrasonically cleaning with acetone for 20 min; 0.01mol/L Zn (NO) is prepared3)2·6H2Putting the O solution into a water bath kettle with the constant temperature of 65 ℃ for 2 h; controlling the voltage to be 1.8V by adopting a direct current stabilized voltage supply, and depositing for 10min to deposit a ZnO seed layer on the stainless steel sheet; zn (NO) with the concentration of 0.1mol/L is prepared3)2·6H2Dropwise adding ammonia water into the O solution, adjusting the pH value to 12, and completely dissolving the precipitate generated by the reaction; putting the stainless steel sheet with the surface deposited with ZnO into a reaction kettle, and pouring prepared Zn (NO)3)2Putting the reaction kettle into a vacuum drying oven at 120 ℃ for drying for 4 hours, cooling to room temperature, taking out a sample, washing and drying; putting the preserved sample into a vacuum sintering furnace for constant temperature sintering, wherein the sintering temperature is 200 ℃, the sintering time is 4 hours, and the sample is cooled to room temperature along with the furnace after sintering; preparation 1: 1000, soaking the sintered sample in a prepared solution for 10min, taking out and drying to obtain a super-hydrophobic ZnO sample, and dividing the sample into three batches; measuring the contact angle of the ZnO surface of the first batch of samples by using a contact angle measuring instrument to obtain the surface contact angle of 166.33 degrees and the rolling angle of 4.1 degrees; respectively irradiating the second batch of samples and the third batch of samples for 12h and 24h by using ultraviolet light to obtain a hydrophobic ZnO sample and a hydrophilic ZnO sample; the three samples were placed on a refrigeration table and 4. mu.L of water droplets were dropped below the three samples, respectively, and the freezing times of the water droplets at-5 ℃, -10 ℃, -15 ℃ were recorded, respectively.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (3)
1. A preparation method of a durable anti-ice super-hydrophobic stainless steel coating is characterized by comprising the following steps: the method comprises the following steps of,
firstly, polishing a stainless steel sheet by using sand paper, and then ultrasonically cleaning the stainless steel sheet by using acetone;
secondly, preparing 0.01-0.1 mol/L Zn (NO)3)2·6H2Placing the O solution in a constant-temperature water bath kettle for 1-3 h;
thirdly, controlling the voltage to be 1-3V by using a direct current stabilized voltage supply, and controlling the electrodeposition time to be 1-10 min;
fourthly, preparing Zn (NO) with the concentration of 0.05 to 0.5mol/L3)2·6H2Dropwise adding ammonia water into the O solution until the measured value of a PH meter is 9-12;
fifthly, placing the stainless steel sheet with the surface deposited with the ZnO into a reaction kettle, pouring the solution prepared in the fourth step, and placing the reaction kettle into a vacuum drying oven at 80-120 ℃ for 3-6 hours;
sixthly, putting the preserved sample into a vacuum sintering furnace for sintering;
seventhly, placing the sintered sample in a dodecanethiol ethanol solution with the preparation ratio of 1: 500-1000, soaking for 1-10 min, preparing a super-hydrophobic ZnO sample, and dividing the super-hydrophobic ZnO sample into three batches;
eighthly, measuring contact angles and rolling angles of the first batch of samples, wherein the surface contact angle is 155-165 degrees, and the rolling angle is 3-6 degrees;
ninth, irradiating the second batch of samples with ultraviolet light for 10-20 hours to prepare a hydrophobic ZnO sample;
tenthly, irradiating the third batch of samples by using ultraviolet light for 20-30 h to prepare a hydrophilic ZnO sample;
eleven, placing the three samples on a refrigeration table, adjusting the temperature of the refrigeration table to be 0-15 ℃, respectively dripping 2-5 mu L of water drops on the three samples, and recording the time for freezing the water drops.
2. The method for preparing the durable ice-resistant super-hydrophobic stainless steel coating according to claim 1, wherein the method comprises the following steps: and in the first step, the ultrasonic cleaning with acetone is carried out for 10-20 min.
3. The method for preparing the durable ice-resistant super-hydrophobic stainless steel coating according to claim 1, wherein the method comprises the following steps: in the sixth step, the sintering temperature is 180-250 ℃, and the calcining time is 3-6 h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112301396A (en) * | 2020-09-22 | 2021-02-02 | 南昌航空大学 | Preparation method of surface ZnO superhydrophobic of Cu-Be alloy suitable for aviation sensor |
| CN113549966A (en) * | 2021-06-29 | 2021-10-26 | 安徽工业大学 | Anti-icing super-hydrophobic coating on metal surface and preparation method thereof |
| CN114702863A (en) * | 2022-03-10 | 2022-07-05 | 江苏理工学院 | Preparation method of photo-thermal super-hydrophobic deicing coating |
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2020
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112301396A (en) * | 2020-09-22 | 2021-02-02 | 南昌航空大学 | Preparation method of surface ZnO superhydrophobic of Cu-Be alloy suitable for aviation sensor |
| CN113549966A (en) * | 2021-06-29 | 2021-10-26 | 安徽工业大学 | Anti-icing super-hydrophobic coating on metal surface and preparation method thereof |
| CN114702863A (en) * | 2022-03-10 | 2022-07-05 | 江苏理工学院 | Preparation method of photo-thermal super-hydrophobic deicing coating |
| CN114702863B (en) * | 2022-03-10 | 2023-12-01 | 江苏理工学院 | Preparation method of photo-thermal super-hydrophobic deicing coating |
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Application publication date: 20200515 |