CN112813426B - Surface treatment liquid and preparation method thereof, super-hydrophobic corrosion-resistant composite conversion film and preparation method thereof - Google Patents

Surface treatment liquid and preparation method thereof, super-hydrophobic corrosion-resistant composite conversion film and preparation method thereof Download PDF

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CN112813426B
CN112813426B CN202011641875.1A CN202011641875A CN112813426B CN 112813426 B CN112813426 B CN 112813426B CN 202011641875 A CN202011641875 A CN 202011641875A CN 112813426 B CN112813426 B CN 112813426B
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preparation
cerium salt
super
silane
film
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CN112813426A (en
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孔纲
黄奶兴
周业洋
车淳山
赖德林
万先兰
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Zhaoqing Hongyang Steel Structure Hot Dip Galvanizing Co ltd
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Zhaoqing Hongyang Steel Structure Hot Dip Galvanizing Co ltd
South China University of Technology SCUT
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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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
    • 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
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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Abstract

The invention relates to a surface treatment liquid and a preparation method thereof, and a super-hydrophobic corrosion-resistant composite conversion film and a preparation method thereof. The preparation method of the surface treatment liquid comprises the following steps: mixing the nano particles, the first cerium salt and water to prepare a nano modified solution; mixing the nano modified liquid, silane and a solvent, and hydrolyzing to prepare silane hydrolysate; mixing the second cerium salt, hydrogen peroxide and water to prepare a passivation solution; and mixing the silane hydrolysate and the passivation solution. After the surface treatment liquid prepared by the preparation method is used for treating zinc, a super-hydrophobic composite conversion film can be formed on the surface of the zinc by a one-step method, the process is simple, and the cost is low. The compactness of the composite conversion film can be effectively improved, the problem of easy cracking of the composite conversion film is solved, and the corrosivity of the film layer can be improved.

Description

Surface treatment liquid and preparation method thereof, and super-hydrophobic corrosion-resistant composite conversion film and preparation method thereof
Technical Field
The invention relates to the technical field of metal film materials, in particular to a surface treatment liquid and a preparation method thereof, a super-hydrophobic corrosion-resistant composite conversion film and a preparation method thereof.
Background
Because the oxidation product of zinc can form a compact protective layer, the zinc has good corrosion resistance, so that the zinc is widely used in industry. However, white rust is easily generated in the process of storage or transportation of the zinc or galvanized parts, and the appearance and the quality of the zinc or galvanized parts are affected.
In order to reduce the generation of white rust on the surface of zinc, the traditional treatment method is to perform chromate passivation on the surface of a zinc layer, but hexavalent chromium ions in chromate have serious harm to human bodies and the natural environment and are gradually forbidden. The cerium salt passivation treatment has become a hotspot in the chromium-free passivation technology due to the advantages of no toxicity, no pollution, better corrosion resistance, simple and convenient operation and the like. However, the single cerium salt passive film has the problems of being not uniform and compact enough, being easy to crack and the like, so that the performance improvement of the single cerium salt film is limited.
Therefore, the super-hydrophobic cerium salt conversion film on the metal surface enters the visual field of people, and the super-hydrophobic surface refers to a surface with a water contact angle of more than 150 degrees and a rolling angle of less than 10 degrees. The super-hydrophobic surface has been widely noticed by domestic and foreign scholars due to its excellent performances in self-cleaning, drag reduction, corrosion resistance, water resistance, antifouling and anti-freezing aspects. In terms of corrosion resistance, the super-hydrophobic surface can minimize the contact area between a corrosion medium and the surface due to the existence of an air layer captured by super-hydrophobicity, play a role in isolation and protection, and simultaneously can effectively inhibit the electron transfer between a matrix and the medium to slow down the occurrence of corrosion reaction, thereby effectively improving the corrosion resistance of the film.
At present, the preparation method of the super-hydrophobic cerium salt conversion film on the metal surface is mainly a two-step method. The first step is to construct rough structure on the metal surface, and the second step is to modify the rough structure with low surface energy. For example, patent 201711024427.5 adopts the steps of firstly phosphating a zinc layer, then roughening a phosphating film by using cerium salt, and finally modifying the surface energy to obtain an ultra-hydrophobic film layer with good corrosion resistance. The two-step method for preparing the super-hydrophobic membrane layer is complicated. Meanwhile, researchers have also studied one-step method for preparing cerium salt hydrophobic or super-hydrophobic membrane layer, lei et al [ DOI 10.1002/sia.5734]Cerium salt and bis- [3- (triethoxysilyl) propyl ] are adopted]The-tetrasulfide is used as a raw material, and the hydrophobic membrane layer is prepared on aluminum through a one-step impregnation method, but the hydrophobic angle of the-tetrasulfide is 112.9 degrees and the-tetrasulfide does not reach a super-hydrophobic state. Zuo et al [ DOI 10.1016/S1003-6326 (14) 63215-5]Cerium salts and bis- [3- (triethoxysilyl) propyl ] are also used]-tetrasulfide as starting material and using ZrO 2 The modified particles have a hydrophobic angle of only 102.5 degrees, and the super-hydrophobic state is not achieved. In patent 201910749444.8, cerium nitrate and graphene are used as raw materials for manufacturing roughness, lauric acid is used as a low-surface-energy modifier, and a cerium salt film layer with super-hydrophobic and self-cleaning functions is prepared on the surface of an aluminum alloy through a one-step method, but the preparation method is an electrodeposition method. In addition, patent 201510749765.X also adopts similar raw materials and a similar method to prepare a super-hydrophobic cerium salt film on the surface of the magnesium alloy, and the preparation method is also an electrodeposition method, which is relatively complex in preparation operation.
Disclosure of Invention
Accordingly, the present invention provides a method for producing a surface treatment liquid. After the surface treatment liquid prepared by the preparation method is used for treating zinc, a super-hydrophobic composite conversion film can be formed on the surface of the zinc by a one-step method, and the preparation method is simple in process and low in cost. And the compactness of the composite conversion film can be effectively improved, the problem of easy cracking of the composite conversion film is solved, and the corrosivity of the film layer can be improved.
The preparation method of the surface treatment liquid comprises the following steps:
mixing the nano particles, the first cerium salt and water to prepare a nano modified solution;
mixing the nano modified liquid, silane and a solvent, and hydrolyzing to prepare silane hydrolysate;
mixing the second cerium salt, hydrogen peroxide and water to prepare a passivation solution;
and mixing the silane hydrolysate and the passivation solution.
In one preferred embodiment, the nanoparticles are ceria.
In one preferred embodiment, the first cerium salt and the second cerium salt are each independently selected from at least one of cerium nitrate and cerium chloride.
In one preferred embodiment, in the nano-modification liquid, the concentration of the nano-particles is 150ppm to 350ppm, and the concentration of the first cerium salt is 150ppm to 350ppm.
In one preferable embodiment, in the passivation solution, the concentration of the second cerium salt is 30-45 g/L, and the concentration of the hydrogen peroxide is 5-20 mL/L.
In one preferred embodiment, the silane is selected from at least one of vinyltriethoxysilane, gamma-aminopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and vinyltrimethoxysilane.
In one preferred embodiment, the solvent is ethanol.
In one preferred embodiment, the volume ratio of the silane to the nano-modification liquid to the solvent is (5-10): (5-10): (80-100).
In one preferred embodiment, the hydrolysis time is 36h to 60h.
In one preferred embodiment, the volume ratio of the silane hydrolysis liquid to the passivation liquid is (1-2): (1-2).
The invention also provides the surface treatment liquid prepared by the preparation method.
The invention also provides a preparation method of the super-hydrophobic corrosion-resistant composite conversion film. The surface of the zinc matrix is treated by a one-step method to form the super-hydrophobic corrosion-resistant composite conversion coating.
The preparation method of the super-hydrophobic corrosion-resistant composite conversion film comprises the following steps:
the surface of the zinc matrix is contacted with the surface treatment liquid by a dipping or spraying method, and then dried to form a film.
In one preferred embodiment, the time for the impregnation is 0.5h to 3h.
The invention also provides the super-hydrophobic corrosion-resistant composite conversion coating prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
in the surface treatment liquid of the present invention, H is added 2 O 2 In order to promote the film formation of cerium salt. The existence of the nano particles is beneficial to providing a micro-nano rough structure for a subsequent super-hydrophobic composite conversion film, and the nano particles are added before hydrolysis so as to be doped into a silica network to construct and improve the barrier property of the silane film. And the existence of the second cerium salt can establish a Si-O-Ce bond with silane, so that the dispersibility of the nano particles is improved, the porosity and the conductivity of a silica network are reduced, and the barrier property is further improved. The silane is favorable for improving the compactness of a subsequent super-hydrophobic composite conversion film and solving the problem of easy cracking of the subsequent super-hydrophobic composite conversion film, and the super-hydrophobic cerium salt-silane composite conversion film with super-hydrophobic performance and a water sliding angle of less than 10 degrees can be obtained by adopting the surface treatment liquid to treat the surface of the zinc layer by a one-step method, shows good corrosion resistance and plays a good role in protecting the zinc layer.
Drawings
FIG. 1 is a water contact angle diagram of a superhydrophobic corrosion-resistant composite conversion film prepared in example 1;
FIG. 2 is an SEM image of a superhydrophobic corrosion resistant composite conversion coating prepared in example 1;
FIG. 3 is a Nyquist plot of the superhydrophobic corrosion-resistant composite conversion coating prepared in example 1;
FIG. 4 is a Tafel plot of the superhydrophobic corrosion-resistant composite conversion coating prepared in example 1;
FIG. 5 is a water contact angle diagram of the superhydrophobic corrosion-resistant composite conversion coating prepared in example 2;
FIG. 6 is an SEM image of a superhydrophobic corrosion-resistant composite conversion film prepared in example 2;
FIG. 7 is a Nyquist plot of the superhydrophobic corrosion resistant composite conversion coating prepared in example 2;
FIG. 8 is a Tafel plot of the superhydrophobic corrosion resistant composite conversion coating prepared in example 2;
FIG. 9 is a water contact angle graph of the superhydrophobic corrosion resistant composite conversion coating prepared in example 3;
FIG. 10 is an SEM image of a superhydrophobic corrosion-resistant composite conversion film prepared in example 3;
FIG. 11 is a Nyquist plot of the superhydrophobic corrosion-resistant composite conversion coating prepared in example 3;
FIG. 12 is a Tafel plot of the superhydrophobic corrosion resistant composite conversion coating prepared in example 3;
FIG. 13 is a water contact angle plot for the corrosion resistant composite conversion coating prepared in comparative example 1;
FIG. 14 is an SEM image of a corrosion-resistant composite conversion coating prepared in comparative example 1;
FIG. 15 is a Nyquist plot of the corrosion-resistant composite conversion coating prepared in comparative example 1;
fig. 16 is a Tafel plot of the corrosion resistant composite conversion coating prepared in comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
A preparation method of a surface treatment liquid comprises the following steps:
mixing the nano particles, the first cerium salt and water to prepare a nano modified solution;
mixing the nano modified liquid, silane and a solvent, and hydrolyzing to prepare silane hydrolysate;
mixing second cerium salt, hydrogen peroxide and water to prepare passivation solution;
and mixing the silane hydrolysate and the passivation solution.
And the nano particles are added, so that a micro-nano rough structure is provided for a subsequent super-hydrophobic composite conversion film. The nano particles are added before hydrolysis, so that the nano particles can be doped into the construction of a silica network, and the barrier property of the silane film is improved.
Preferably, the nanoparticles are ceria.
In one embodiment, the concentration of the nanoparticles in the nano-modification liquid is 150ppm to 350ppm, and the concentration of the first cerium salt is 150ppm to 350ppm.
Preferably, the first cerium salt is selected from at least one of cerium nitrate and cerium chloride.
And silane is added, so that the compactness of a subsequent super-hydrophobic composite conversion film is improved, and the problem of easy cracking of the film is solved.
Preferably, the silane is selected from at least one of vinyltriethoxysilane, gamma-aminopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane.
In one embodiment, the volume ratio of the silane to the nano-modification liquid to the solvent is (5-10): (5-10): (80-100).
In one embodiment, the hydrolysis time is 36h to 60h.
In one embodiment, the solvent is ethanol.
The presence of the second cerium salt can establish Si-O-Ce bonds with silane, thereby improving the dispersibility of the nanoparticles, contributing to the reduction of the porosity and conductivity of the silica network, and further improving the barrier properties.
In one embodiment, in the passivation solution, the concentration of the second cerium salt is 30-45 g/L, and the concentration of the hydrogen peroxide is 5-20 mL/L.
Preferably, the second cerium salt is selected from at least one of cerium nitrate and cerium chloride.
It is understood that the first cerium salt and the second cerium salt may be the same or different.
The volume ratio of the silane hydrolysate to the passivating solution is (1-2): (1-2).
A surface treatment fluid prepared by the above preparation method.
The surface of the zinc layer is treated by the surface treatment liquid one-step method, so that the super-hydrophobic cerium salt-silane composite conversion film which has super-hydrophobic performance and has a water sliding angle of less than 10 degrees can be obtained, the corrosion resistance is good, and the zinc layer is well protected.
A preparation method of a super-hydrophobic corrosion-resistant composite conversion coating comprises the following steps:
the surface of the zinc matrix is contacted with the surface treatment liquid by a dipping or spraying method, and then dried to form a film.
Preferably, the time of the impregnation is between 0.5h and 3h.
It is understood that the zinc substrate further comprises a step of pre-treating the zinc substrate before contacting the surface treatment liquid.
The pretreatment comprises the following steps: one or more of sanding, alcohol treatment and alkali treatment.
In a preferred embodiment, the pre-treatment comprises sanding and alkali treatment.
In a preferred embodiment, the pre-treatment comprises sanding and alcohol treatment.
In a preferred embodiment, the pre-treatment comprises sanding, alcohol treatment and alkali treatment.
The alcohol treatment method comprises the following steps: the zinc matrix is soaked in alcohol.
The alkali treatment method is to soak the zinc matrix in alkali.
After the zinc matrix is pretreated, the zinc matrix can be washed by water, dried and then contacted with the surface treatment liquid.
The preparation method has simple process and simple and convenient operation.
The super-hydrophobic corrosion-resistant composite conversion film prepared by the preparation method.
The following examples and comparative examples are further described below, and the starting materials used in the following examples can be commercially available, unless otherwise specified, and the equipment used therein can be commercially available, unless otherwise specified.
Example 1
The embodiment provides a surface treatment liquid and a preparation method thereof, a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) Adding CeO 2 Nanoparticles and Ce (NO) 3 Are uniformly dispersed in distilled water by ultrasonic with the content of 350ppm to obtain the nano modified liquid. Mixing methyltrimethoxysilane, the nano modified liquid and ethanol according to a volume ratio of 8. Mixing Ce (NO) 3 、H 2 O 2 Mixing with distilled water to obtain a mixture containing 30g/L of Ce (NO) 3 And 5ml/L of H 2 O 2 And uniformly mixing the stirred silane hydrolysis liquid and the passivation solution according to the volume ratio of 1.
2) Polishing a 2cm × 2cm pure zinc plate by using sand paper, soaking the polished pure zinc plate in 1M NaOH for 2min, washing the polished pure zinc plate with distilled water after finishing the soaking, and drying the polished pure zinc plate with cold air. Immersing the pretreated pure zinc plate into the surface treatment liquid, taking out after immersing for 1h, and drying for 3min at 80 ℃. The super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating is obtained.
The test methods and results are as follows:
the test method comprises the following steps: the Water Contact Angle (WCA) of a 5 μ L drop of water at ambient temperature was measured using a surface tension surface contact angle tester (OCA 20, dataPhysics Instruments GmbH, germany). The topography of the sample surface was characterized using an environmental scanning electron microscope (NOVA NANOSE EM 430, FEI, netherlands). The electrochemical performance of the membrane layer was tested using an electrochemical workstation (shanghai chenhua instruments ltd, china, CHI 660E).
And (3) testing results: fig. 1 is a water contact angle diagram of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating, and it can be seen from fig. 1 that the hydrophobic angle of the coating is 151.2 °. Fig. 2 is an SEM image of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film, and it can be seen from fig. 2 that compared with the single cerium salt film of other documents, the film has better density and fewer cracks, and the surface-coated nanoparticles provide a rough structure required for preparing the super-hydrophobic surface while playing a role of barrier. Electrochemical tests show that the FIG. 3 is a Nyquist diagram of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film, and the EIS impedance value of the film layer is 0.35M omega cm 2 The impedance value of the film is much larger than 4958 omega cm of a single cerium salt film 2 FIG. 4 is Tafel plot of the above super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating, and it can be known through software fitting of an electrochemical workstation that the corrosion current density is 0.738 μ A/m 2 Much less than the corrosion current density of 3.94 muA/m of a single cerium salt film 2 It shows that the corrosion resistance of the film is far better than that of a single cerium salt film.
Example 2
The embodiment provides a surface treatment liquid and a preparation method thereof, a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) Adding CeO 2 Nanoparticles and Ce (NO) 3 Uniformly dispersing the nano modified solution in distilled water by ultrasonic waves according to the content of 250ppm to obtain the nano modified solution. Mixing vinyl triethoxysilane, the nano modified solution and ethanol according to a volume ratio of 10. Reacting CeCl 3 、H 2 O 2 Mixing with distilled water to obtain CeCl solution containing 35g/L 3 And 10ml/L of H 2 O 2 And the stirred silicon is addedAnd (3) uniformly mixing the alkane hydrolysate with the passivation solution according to the volume ratio of 1.2.
2) Polishing a 2cm × 2cm pure zinc plate by using sand paper, soaking in absolute ethyl alcohol for 3min after polishing, washing with distilled water after polishing, and drying by using cold air. And (3) immersing the pretreated pure zinc plate into the surface treatment liquid for 1.5h, taking out, and drying at 80 ℃ for 10min. The super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating is obtained.
The test method is the same as that of the example 1, and the test result is as follows: fig. 5 is a water contact angle diagram of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating, and the contact angle of the coating is 158.6 °. Fig. 6 is an SEM image of the superhydrophobic corrosion-resistant cerium salt-silane composite conversion film, and it can be seen from fig. 6 that the film has better density and fewer cracks than the single cerium salt film of other documents, and the surface-coated nanoparticles provide a rough structure required for preparing the superhydrophobic surface while playing a role in blocking. Electrochemical tests show that FIG. 7 is a Nyquist diagram of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film, and the EIS impedance value of the film layer is 1.18M omega cm 2 The impedance value of the film is much larger than 4958 omega cm of a single cerium salt film 2 FIG. 8 is a Tafel plot of the above super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film, and the corrosion current density is 1.41 × 10 by software fitting -2 μA/m 2 Much less than the corrosion current density of 3.94 muA/m of a single cerium salt film 2 The corrosion resistance of the film is much better than that of a single cerium salt film.
Example 3
The embodiment provides a surface treatment liquid and a preparation method thereof, a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) CeO is added 2 Nanoparticles and CeCl 3 Uniformly dispersing the nano modified solution in distilled water by ultrasonic waves according to the content of 250ppm to obtain the nano modified solution. Mixing vinyl trimethoxy silane, the nano modified liquid and ethanol according to a volume ratio of 5. Mixing Ce (NO) 3 、H 2 O 2 Mixing with distilled water to obtain a mixture containing 35g/L of Ce (NO) 3 And 20ml/L of H 2 O 2 And uniformly mixing the stirred silane hydrolysis liquid and the passivation solution according to the volume ratio of 1.
2) Polishing a 2cm × 2cm pure zinc plate by using sand paper, soaking in absolute ethyl alcohol for 3min after polishing, then soaking in 1M NaOH for 2min, washing with distilled water after finishing, and drying by cold air. And (3) immersing the pretreated pure zinc plate into the surface treatment liquid for 3 hours, taking out the pure zinc plate, and drying the pure zinc plate for 1min at 110 ℃. The super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating is obtained.
The test method is the same as that of the example 1, and the test result is as follows: fig. 9 is a water contact angle diagram of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating, and the contact angle of the coating is 158 °. Fig. 10 is an SEM image of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film, and it can be seen from fig. 10 that compared with the single cerium salt film of other documents, the film has better density and fewer cracks, and the surface-coated nanoparticles provide a rough structure required for preparing the super-hydrophobic surface while playing a role of barrier. Electrochemical tests show that FIG. 11 is a Nyquist diagram of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film, and the EIS impedance value of the film layer is 0.97M omega cm 2 The impedance value of the film is 4958 omega cm far greater than that of a single cerium salt film 2 FIG. 12 is a Tafel plot of the above super-hydrophobic corrosion-resistant Ce salt-silane composite conversion coating, and the corrosion current density is 1.97 × 10 by software fitting -3 μA/m 2 Much less than the corrosion current density of 3.94 muA/m of a single cerium salt film 2 The corrosion resistance of the film is much better than that of a single cerium salt film.
Example 4
The embodiment provides a surface treatment liquid and a preparation method thereof, a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) Adding CeO 2 Nanoparticles and Ce (NO) 3 Uniformly dispersing the mixture in distilled water by ultrasonic treatment according to the content of 300ppm to obtain the nano modified liquid. Mixing vinyl trimethoxy silane, the nano modified solution and ethanol according to the volume ratio of 5. Reacting CeCl 3 、H 2 O 2 Mixing with distilled water, and makingContaining 40g/L of CeCl 3 And 5ml/L of H 2 O 2 And uniformly mixing the stirred silane hydrolysis liquid and the passivation solution according to a volume ratio of 1.
2) Polishing a 2cm × 2cm pure zinc plate by using sand paper, soaking the polished pure zinc plate in absolute ethyl alcohol for 5min, washing the polished pure zinc plate with distilled water after finishing the soaking, and drying the polished pure zinc plate with cold air. And (3) immersing the pretreated pure zinc plate into the surface treatment liquid for 3 hours, taking out the pure zinc plate, and drying the pure zinc plate for 1min at 110 ℃. The super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating is obtained.
The test method is the same as that of the example 1, and the test result is as follows: the hydrophobic angle of the membrane layer was 155.3 °. Compared with the single cerium salt film layer of other documents, the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film has better density and fewer cracks, and the nano particles covered on the surface can play a role in blocking and provide a rough structure required by the preparation of a super-hydrophobic surface. Electrochemical tests show that the EIS impedance value of the film layer is 0.72M omega cm 2 The impedance value of the film is much larger than 4958 omega cm of a single cerium salt film 2 The corrosion current density is 6.45 multiplied by 10 -2 μA/m 2 Much less than the corrosion current density of 3.94 muA/m of a single cerium salt film 2 The corrosion resistance of the film is much better than that of a single cerium salt film.
Example 5
The embodiment provides a surface treatment liquid and a preparation method thereof, and a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) Adding CeO 2 Nanoparticles and Ce (NO) 3 Uniformly dispersing the nano modified solution in distilled water by ultrasonic waves according to the content of 250ppm to obtain the nano modified solution. And mixing the methyltriethoxysilane, the nano modified solution and ethanol according to the volume ratio of 5. Mixing Ce (NO) 3 、H 2 O 2 Mixing with distilled water to prepare a mixture containing 45g/L of Ce (NO) 3 And 5ml/L of H 2 O 2 And uniformly mixing the stirred silane hydrolysis liquid and the passivation solution according to the volume ratio of 1.5.
2) Polishing a 2cm multiplied by 2cm pure zinc plate by using sand paper, soaking the polished pure zinc plate in absolute ethyl alcohol for 3min, soaking the polished pure zinc plate in 1M NaOH for 2min, washing the polished pure zinc plate with distilled water after finishing, and drying the polished pure zinc plate with cold air. Immersing the pretreated pure zinc plate into the surface treatment liquid, taking out after immersing for 45min, and drying for 3min at 80 ℃. The super-hydrophobic corrosion-resistant cerium salt-silane composite conversion coating is obtained.
The test method is the same as that of example 1, and the test results are as follows: the hydrophobic angle of the film layer reaches 150.8 degrees, compared with the single cerium salt film layer of other documents, the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film has better density and fewer cracks compared with the former example, and the nano particles covered on the surface provide a rough structure required by preparing a super-hydrophobic surface. Electrochemical tests show that the EIS impedance value of the film layer is 0.33 MOmega cm 2 The impedance value of the film is much larger than 4958 omega cm of a single cerium salt film 2 (ii) a The corrosion current density is 0.21 muA/m 2 Much less than the corrosion current density of 3.94 muA/m of a single cerium salt film 2 The corrosion resistance of the film is much better than that of a single cerium salt film.
Comparative example 1
The comparative example provides a surface treatment fluid and a preparation method thereof, and a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) Mixing methyltrimethoxysilane and ethanol according to the volume ratio of 8. Mixing Ce (NO) 3 、H 2 O 2 Mixing with distilled water to obtain a mixture containing 30g/L of Ce (NO) 3 And 5ml/L of H 2 O 2 And uniformly mixing the stirred silane hydrolysis liquid and the passivation solution according to the volume ratio of 1.
2) Polishing a 2cm × 2cm pure zinc plate by using sand paper, soaking the polished pure zinc plate in 1M NaOH for 2min, washing the polished pure zinc plate with distilled water after finishing the soaking, and drying the polished pure zinc plate with cold air. Immersing the pretreated pure zinc plate into the surface treatment liquid, taking out after immersing for 1h, and drying for 3min at 80 ℃. The cerium salt-silane composite conversion coating is obtained.
The test method is the same as that of example 1, and the test results are as follows: FIG. 13 is a water contact angle diagram of the cerium salt-silane composite conversion coating, and it can be seen from FIG. 13 thatThe hydrophobic angle of the membrane layer is 123.6 degrees, and the super-hydrophobic state is not achieved. Fig. 13 is an SEM image of the cerium salt-silane composite conversion film, and fig. 14 shows that the film layer modified without nanoparticles has reduced cracks on the surface, but the film layer is not modified with nanoparticles, and has no nanoparticle coating layer. Electrochemical tests show that FIG. 15 is a Nyquist diagram of the cerium salt-silane composite conversion film, and the EIS impedance value of the film layer is 3060 Ω · cm 2 The impedance value of the film is not as good as 4958 omega cm 2 However, as can be seen from the Tafel plot and the software fitting results of the above-mentioned super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film in FIG. 16, the corrosion current density is 0.952 μ A/m 2 Less than 3.94 μ A/m of corrosion current density of single cerium salt film 2 。
Comparative example 2
The comparative example provides a surface treatment fluid and a preparation method thereof, and a super-hydrophobic corrosion-resistant composite conversion coating and a preparation method thereof, and the preparation method comprises the following steps:
1) Mixing methyltrimethoxysilane and ethanol according to the volume ratio of 8. Mixing Ce (NO) 3 、H 2 O 2 Mixing with distilled water to obtain a mixture containing 30g/L of Ce (NO) 3 And 5ml/L of H 2 O 2 Uniformly mixing the stirred silane hydrolysate with the passivating solution according to the volume ratio of 1 2 And (4) uniformly dispersing the nano particles by ultrasonic to obtain the surface treatment liquid.
2) Polishing a pure zinc plate with the thickness of 2cm multiplied by 2cm by using sand paper, soaking the pure zinc plate in 1M NaOH for 2min after polishing, washing the pure zinc plate with distilled water after polishing, and drying the pure zinc plate with cold air. And (3) immersing the pretreated pure zinc plate into the surface treatment liquid for 1h, taking out the pure zinc plate, and drying the pure zinc plate for 3min at the temperature of 80 ℃. The cerium salt-silane composite conversion coating is obtained.
The test method is the same as that of the example 1, and the test result is as follows: the hydrophobic angle of the film layer reaches 130.2 degrees, and the film layer does not reach super-hydrophobicity, the cerium salt-silane composite conversion film is the same as the comparative example 1, although the cracks on the surface of the film layer are reduced, the improvement degree is not as good as that after the modification, but the quantity of the nano particles covered on the film layer is more than that of the nano particles which are not addedAnd (5) compounding the film layer. Electrochemical tests show that the EIS impedance value of the film layer is 14230 omega cm 2 (ii) a Impedance value of 4958 omega cm greater than that of single cerium salt film 2 The corrosion current density is 0.483 mu A/m 2 The corrosion current density of the film is less than 3.94 mu A/m of a single cerium salt film 2 The corrosion resistance of the film is better than that of a single cerium salt film and a composite film without nano particles.
From the above results, it can be seen that the film prepared without adding nanoparticles or after hydrolysis, adding nanoparticles, cannot obtain superhydrophobicity, and the film density and the corrosion resistance reflected in the electrochemical characterization have a certain difference from those of the film prepared by adding nanoparticles before hydrolysis. The preparation method of the super-hydrophobic corrosion-resistant cerium salt-silane composite conversion film provided by the invention is simple in process and convenient to operate, can effectively solve the problems that the cerium salt film is easy to crack and has overlarge cracks, has good super-hydrophobicity, and the corrosion resistance of the film layer is excellent and far better than that of a single cerium salt film.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (9)

1. A preparation method of a surface treatment liquid is characterized by comprising the following steps:
mixing the nano particles, the first cerium salt and water to prepare a nano modified solution;
mixing the nanometer modified solution, silane and a solvent, and hydrolyzing to prepare silane hydrolysate;
mixing the second cerium salt, hydrogen peroxide and water to prepare a passivation solution;
mixing the silane hydrolysate and the passivation solution;
the silane is selected from at least one of vinyltriethoxysilane, gamma-aminopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and vinyltrimethoxysilane; and/or the presence of a catalyst in the reaction mixture,
the solvent is ethanol.
2. The method of preparing a surface treatment liquid according to claim 1, wherein the nanoparticles are cerium oxide; and/or the presence of a catalyst in the reaction mixture,
the first cerium salt and the second cerium salt are respectively and independently selected from at least one of cerium nitrate and cerium chloride.
3. The method according to claim 1, wherein the concentration of the nanoparticles is 150ppm to 350ppm, and the concentration of the first cerium salt is 150ppm to 350ppm; and/or the like, and/or,
in the passivation solution, the concentration of the second cerium salt is 30-45 g/L, and the concentration of hydrogen peroxide is 5-20 mL/L.
4. The method for preparing the surface treatment fluid according to any one of claims 1 to 3, wherein the silane, the nano-modification fluid and the solvent are present in a volume ratio of (5-10) to (80-100); and/or the presence of a catalyst in the reaction mixture,
the hydrolysis time is 36-60 h.
5. The method for preparing the surface treatment liquid according to any one of claims 1 to 3, wherein the volume ratio of the silane hydrolysis liquid to the passivating liquid is (1-2) to (1-2).
6. A surface treatment liquid prepared by the preparation method according to any one of claims 1 to 5.
7. The preparation method of the super-hydrophobic corrosion-resistant composite conversion coating is characterized by comprising the following steps:
a zinc substrate surface is contacted with the surface treatment liquid according to any one of claims 1 to 5 by a dipping or spraying method, and then dried to form a film.
8. The method for preparing the superhydrophobic corrosion-resistant composite conversion coating according to claim 7, wherein the immersion time is 0.5h-3h.
9. The super-hydrophobic corrosion-resistant composite conversion film prepared by the preparation method of any one of claims 7 to 8.
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