CN112941494A - A kind of (SiC) with lotus leaf effectPPreparation method of super-hydrophobic membrane layer - Google Patents

A kind of (SiC) with lotus leaf effectPPreparation method of super-hydrophobic membrane layer Download PDF

Info

Publication number
CN112941494A
CN112941494A CN202110256815.6A CN202110256815A CN112941494A CN 112941494 A CN112941494 A CN 112941494A CN 202110256815 A CN202110256815 A CN 202110256815A CN 112941494 A CN112941494 A CN 112941494A
Authority
CN
China
Prior art keywords
sic
silicon carbide
super
film layer
lotus leaf
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110256815.6A
Other languages
Chinese (zh)
Other versions
CN112941494B (en
Inventor
宿辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heilongjiang Institute of Technology
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN202110256815.6A priority Critical patent/CN112941494B/en
Publication of CN112941494A publication Critical patent/CN112941494A/en
Application granted granted Critical
Publication of CN112941494B publication Critical patent/CN112941494B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

A kind of (SiC) with lotus leaf effectPA method for preparing super-hydrophobic film layer belongs to the technical field of material surface modification, and adopts a simple chemical deposition method to construct a micro-nano structure under the conditions of normal pressure and normal temperature to realize (SiC)PAnd (3) preparing the super-hydrophobic membrane layer. The preparation process comprises (SiC)PPretreatment, (SiC)PSurface chemical deposition modification and after modification (SiC)PStanding for a longer time. The static water contact angle of the prepared film layer is 150-160 degrees, the rolling angle is less than 10 degrees, and good super-hydrophobicity is shown at 10-80 degrees. For use in the invention (SiC)PThe method has the advantages of being waste materials generated in the industrial production process, low in requirement on raw materials, beneficial to resource recycling, simple to operate, environment-friendly, low in equipment requirement, good in hydrophobic effect and the like, and is convenient to popularize. The silicon carbide particles with super-hydrophobicity are combined with the excellent performances of wear resistance, corrosion resistance and the like, and can be used for self-cleaning and preventionThe coating is widely applied to the fields of ice, fog prevention, pollution prevention and the like.

Description

A kind of (SiC) with lotus leaf effectPPreparation method of super-hydrophobic membrane layer
Technical Field
The invention relates to the technical field of preparation and surface modification of inorganic powder materials, in particular to a preparation method of a silicon carbide super-hydrophobic film layer with a lotus leaf effect.
Background
Because the contact area of the super-hydrophobic surface and water is limited, the chemical reaction and chemical bond combination of the super-hydrophobic surface and the water are inhibited, and the super-hydrophobic surface has the advantages of pollution resistance, self-cleaning, ice and snow prevention, oxidation resistance, corrosion resistance and the like. In nature, leaves of many plants and some parts of animals have super-hydrophobic properties, such as lotus leaves, dragonfly wings, mosquito compound eyes, and the like. The lotus leaf is a plant which is firstly discovered to have super-hydrophobicity, and researches show that the surfaces with the super-hydrophobic characteristic in the nature all have a micro-nano structure similar to the surfaces of the lotus leaf, and the micro-nano structure is called as' lotus leafLeaf effect ". The wettability of a solid surface is determined by its surface chemical composition and roughness, and lower surface free energy and suitable roughness are important factors for preparing a superhydrophobic surface. The lower the free energy of the material surface, the stronger the hydrophobic properties of the membrane. Common methods for preparing the superhydrophobic film layer include phase separation, sol-gel method, chemical deposition, electrodeposition method, laser etching method, and the like. In general, hydrophobic groups in organic modifiers are introduced into particles to make the particles hydrophobic due to organic long chains grafted on the surfaces of the particles, and metal oxides such as TiO are more studied2、Al2O3ZnO, etc. How to Li Red, etc. of the related documents silane coupling agent surface modified titanium dioxide particles have super-hydrophobic property [ J]Fine chemical industry, 2014; single spray displacement of a hot water-repeat and oil-water separation of hydrophilic organic polymers modification of hydrophilic nano-alumina [ J]Progress in Organic Coatings, 2018. Populus and the like, a preparation method of a ZnO/AAO composite film with hydrophobic/super-hydrophobic performance, wherein patent numbers CN111996516A and CN101932661A are used for grafting fluoroalkyl silane to the surface of inorganic particles to obtain hydrophobic and oleophobic inorganic particles. However, the above preparation methods mostly require the use of organic solvents, and have high preparation cost, no environmental protection, complex process, or high requirements for raw materials and equipment.
Silicon carbide particles [ abbreviated as (SiC)P]Has the advantages of high hardness, wear resistance, high temperature resistance and the like, but shows hydrophilicity, particularly, the silicon carbide micro powder has small granularity, large specific surface area and strong hydrophilicity, and is related to (SiC)PThe preparation method of the super-hydrophobic membrane has few reports. The silicon carbide particles have super-hydrophobicity by an environment-friendly and simple method, are combined with excellent performances such as wear resistance, corrosion resistance and the like, can be widely applied to the fields such as self-cleaning, anti-icing, anti-fogging and anti-fouling, and have important value in the fields of scientific research, production, life and the like.
Disclosure of Invention
The invention aims to provide (SiC) which is environment-friendly, has low requirements on raw materials and can keep hydrophobicity for a long timePSuper-hydrophobic film layerThe preparation method of (1).
Based on accumulated experimental and theoretical experience, industrial waste (SiC) produced by Raymond mill and supersonic jet milling in the production processPUsing chemical deposition method to treat the irregular shape waste (SiC)PCarrying out surface modification and simple post-treatment, spontaneously constructing a micro-nano structure to obtain (SiC) with lotus leaf effectPA super-hydrophobic membrane layer.
The invention relates to a (SiC) with lotus leaf effectPThe preparation method of the super-hydrophobic membrane layer is carried out according to the following steps:
step one, (SiC)PPretreatment
Carrying out oxidation etching treatment by using a resistance furnace at the temperature of 900-1500 ℃ for 2-4 hours; carrying out hydrophilic treatment for 15-30 minutes at room temperature in a mixed solution of HF, HCl and distilled water with the volume ratio of 1:1: 10-15; then in the range of 0.2-1.5mol · L-1 TiCl3、0.5-2.0 g · L-1 PdCl2Activating in HCl mixed solution for 20-40 min at room temperature;
step two, preparation of deposition solution
Sequentially adding 50-80 g.L of oxidant-110 to 20 g/L of an accelerator-115-30 g.L of revival complexing agent-11.5-3.5 mg.L of rare earth-120 to 30 g.L of a reducing agent-1And 0.1-1.0 mg.L of stabilizer-1After uniformly mixing, adjusting the pH value to 7.0-8.5;
step three, preparation of the super-hydrophobic film layer
After the pretreatment of the first Step (SiC)PPreparing slurry by using distilled water as a solvent; wherein, (SiC)PMass ratio to distilled water: 1: 10-15. Adding into the deposition solution after ultrasonic dispersion, mechanically stirring, heating to 30-50 deg.C, depositing for 1-3 hr under the condition that pH value of the solution is 7.0-8.5, filtering, cleaning, drying, standing for more than 12 months to obtain the (SiC) with lotus leaf effectPAnd (3) preparing the super-hydrophobic membrane layer.
Furthermore, the oxidant is nickel sulfate or nickel chloride, the accelerator is sodium molybdate, the reactivation complexing agent is boric acid and sodium pyrophosphate, the reducing agent is sodium hypophosphite, and the stabilizer is thiourea or lead nitrate.
Further, the deposition solution is prepared as follows:
adding 50-80 g.L of nickel sulfate in sequence-110-20 g.L of sodium molybdate-110 to 20 g.L of sodium pyrophosphate-1Boric acid 5-10 g.L-11.5-3.5 mg.L of rare earth-1Sodium hypophosphite 20-30 g.L-1And 0.1-1.0 mg.L stabilizer-1After mixing evenly, adjusting the pH value to 7.0-8.5 by ammonia water.
Further, the volume ratio of the slurry to the deposition solution in the third step is 1: 8 to 20.
Further, the standing in the third step is performed under normal temperature conditions.
The beneficial technical effects of the invention are embodied in the following aspects:
(1) the invention firstly discovers that after the silicon carbide particles subjected to the chemical deposition treatment are placed for a long time, the silicon carbide particles can form obvious hydrophobic performance, and can form a super-hydrophobic film layer when meeting water and can be kept for a long time.
(2) Used (SiC)PFor industrial production 1200#In the process of monocrystalline silicon, the waste materials generated by Raymond mill and supersonic speed airflow pulverization are utilized, and the method is favorable for resource reutilization. Meanwhile, the used silicon carbide is micron-sized and irregular in shape, and the method has low requirements on raw materials and a wide application range.
(3) The method adopts environment-friendly pre-treatment, chemical deposition and post-treatment methods, does not generate secondary pollution, and is beneficial to
And (5) environmental protection. In the preparation process, the hydrophobic effect can be controlled by adjusting the formula of the deposition solution, process parameters, post-treatment conditions and the like, the repeatability and controllability of the process are improved, and the process gradually develops to scale.
(4) After surface modification (SiC)PThe appearance and the property are greatly changed, and the appearance color is changed from grey white to grey black. After being placed for more than 12 months, the water is changed from hydrophilicity to super hydrophobicity, and a super-hydrophobic film layer is formed. The contact angle test result shows that the static waterThe contact angle is 150-160 degrees, the rolling angle is less than 10 degrees, and good super-hydrophobicity is shown.
(5) The method disclosed by the invention is environment-friendly, simple to operate, low in requirements on equipment and raw materials, less in influence of temperature on the hydrophobic membrane, good in hydrophobicity within the temperature range of 10-80 ℃, and convenient to popularize and use.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a comparative picture of "silicon carbide raw powder, modified silicon carbide and photograph thereof dissolved in water in substance after standing for 18 months" in example 1; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, and the right picture (c) is modified silicon carbide after standing for 18 months;
FIG. 2 shows "raw powder of silicon carbide, modified silicon carbide and the results obtained after standing still for 18 months" in example 1
A physical photograph comparison; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, and the right picture (c) is modified silicon carbide after standing for 18 months;
FIG. 3 shows a comparative photograph of "silicon carbide raw powder, modified silicon carbide and their dispersion in water after standing for 18 months" of example 1; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, and the right picture (c) is modified silicon carbide after standing for 18 months;
FIG. 4 shows "silicon carbide raw powder, modified silicon carbide and SEM image contrast map thereof after standing for 18 months" of example 1; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, the right picture (c) is modified silicon carbide after standing for 18 months, and (d) is modified silicon carbide after 18 months of high power;
FIG. 5 shows a comparison graph of "raw powder of silicon carbide, modified silicon carbide and EDS thereof after standing for 18 months" of example 1; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, the right picture (c) is modified silicon carbide after standing for 18 months, and the right picture (d) is a selected area of the picture (c);
FIG. 6 shows "silicon carbide raw powder, modified silicon carbide and XRD contrast thereof after standing for 18 months" of example 1; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, and the right picture (c) is modified silicon carbide after standing for 18 months;
FIG. 7 is a graph showing a comparison of "silicon carbide raw powder, modified silicon carbide and contact angle thereof after standing for 18 months" of example 1; wherein, the left picture (a) is silicon carbide raw powder, the middle picture (b) is modified silicon carbide, and the right picture (c) is modified silicon carbide after standing for 18 months.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to the following examples and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
Step one, (SiC)PSurface pretreatment
Will (SiC)PPutting the mixture into a resistance furnace, heating the mixture to 1200 ℃, and preserving the heat for 2 hours to carry out oxidation etching treatment. Taking 5g of the sample after oxidation etching, adding the sample into 200ml of mixed solution of HF, HCl and distilled water in a volume ratio of 1:1:10, and carrying out hydrophilic treatment for 20 minutes at room temperature; then the hydrophilic treated (SiC)PAdding 1.0 mol.L to 200ml-1 TiCl3、1.5 g · L-1 PdCl2Activating for 30 minutes at room temperature in an HCl mixed solution;
step two, preparation of deposition solution
Weighing 60 g.L of nickel carbonate-115 g.L of sodium molybdate-1Sodium pyrophosphate 15 g.L-1 Boric acid 8 g.L-12.4 mg. L of rare earth-124 g.L of sodium hypophosphite-10.3 mg.L stabilizer-1Dissolving in distilled water to prepare 1L solution, and adjusting pH to 7.5 with ammonia water;
step three, preparation of the super-hydrophobic film layer
After pretreatment (SiC)PPreparing slurry by using distilled water as a solvent; wherein， (SiC)PMass ratio to distilled water: 1:12. After ultrasonic dispersion, adding the slurry into chemical deposition liquid under the conditions of normal pressure and normal temperature, wherein the volume ratio of the slurry to the deposition liquid is 1: stirring at 40 deg.C and pH 7.5, depositing for 2 hr, filtering, washing and drying. Will prepare (SiC)PPackaging in bags, and standing for 18 months.
Test method
Observing the micro morphology of the hydrophobic membrane by using a VEGA3 XMU type scanning electron microscope, and analyzing the element composition of the membrane layer by using an energy spectrometer; qualitatively analyzing the phase of the hydrophobic membrane by using an Shimadzu XRD-6100X-ray diffractometer; the contact angle of the hydrophobic membrane is tested by adopting a JCY series contact angle measuring instrument, the contact angle measuring instrument uses a digital camera, the highest resolution is 1280 multiplied by 1024, the frame frequency is 15-45/second, and simultaneously a micro-sampling device is adopted for sampling, and the highest injection precision can reach 0.005 mu l.
Test results
After surface modification (SiC)PThe appearance and the property of the material are greatly changed, the appearance color is changed from grey white to grey black, the material is mixed with water to form turbid liquid, the density of the turbid liquid is higher than that of the water, and the turbid liquid is settled at the bottom of a beaker after standing. The color remained grey-black after standing for 18 months, but when the particles were put into the water solution, the particles floated on the water surface and automatically dispersed to form a film [ FIG. 1 is a photograph of silicon carbide raw powder (a), modified silicon carbide (b) and water-soluble substance (c) after standing for 18 months](ii) a After magnetic rapid stirring and mixing, the mixture still had distinct layering with the aqueous solution as shown in FIG. 2 [ FIG. 2 is a photograph showing a comparison of the original powder of silicon carbide (a), the modified silicon carbide (b) and the actual photographs thereof after standing for 18 months (c) under magnetic stirring]. After the stirring is stopped, the particles spontaneously gather on the liquid surface again to form a hydrophobic film layer, as shown in fig. 3.
FIG. 4 is a SEM comparison of raw silicon carbide powder (a), modified silicon carbide powder (b) and its rest 18 months later (c), and it can be seen that the raw powder silicon carbide surface is smooth, and the deposits are crumbs generated in the crushing process and have different shapes; a new layer of substance is deposited on the surface of the modified silicon carbide, the coating is relatively flat, and the crushing is not obvious; after standing for 18 months, cellular micro-nano structures with different sizes are formed on the surface of the silicon carbide. FIG. 5 is a comparison of EDS of silicon carbide raw powder (a), modified silicon carbide (b) and its (c) after standing for 18 months. The observation shows that the EDS spectrum of the raw powder silicon carbide is mainly a Si peak, and the Ni peak content is zero; the EDS spectrum of the modified silicon carbide shows an obvious Ni peak; the EDS spectrum of the silicon carbide still shows obvious Ni peak after standing for 18 months.
FIG. 6 is a XRD comparison of silicon carbide raw powder (a), modified silicon carbide (b) and its (c) after standing for 18 months. As can be seen from FIG. 6, the raw powder silicon carbide isαSilicon carbide, XRD only observes silicon carbide phases; XRD of modified silicon carbide is 2θ=45 DEG has obvious Ni characteristic diffraction peak; XRD of silicon carbide after standing for 18 months is 2θAnd the diffraction peak of Ni is obvious when the angle is 45 degrees. Fig. 7 is a comparison of contact angle tests of silicon carbide raw powder (a), modified silicon carbide (b) and silicon carbide (c) after standing for 18 months, and the results show that the silicon carbide raw powder and the modified silicon carbide have no hydrophobicity, the static water contact angle of the silicon carbide after standing for 18 months is 156 degrees, the rolling angle is 5 degrees, good superhydrophobicity is shown, and the silicon carbide can be stored for more than 3 months.
Example 2
Step one, (SiC)PSurface pretreatment
Will (SiC)PPutting the mixture into a resistance furnace, heating the mixture to 1000 ℃, and preserving heat for 3 hours for oxidation etching treatment. Taking 7g of the sample after oxidation etching, adding the sample into 300ml of mixed solution of HF, HCl and distilled water in a volume ratio of 1:1:12, and carrying out hydrophilic treatment for 25 minutes at room temperature; then the hydrophilic treated (SiC)P300ml of 0.8 mol. L was added-1TiCl3、1.0 g·L- 1PdCl2Activating for 35 minutes at room temperature in an HCl mixed solution;
step two, preparation of deposition solution
Weighing 70 g.L of nickel carbonate-118 g.L of sodium molybdate-1Sodium pyrophosphate 16 g.L-1Boric acid 6 g.L-12.6 mg. L of rare earth-126 g.L of sodium hypophosphite-10.5 mg.L stabilizer-1Dissolving in distilled water to prepare 1L solution, and adjusting pH to 8.0 with ammonia water;
step three, preparation of the super-hydrophobic film layer
After pretreatment (SiC)PDistilled water as solventPreparing slurry; wherein, (SiC)PMass ratio to distilled water: 1:14. After ultrasonic dispersion, adding the slurry into chemical deposition liquid under the conditions of normal pressure and normal temperature, wherein the volume ratio of the slurry to the deposition liquid is 1: 15, stirring, reacting at 45 ℃ and pH value of 8.0, depositing for 2 hours, filtering, cleaning and drying. Will prepare (SiC)PPackaging in bags, and standing for 15 months.
Test method
Observing the micro morphology of the hydrophobic membrane by using a VEGA3 XMU type scanning electron microscope, and analyzing the element composition of the membrane layer by using an energy spectrometer; qualitatively analyzing the phase of the hydrophobic membrane by using an Shimadzu XRD-6100X-ray diffractometer; the contact angle of the hydrophobic membrane is tested by adopting a JCY series contact angle measuring instrument, the contact angle measuring instrument uses a digital camera, the highest resolution is 1280 multiplied by 1024, the frame frequency is 15-45/second, and simultaneously a micro-sampling device is adopted for sampling, and the highest injection precision can reach 0.005 mu l.
Test results
After surface modification (SiC)PThe appearance and the property are greatly changed, the appearance color is changed from grey white to grey black, the grey black is mixed with water to form turbid liquid, the density is higher than that of the water, and the turbid liquid is settled at the bottom of a beaker after standing. After being placed for 15 months, the color is still grey black, but when the water-based organic silicon gel is placed in the water solution, the particles float on the water surface and automatically disperse to form a film, the film forming effect is the same as that shown in figure 1, and after the magnetic force is rapidly stirred and mixed, the particles still have obvious layering with the water solution, and the layering effect is the same as that shown in figure 2. After stirring is stopped, the particles spontaneously gather on the liquid surface again to form a hydrophobic membrane layer, and the same hydrophobic membrane layer effect as that of the figure 3 is shown. The contrast observation of the silicon carbide raw powder, the modified silicon carbide and SEM of the silicon carbide raw powder and the modified silicon carbide after standing for 15 months shows that the silicon carbide surface of the raw powder is smooth, the sediment is crushed powder generated in the crushing process, and the shapes of the sediment are different; a new layer of substance is deposited on the surface of the modified silicon carbide, the coating is relatively flat, and the crushing is not obvious; after standing for 15 months, cellular micro-nano structures with different sizes are formed on the surface of the silicon carbide. The comparison of the silicon carbide raw powder, the modified silicon carbide and the EDS (ethylene diamine tetraacetic acid) after the silicon carbide raw powder and the modified silicon carbide are kept still for 15 months shows that the silicon carbide raw powder mainly shows a Si peak and has no Ni peak; the EDS spectrum of the modified silicon carbide shows an obvious Ni peak; EDS spectra of silicon carbide after 15 months of standingA significant Ni peak still appears. The comparison of XRD (X-ray diffraction) of the silicon carbide raw powder, the modified silicon carbide and the silicon carbide after standing for 15 months shows that the silicon carbide raw powder is silicon carbideαSilicon carbide, only the silicon carbide diffraction peaks are observed; modified silicon carbide is in 2θ=45 DEG has obvious Ni characteristic diffraction peak; of silicon carbide after 15 months of standing at 2θAnd the diffraction peak of Ni is obvious when the angle is 45 degrees. Contact angle tests show that the silicon carbide raw powder and the modified silicon carbide have no hydrophobicity, the static water contact angle of the modified silicon carbide is 152 degrees and the rolling angle is 8 degrees after the silicon carbide raw powder and the modified silicon carbide are kept for 15 months, the silicon carbide is good in super-hydrophobicity, and the silicon carbide can be stored for more than 3 months.
The above embodiments are only exemplary of the invention, and it should be noted that any simple variation, modification or other equivalent replacement by those skilled in the art without inventive work falls within the scope of the present invention without departing from the core of the present invention.

Claims (6)

1.一种具有荷叶效应的(SiC)P超疏水膜层的制备方法，其特征在于它是按照以下步骤进行的：1. a preparation method of (SiC) P super-hydrophobic film layer with lotus leaf effect is characterized in that it is carried out according to the following steps: 步骤一、(SiC)P前处理Step 1. (SiC) P pretreatment 利用电阻炉进行的氧化刻蚀处理，温度为900-1500℃，处理时间2-4小时；在体积比1:1:10-15 的HF、HCl、蒸馏水混合溶液中，室温下进行亲水性处理15-30分钟；然后在0.2-1.5mol· L-1 TiCl3、0.5-2.0 g·L-1 PdCl2、HCl混合溶液中，室温下进行活化处理20-40分钟；Oxidation etching treatment using a resistance furnace, the temperature is 900-1500 ° C, the treatment time is 2-4 hours; in a mixed solution of HF, HCl, and distilled water with a volume ratio of 1:1:10-15, the hydrophilicity is carried out at room temperature. Treat for 15-30 minutes; then in a mixed solution of 0.2-1.5mol·L -1 TiCl 3 , 0.5-2.0 g·L -1 PdCl 2 , and HCl, perform activation treatment at room temperature for 20-40 minutes; 步骤二、沉积液配制Step 2: Preparation of Sedimentation Liquid 依次添加氧化剂50~80g·L-1、促进剂10~20g·L-1、复活络合剂15~30g·L-1、稀土1.5~3.5mg·L-1、还原剂20~30g·L-1和稳定剂0.1~1.0 mg•L-1混合均匀后，调节pH值至7.0~8.5；Add oxidant 50~80g·L -1 , accelerator 10~20g·L -1 , resurrection complexing agent 15~30g·L -1 , rare earth 1.5~3.5mg·L -1 , reducing agent 20~30g·L -1 in turn After mixing -1 and stabilizer 0.1~1.0 mg•L -1 evenly, adjust the pH value to 7.0~8.5; 步骤三、超疏水膜层的制备Step 3. Preparation of superhydrophobic film layer 将步骤一前处理后的(SiC)P以蒸馏水为溶剂，配成浆液；其中， (SiC)P与蒸馏水的质量比：1:10~15；超声分散后加入到沉积液中，搅拌，加热至30℃-50℃后，在溶液pH值为7.0-8.5的条件下，沉积1-3小时，过滤，清洗，干燥，静置12个月以上，即完成所述的具有荷叶效应的(SiC)P超疏水膜层的制备。The (SiC) P after the pretreatment in step 1 is made into a slurry with distilled water as a solvent; wherein, the mass ratio of (SiC) P to distilled water: 1:10~15; after ultrasonic dispersion, it is added to the sedimentation solution, stirred, and heated. After reaching 30°C-50°C, under the condition that the pH value of the solution is 7.0-8.5, deposit for 1-3 hours, filter, wash, dry, and let stand for more than 12 months, that is, to complete the described solution with lotus leaf effect ( Preparation of SiC) P superhydrophobic films. 2.根据权利要求1所述的一种具有荷叶效应的(SiC)P超疏水膜层的制备方法，其特征在于所述的氧化剂为硫酸镍或氯化镍，促进剂为钼酸钠，复活络合剂为硼酸和焦磷酸钠，还原剂为次亚磷酸钠，稳定剂为硫脲或硝酸铅。2. the preparation method of a kind of (SiC) P super-hydrophobic film layer with lotus leaf effect according to claim 1, is characterized in that described oxidant is nickel sulfate or nickel chloride, and accelerator is sodium molybdate, The resurrection complexing agent is boric acid and sodium pyrophosphate, the reducing agent is sodium hypophosphite, and the stabilizer is thiourea or lead nitrate. 3.根据权利要求1所述的一种具有荷叶效应的(SiC)P超疏水膜层的制备方法，其特征在于所述的沉积液配制为：3. the preparation method of a kind of (SiC) P super-hydrophobic film layer with lotus leaf effect according to claim 1, is characterized in that described deposition liquid is formulated as: 依次添加硫酸镍50-80g·L-1、钼酸钠10~20g·L-1、焦磷酸钠10~20g·L-1、硼酸5-10g·L-1、稀土1.5-3.5mg·L-1、次亚磷酸钠20-30g·L-1和稳定剂0.1-1.0 mg•L-1混合均匀后，用氨水调节pH值至7.0-8.5。Add nickel sulfate 50-80g·L -1 , sodium molybdate 10~20g·L -1 , sodium pyrophosphate 10~20g·L -1 , boric acid 5-10g·L -1 , rare earth 1.5-3.5mg·L in turn -1 , 20-30g·L -1 of sodium hypophosphite and 0.1-1.0 mg·L -1 of stabilizer are mixed evenly, and the pH value is adjusted to 7.0-8.5 with ammonia water. 4.根据权利要求1所述的一种具有荷叶效应的(SiC)P超疏水膜层的制备方法，其特征在于步骤三中的浆液与沉积液的体积比为1：8~20。4. the preparation method of a kind of (SiC) P super-hydrophobic film layer with lotus leaf effect according to claim 1, is characterized in that the volume ratio of the slurry in step 3 and deposition liquid is 1:8～20. 5.根据权利要求1所述的一种具有荷叶效应的(SiC)P超疏水膜层的制备方法，其特征在于步骤三中所述的静置是在常温条件下进行的。5 . The method for preparing a (SiC) P superhydrophobic film layer with lotus leaf effect according to claim 1 , wherein the standing described in the step 3 is carried out under normal temperature conditions. 6 . 6.如权利要求1所制备一种具有荷叶效应的(SiC)P超疏水膜层，其特征在于静态水接触角为150-160°，滚动角小于10°。6. A (SiC) P superhydrophobic film layer with lotus leaf effect prepared as claimed in claim 1, characterized in that the static water contact angle is 150-160°, and the rolling angle is less than 10°.
CN202110256815.6A 2021-03-10 2021-03-10 A kind of (SiC) with lotus leaf effect P Preparation method of super-hydrophobic membrane layer Active CN112941494B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110256815.6A CN112941494B (en) 2021-03-10 2021-03-10 A kind of (SiC) with lotus leaf effect P Preparation method of super-hydrophobic membrane layer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110256815.6A CN112941494B (en) 2021-03-10 2021-03-10 A kind of (SiC) with lotus leaf effect P Preparation method of super-hydrophobic membrane layer

Publications (2)

Publication Number Publication Date
CN112941494A true CN112941494A (en) 2021-06-11
CN112941494B CN112941494B (en) 2022-08-30

Family

ID=76229030

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110256815.6A Active CN112941494B (en) 2021-03-10 2021-03-10 A kind of (SiC) with lotus leaf effect P Preparation method of super-hydrophobic membrane layer

Country Status (1)

Country Link
CN (1) CN112941494B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115318210A (en) * 2022-08-11 2022-11-11 宿辉 Preparation method and application of cobalt disulfide/porous carbon/silicon carbide aerogel composite material for electromagnetic shielding

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6167770A (en) * 1984-09-07 1986-04-07 Kizai Kk Plating method of magnesium and magnesium alloy
JPS6230885A (en) * 1985-04-01 1987-02-09 Nippon Chem Ind Co Ltd:The Manufacturing method of nickel plating material
CN101962761A (en) * 2010-11-04 2011-02-02 吉林大学 Preparation method of bionic hydrophobic coating on surface of magnesium alloy
CN102380470A (en) * 2011-11-09 2012-03-21 西北师范大学 Electrochemical deposition method for preparing super-hydrophobic and super-oleophilic surface
CN102877047A (en) * 2012-10-25 2013-01-16 武汉工程大学 Method for preparing super hydrophobic coating on copper or copper alloy net
CN105648490A (en) * 2016-01-07 2016-06-08 东南大学 Super-hydrophobic surface without modification of low surface energy matter and preparation method thereof
CN107502003A (en) * 2016-06-14 2017-12-22 中国科学院理化技术研究所 Preparation method of hydrophobic inorganic powder material
CN109518238A (en) * 2018-12-10 2019-03-26 南京航空航天大学 The method that metal surface prepares super-hydrophobic nickel carbon SiClx composite deposite

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6167770A (en) * 1984-09-07 1986-04-07 Kizai Kk Plating method of magnesium and magnesium alloy
JPS6230885A (en) * 1985-04-01 1987-02-09 Nippon Chem Ind Co Ltd:The Manufacturing method of nickel plating material
CN101962761A (en) * 2010-11-04 2011-02-02 吉林大学 Preparation method of bionic hydrophobic coating on surface of magnesium alloy
CN102380470A (en) * 2011-11-09 2012-03-21 西北师范大学 Electrochemical deposition method for preparing super-hydrophobic and super-oleophilic surface
CN102877047A (en) * 2012-10-25 2013-01-16 武汉工程大学 Method for preparing super hydrophobic coating on copper or copper alloy net
CN105648490A (en) * 2016-01-07 2016-06-08 东南大学 Super-hydrophobic surface without modification of low surface energy matter and preparation method thereof
CN107502003A (en) * 2016-06-14 2017-12-22 中国科学院理化技术研究所 Preparation method of hydrophobic inorganic powder material
CN109518238A (en) * 2018-12-10 2019-03-26 南京航空航天大学 The method that metal surface prepares super-hydrophobic nickel carbon SiClx composite deposite

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
北京市科学技术协会: "《新世纪 新科技 新北京》", 31 January 2002, 科学技术文献出版社 *
宿辉等: "纳米碳化硅表面修饰的工艺研究及结构表征", 《电镀与精饰》 *
黄拿灿等: "《稀土表面改性及其应用》", 30 July 2007, 国防工业出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115318210A (en) * 2022-08-11 2022-11-11 宿辉 Preparation method and application of cobalt disulfide/porous carbon/silicon carbide aerogel composite material for electromagnetic shielding
CN115318210B (en) * 2022-08-11 2024-04-02 宿辉 Preparation method and application of cobalt disulfide/porous carbon/silicon carbide airgel composite material for electromagnetic shielding

Also Published As

Publication number Publication date
CN112941494B (en) 2022-08-30

Similar Documents

Publication Publication Date Title
CN103938431B (en) The super-hydrophobic cloth adopting layered double-hydroxide to prepare and preparation technology thereof
CN104910656B (en) A kind of method that super-hydrophobic silica powder and super-hydrophobic coat are prepared with compound silicon source
Wang et al. In situ growth of hierarchical boehmite on 2024 aluminum alloy surface as superhydrophobic materials
CN111534162B (en) Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof
Jiang et al. Anti-corrosion and anti-fouling superhydrophobic silicone coating with continuous micro/nano structure
Zhao et al. A robust surface with superhydrophobicity and underwater superoleophobicity for on-demand oil/water separation
CN109289550A (en) A kind of preparation method and application of anti-pollution polyvinylidene fluoride hybrid ultrafiltration membrane
CN108610786B (en) A three-dimensional graphene-based superhydrophobic coating and its preparation method
CN110305580A (en) A kind of graphene-based hydrophobic anti-corrosion coating and its preparation method and application
CN110499073A (en) A method for preparing superhydrophobic coatings by using nanocellulose and nanoparticles as raw materials in aqueous solution without fluorine modifier modification
CN112941494A (en) A kind of (SiC) with lotus leaf effectPPreparation method of super-hydrophobic membrane layer
CN105885611A (en) Polymer metallic copper anticorrosive coating and preparation method thereof
CN103524779A (en) Cuprous oxide/ion exchange resin composite and preparation method thereof
KR20070112772A (en) Manufacturing Method of Titanium Film Coating Resin Substrate
JP7513339B1 (en) Method for producing alkaline red mud coatings to prevent marine biofouling
CN109251635A (en) A kind of modified meerschaum cladding titanium nanometer anticorrosive paint and preparation method thereof
CN106047030A (en) Resin-based metal copper anticorrosion coating and preparation method thereof
CN114539885B (en) Special high-penetration moisture-curing sealing primer for concrete and its preparation method and application
CN114806326B (en) Preparation method of nitrogen-containing carbon quantum dot/polyaniline modified epoxy anticorrosive paint
EP1925590A1 (en) Light-resistant titanic acid coating film and resin bases with the coating film
Sun et al. Construction of a hydrophobic composite coating with waterborne acrylic resin and flower-shaped ZnO
CN114276751A (en) Preparation method and application of substrate-unlimited super-hydrophobic coating
CN113230909A (en) Preparation method of super-amphiphilic cellulose nitrate film
Wu et al. Study on corrosion resistance of superhydrophobic surface on aluminum alloy
CN113684476A (en) Method for preparing ZnAl-LDHs film on surface of titanium alloy

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Su Hui

Inventor after: Liu Ying

Inventor after: Luan Bairui

Inventor before: Su Hui

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20221116

Address after: 150050, Hongqi Avenue, Daowai District, Heilongjiang, Harbin province 999

Patentee after: HEILONGJIANG INSTITUTE OF TECHNOLOGY

Address before: 150050 701, building 6, Jiajia District, 234 Dongzhi Road, Daowai District, Harbin City, Heilongjiang Province

Patentee before: Su Hui