CN110105871A - A kind of preparation method pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material - Google Patents

A kind of preparation method pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material Download PDF

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CN110105871A
CN110105871A CN201910483390.5A CN201910483390A CN110105871A CN 110105871 A CN110105871 A CN 110105871A CN 201910483390 A CN201910483390 A CN 201910483390A CN 110105871 A CN110105871 A CN 110105871A
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thermal
coating
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preparation
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CN110105871B (en
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王成毓
王蒙
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Northeast Forestry University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254After-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/56Three layers or more
    • B05D7/58No clear coat specified
    • B05D7/584No clear coat specified at least some layers being let to dry, at least partially, before applying the next layer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00Other type of polymers
    • B05D2518/10Silicon-containing polymers
    • B05D2518/12Ceramic precursors (polysiloxanes, polysilazanes)
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

A kind of preparation method pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material, the present invention relates to a kind of preparation methods of super-hydrophobic photo-thermal suppression ice coating.Solve the problem of existing suppression ice material result it is single can not reach simultaneously prevent freeze and freeze after can efficient deicing.Preparation method: one, solar energy optical-thermal powder is prepared;Two, nanoparticles solution is prepared;Three, solar heat matrix is prepared;Four, it sprays, obtains super-hydrophobic photo-thermal suppression ice coating.Preparation of the present invention for super-hydrophobic photo-thermal suppression ice coating.

Description

It is a kind of to press down using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material The preparation method of ice coating
Technical field
The present invention relates to a kind of preparation methods of super-hydrophobic photo-thermal suppression ice coating.
Background technique
With the deterioration of global climate and the destruction of environment, the natural phenomena of icing certain fields of human society gradually Develop into a problem, the formation of ice and snow often produces transportation, transmission line of electricity, aircraft, building and communal facility etc. Raw tremendous influence.Therefore, new deicing, anti-icing system are researched and developed, avoid ice disaster caused by human society Harm is of great significance.Wherein, the material for being related to pressing down ice is broadly divided into active deicing and passive deicing material, and every kind of material Expect single effect, can not reach simultaneously prevent freeze and freeze after can efficiently deicing technical effect.
Summary of the invention
The invention solves existing suppression ice material result is single, can not reach simultaneously prevents from freezing and can efficiently remove after freezing The problem of ice, and a kind of system for pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material is provided Preparation Method.
A kind of preparation method pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material, It is to sequentially include the following steps:
One, solar energy optical-thermal powder is prepared:
Nine water ferric nitrates, nitrate trihydrate copper, tetrahydrate manganese chloride and water are mixed, mixed solution is obtained, then by quality hundred The sodium hydroxide solution that score is 3%~8% is instilled in container simultaneously and is stirred with mixed solution, obtains mixture, and be added dropwise It is 10.5~11.5 that process control rate of addition, which keeps mixture pH, then mixture is stood 1h~4h at room temperature, discarded Supernatant simultaneously filters, and is precipitated, and under conditions of temperature is 50 DEG C~120 DEG C, will precipitate dry 1h~3h, then grinds, Finally with heating rate for 5 DEG C/min~20 DEG C/min, temperature is warming up to 600 DEG C~800 DEG C, and temperature be 600 DEG C~ Under 800 DEG C and air atmosphere, 1h~2h is calcined, solar energy optical-thermal powder is obtained;
The quality of the nine water ferric nitrates and the volume ratio of water are 1g:(10~20) mL;In the nine water ferric nitrates Iron ion and nitrate trihydrate copper in copper ion molar ratio be 1:(0.9~2);Iron ion in the nine water ferric nitrates Molar ratio with the manganese ion in tetrahydrate manganese chloride is 1:(0.9~2);The hydroxide that the mass percent is 3%~8% Hydroxyl molal quantity in sodium solution is identical as the anion mol number in mixed solution;
Two, nanoparticles solution is prepared:
By gas phase SiO2Nano particle is added in hexamethylene, obtains gas phase SiO2Nanoparticles solution, by gas phase SiO2It receives Rice grain solution ultrasonic disperse 5min~30min, obtains uniform SiO2Suspension, under room temperature and stirring condition, by 16 Alkyl trimethoxysilane and glacial acetic acid are added dropwise to uniform SiO2In suspension, stirs 1 day~2 days, obtain nanometer Grain solution;
The gas phase SiO2The concentration of nanoparticles solution is 5mg/mL~25mg/mL;The gas phase SiO2Nanometer The mass ratio of grain and hexadecyl trimethoxy silane is 1:(2~4);The gas phase SiO2The matter of nano particle and glacial acetic acid Amount is than being 1:(0.5~1);
Three, solar heat matrix is prepared:
The curing agent of solar energy optical-thermal powder, dimethyl silicone polymer and dimethyl silicone polymer is mixed, then in ball 1h~3h is ground in grinding machine, obtains coating, and under conditions of being 100 μm~600 μm with coating thickness, coating is coated in substrate On, obtain solar heat matrix;
The mass ratio of the solar energy optical-thermal powder and dimethyl silicone polymer is 1:(5~15);
Four, it sprays:
1., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, 15 layers~50 layers nanoparticle coating are sprayed in solar heat substrate upper surface, are then 100 DEG C in temperature Under conditions of~135 DEG C, 10min~20min is heated, obtains the matrix after spraying for the first time;
2., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, the substrate upper surface after first time sprays continues to spray 15 layers~50 layers nanoparticle coating, then exists Under conditions of temperature is 100 DEG C~135 DEG C, 20min~30min, the matrix after obtaining second of spraying are heated;
3., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, the substrate upper surface after spraying at second continues to spray 15 layers~50 layers nanoparticle coating, then exists Under conditions of temperature is 100 DEG C~135 DEG C, 30min~50min is heated, obtains the matrix after third time sprays;
4., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, the substrate upper surface after third time sprays continues to spray 15 layers~50 layers nanoparticle coating, then exists Under conditions of temperature is 100 DEG C~135 DEG C, solidify 1h~3h, obtains super-hydrophobic photo-thermal suppression ice coating.
Principle: single super hydrophobic surface is unable to reach excellent super-hydrophobic effect under high humidity, cryogenic conditions, but utilizes The temperature that solar energy improves modified surface is a kind of method for effectively improving suppression ice performance.First by the nanoparticles solution of preparation It is implanted in solar heat matrix, photo-thermal substrate is made to reach super-hydrophobic effect, assign its passive anti-icing performance.Simultaneously in sunlight Under (or simulation sunlight) irradiation, surface temperature is increased using photothermal conversion effect, assigns coating active deicing by thermal compensation Performance, to reach good suppression ice effect.
The beneficial effects of the present invention are:
The present invention is using iron copper manganese Metal salt and silica as raw material, the super-hydrophobic photo-thermal suppression ice coating being prepared, tool There is the features such as economic cost is low, preparation process is simple, with short production cycle, photo-thermal effect is good, is a kind of novel suppression ice material.
1, use metal salt and silica as raw material, there are rich reserves, it is cheap and easy to get and environmental-friendly, easily In recycling the features such as.
2, the photo-thermal super hydrophobic composite coating that the present invention is prepared, the contact angle with water are 157 °, and roll angle is 2 °; In -15 DEG C of low temperature environments and certain Power Xenon Light (400mW/cm2) under irradiation, coating shows excellent super-hydrophobicity, heating Amplitude keeps stable up to 40 DEG C or more, to reach suppression ice effect;It is 2000mW/cm using power in room temperature2Xenon lamp, It adjusts the distance the super-hydrophobic photo-thermal suppression ice coating irradiation of xenon lamp 10cm, 185 DEG C can be warming up in the time of 180s, there is good liter Temp effect;For the super-hydrophobic photo-thermal suppression ice coating coating of preparation in simulation sleet experiment in 25 minutes, surface does not form ice crystal, It can achieve complete suppression ice effect under xenon lamp irradiation;Coating is under xenon lamp irradiation to the adhesion strength of ice down to 2.1KPa.
3, the photo-thermal super hydrophobic composite coating that the present invention is prepared can be widely applied to building appearance, industrial production Anti-icing, pipeline suppression ice etc..
4, the method for the present invention feasibility is high, and operating procedure is simple, and capital investment is few, and short preparation period, reaction condition is mild, Large-scale instrument and equipment is not needed, large-scale industrial production processing may be implemented, there is very broad application prospect, can be used as The suppression ice coating of building or certain particular surfaces.
The present invention presses down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material for a kind of Preparation method.
Detailed description of the invention
Fig. 1 is the photo in kind that super-hydrophobic photo-thermal prepared by embodiment one presses down ice coating;
Fig. 2 is that super-hydrophobic photo-thermal prepared by embodiment one presses down the electromicroscopic photograph that ice coating amplifies 50000 times;
Fig. 3 is that super-hydrophobic photo-thermal prepared by embodiment one presses down the electromicroscopic photograph that ice coating amplifies 100000 times;
Fig. 4 is the electromicroscopic photograph that the solar energy optical-thermal powder of one step 1 of embodiment preparation amplifies 60000 times;
Fig. 5 is the electromicroscopic photograph that the solar energy optical-thermal powder of one step 1 of embodiment preparation amplifies 80000 times;
Fig. 6 is the X-ray diffraction spectrogram of the solar energy optical-thermal powder of one step 1 of embodiment preparation;
Fig. 7 is the contact angle photo that super-hydrophobic photo-thermal prepared by embodiment one presses down ice coating and water;
Fig. 8 is that super-hydrophobic photo-thermal prepared by embodiment one presses down heating curve of the ice coating under xenon lamp irradiation;
Fig. 9 is the ice condition figure that aluminium sheet continues simulation sleet experiment in 25 minutes at low temperature;
Figure 10 is that super-hydrophobic photo-thermal suppression ice coating prepared by embodiment one continues simulation sleet experiment in 25 minutes at low temperature Ice condition figure.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of using iron copper manganese Metal salt and nano silica as the super thin of raw material Water photo-thermal presses down the preparation method of ice coating, it is to sequentially include the following steps:
One, solar energy optical-thermal powder is prepared:
Nine water ferric nitrates, nitrate trihydrate copper, tetrahydrate manganese chloride and water are mixed, mixed solution is obtained, then by quality hundred The sodium hydroxide solution that score is 3%~8% is instilled in container simultaneously and is stirred with mixed solution, obtains mixture, and be added dropwise It is 10.5~11.5 that process control rate of addition, which keeps mixture pH, then mixture is stood 1h~4h at room temperature, discarded Supernatant simultaneously filters, and is precipitated, and under conditions of temperature is 50 DEG C~120 DEG C, will precipitate dry 1h~3h, then grinds, Finally with heating rate for 5 DEG C/min~20 DEG C/min, temperature is warming up to 600 DEG C~800 DEG C, and temperature be 600 DEG C~ Under 800 DEG C and air atmosphere, 1h~2h is calcined, solar energy optical-thermal powder is obtained;
The quality of the nine water ferric nitrates and the volume ratio of water are 1g:(10~20) mL;In the nine water ferric nitrates Iron ion and nitrate trihydrate copper in copper ion molar ratio be 1:(0.9~2);Iron ion in the nine water ferric nitrates Molar ratio with the manganese ion in tetrahydrate manganese chloride is 1:(0.9~2);The hydroxide that the mass percent is 3%~8% Hydroxyl molal quantity in sodium solution is identical as the anion mol number in mixed solution;
Two, nanoparticles solution is prepared:
By gas phase SiO2Nano particle is added in hexamethylene, obtains gas phase SiO2Nanoparticles solution, by gas phase SiO2It receives Rice grain solution ultrasonic disperse 5min~30min, obtains uniform SiO2Suspension, under room temperature and stirring condition, by 16 Alkyl trimethoxysilane and glacial acetic acid are added dropwise to uniform SiO2In suspension, stirs 1 day~2 days, obtain nanometer Grain solution;
The gas phase SiO2The concentration of nanoparticles solution is 5mg/mL~25mg/mL;The gas phase SiO2Nanometer The mass ratio of grain and hexadecyl trimethoxy silane is 1:(2~4);The gas phase SiO2The matter of nano particle and glacial acetic acid Amount is than being 1:(0.5~1);
Three, solar heat matrix is prepared:
The curing agent of solar energy optical-thermal powder, dimethyl silicone polymer and dimethyl silicone polymer is mixed, then in ball 1h~3h is ground in grinding machine, obtains coating, and under conditions of being 100 μm~600 μm with coating thickness, coating is coated in substrate On, obtain solar heat matrix;
The mass ratio of the solar energy optical-thermal powder and dimethyl silicone polymer is 1:(5~15);
Four, it sprays:
1., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, 15 layers~50 layers nanoparticle coating are sprayed in solar heat substrate upper surface, are then 100 DEG C in temperature Under conditions of~135 DEG C, 10min~20min is heated, obtains the matrix after spraying for the first time;
2., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, the substrate upper surface after first time sprays continues to spray 15 layers~50 layers nanoparticle coating, then exists Under conditions of temperature is 100 DEG C~135 DEG C, 20min~30min, the matrix after obtaining second of spraying are heated;
3., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, the substrate upper surface after spraying at second continues to spray 15 layers~50 layers nanoparticle coating, then exists Under conditions of temperature is 100 DEG C~135 DEG C, 30min~50min is heated, obtains the matrix after third time sprays;
4., using nanoparticles solution as spray coating liquor, spray gun air pressure be 0.4MPa~0.7MPa and distance be 15cm~ Under conditions of 20cm, the substrate upper surface after third time sprays continues to spray 15 layers~50 layers nanoparticle coating, then exists Under conditions of temperature is 100 DEG C~135 DEG C, solidify 1h~3h, obtains super-hydrophobic photo-thermal suppression ice coating.
The beneficial effect of present embodiment is:
For present embodiment using iron copper manganese Metal salt and silica as raw material, the super-hydrophobic photo-thermal being prepared presses down ice Coating has the characteristics that economic cost is low, preparation process is simple, with short production cycle, photo-thermal effect is good, is a kind of novel suppression Ice material.
1, use metal salt and silica as raw material, there are rich reserves, it is cheap and easy to get and environmental-friendly, easily In recycling the features such as.
2, the photo-thermal super hydrophobic composite coating that present embodiment is prepared, the contact angle with water are 157 °, are rolled Angle is 2 °;In -15 DEG C of low temperature environments and certain Power Xenon Light (400mW/cm2) under irradiation, coating shows excellent super-hydrophobic Property, increasing extent of temperature keeps stable up to 40 DEG C or more, to reach suppression ice effect;It is 2000mW/cm using power in room temperature2 Xenon lamp, the super-hydrophobic photo-thermal suppression ice coating irradiation for the xenon lamp 10cm that adjusts the distance can be warming up to 185 DEG C in the time of 180s, have Good temperature rise effect;In simulation sleet experiment in 25 minutes, surface does not have the super-hydrophobic photo-thermal suppression ice coating coating of preparation Ice crystal is formed, can achieve complete suppression ice effect under xenon lamp irradiation;Coating under xenon lamp irradiation to the adhesion strength of ice down to 2.1KPa。
3, the photo-thermal super hydrophobic composite coating that present embodiment is prepared, can be widely applied to building appearance, Industrial production is anti-icing, pipeline presses down ice etc..
4, present embodiment method feasibility is high, and operating procedure is simple, and capital investment is few, short preparation period, reaction Mild condition does not need large-scale instrument and equipment, and large-scale industrial production processing may be implemented, have before being widely applied very much Scape can be used as the suppression ice coating of building or certain particular surfaces.
Specific embodiment 2: the present embodiment is different from the first embodiment in that: gas phase described in step 2 SiO2The average grain diameter of nano particle is 200nm~300nm.It is other same as the specific embodiment one.
Specific embodiment 3: unlike one of present embodiment and specific embodiment one or two: institute in step 3 The mass ratio of the curing agent of the dimethyl silicone polymer and dimethyl silicone polymer stated is 10:1.Other and specific embodiment one Or two is identical.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: in step 1 Under conditions of temperature is 80 DEG C~120 DEG C, dry 1.5h~3h will be precipitated, then ground, finally with heating rate be 10 DEG C/ Temperature is warming up to 700 DEG C~800 DEG C, and in the case where temperature is 700 DEG C~800 DEG C and air atmosphere, forged by min~20 DEG C/min 1h~2h is burnt, solar energy optical-thermal powder is obtained.It is other identical as specific embodiment one to three.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: institute in step 1 The quality for the nine water ferric nitrates stated and the volume ratio of water are 1g:(16~20) mL;In nine water ferric nitrate described in step 1 The molar ratio of copper ion in iron ion and nitrate trihydrate copper is 1:(1~2);Iron in nine water ferric nitrate described in step 1 The molar ratio of manganese ion in ion and tetrahydrate manganese chloride is 1:(1~2).It is other identical as specific embodiment one to four.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: institute in step 2 The gas phase SiO stated2The concentration of nanoparticles solution is 7mg/mL~25mg/mL;Gas phase SiO described in step 22Nano particle Mass ratio with hexadecyl trimethoxy silane is 1:(2~3.5);Gas phase SiO described in step 22Nano particle and ice The mass ratio of acetic acid is 1:(0.6~1).It is other identical as specific embodiment one or five.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: will in step 3 The curing agent of solar energy optical-thermal powder, dimethyl silicone polymer and dimethyl silicone polymer mixes, and then grinds in the ball mill 1h~2h obtains coating, under conditions of being 200 μm~600 μm with coating thickness, coating is coated in substrate, the sun is obtained It can hot radical matter.It is other identical as specific embodiment one to six.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: institute in step 3 The mass ratio of the solar energy optical-thermal powder and dimethyl silicone polymer stated is 1:(9~15).It is other with specific embodiment one to Seven is identical.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: will in step 2 Gas phase SiO2Nano particle is added in hexamethylene, obtains gas phase SiO2Nanoparticles solution, by gas phase SiO2Nanoparticles solution Ultrasonic disperse 5min~20min obtains uniform SiO2Suspension, under room temperature and stirring condition, by cetyl trimethoxy Base silane and glacial acetic acid are added dropwise to uniform SiO2In suspension, stirs 1 day~1.5 days, obtain nanoparticles solution.Its It is identical as specific embodiment one to eight.
Specific embodiment 10: unlike one of present embodiment and specific embodiment one to nine: step 4 1. in Heat 10min;Step 4 is 2. middle to heat 20min;Step 4 is 3. middle to heat 30min;Step 4 is 4. middle to solidify 1.5h.Other and tool Body embodiment one to nine is identical.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one:
A kind of preparation method pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material It is to sequentially include the following steps:
One, solar energy optical-thermal powder is prepared:
Nine water ferric nitrates, nitrate trihydrate copper, tetrahydrate manganese chloride and water are mixed, mixed solution is obtained, then by quality hundred The sodium hydroxide solution that score is 4.2% is instilled in container simultaneously and is stirred with mixed solution, obtains mixture, and process is added dropwise Controlling rate of addition and keeping mixture pH is 11, then mixture is stood 3h at room temperature, discards supernatant liquid and filter, obtain Precipitating will precipitate dry 1.5h, then grind under conditions of temperature is 80 DEG C, will finally with heating rate for 10 DEG C/min Temperature is warming up to 800 DEG C, and in the case where temperature is 800 DEG C and air atmosphere, calcines 1h, obtain solar energy optical-thermal powder;
The quality of the nine water ferric nitrates and the volume ratio of water are 1g:16.5mL;Iron in the nine water ferric nitrates The molar ratio of copper ion in ion and nitrate trihydrate copper is 1:1;Iron ion and four water chlorinations in the nine water ferric nitrates The molar ratio of manganese ion in manganese is 1:1;The hydroxyl mole in sodium hydroxide solution that the mass percent is 4.2% Number is identical as the anion mol number in mixed solution;
Two, nanoparticles solution is prepared:
By gas phase SiO2Nano particle is added in hexamethylene, obtains gas phase SiO2Nanoparticles solution, by gas phase SiO2It receives Rice grain solution ultrasonic disperse 20min, obtains uniform SiO2Suspension, under room temperature and stirring condition, by cetyl three Methoxy silane and glacial acetic acid are added dropwise to uniform SiO2In suspension, stirs 1 day, obtain nanoparticles solution;
The gas phase SiO2The concentration of nanoparticles solution is 7mg/mL;The gas phase SiO2Nano particle and 16 The mass ratio of alkyl trimethoxysilane is 1:3.5;The gas phase SiO2The mass ratio of nano particle and glacial acetic acid is 1: 0.6;
Three, solar heat matrix is prepared:
The curing agent of solar energy optical-thermal powder, dimethyl silicone polymer and dimethyl silicone polymer is mixed, then in ball 1h is ground in grinding machine, obtains coating, under conditions of being 200 μm with coating thickness, coating is coated in substrate, solar energy is obtained Hot radical matter;
The mass ratio of the solar energy optical-thermal powder and dimethyl silicone polymer is 1:9;The substrate is aluminium sheet;
Four, it sprays:
1., using nanoparticles solution as spray coating liquor, under conditions of spray gun air pressure is 0.6MPa and distance is 15cm, too The positive hot substrate upper surface of energy sprays 40 layers of nanoparticle coating, then under conditions of temperature is 100 DEG C, heats 10min, obtains Matrix after spraying for the first time;
2., using nanoparticles solution as spray coating liquor, under conditions of spray gun air pressure is 0.6MPa and distance is 15cm, Substrate upper surface after primary spraying continues to spray 40 layers of nanoparticle coating, then under conditions of temperature is 100 DEG C, heating 20min, the matrix after obtaining second of spraying;
3., using nanoparticles solution as spray coating liquor, under conditions of spray gun air pressure is 0.6MPa and distance is 15cm, Substrate upper surface after secondary spraying continues to spray 40 layers of nanoparticle coating, then under conditions of temperature is 100 DEG C, heating 30min obtains the matrix after third time sprays;
4., using nanoparticles solution as spray coating liquor, under conditions of spray gun air pressure is 0.6MPa and distance is 15cm, Substrate upper surface after spraying three times continues to spray 40 layers of nanoparticle coating, then under conditions of temperature is 100 DEG C, solidification 1.5h obtains super-hydrophobic photo-thermal suppression ice coating;
Gas phase SiO described in step 22The average grain diameter of nano particle is 200nm~300nm;
Dimethyl silicone polymer described in step 3 is DOW CORNING 184;Dimethyl silicone polymer described in step 3 Curing agent be 184 curing agent of DOW CORNING;The solidification of dimethyl silicone polymer described in step 3 and dimethyl silicone polymer The mass ratio of agent is 10:1.
Spray gun in step 4 is Taiwan Pola 116A.
Fig. 1 is the photo in kind that super-hydrophobic photo-thermal prepared by embodiment one presses down ice coating;As seen from the figure, attached on fast black base bottom One layer of translucent powdery white coating, illustrate nanoparticle successful deposition in photo-thermal substrate.
Fig. 2 is that super-hydrophobic photo-thermal prepared by embodiment one presses down the electromicroscopic photograph that ice coating amplifies 50000 times;Fig. 3 is to implement Super-hydrophobic photo-thermal suppression ice coating prepared by example one amplifies 100000 times of electromicroscopic photograph;As seen from the figure, super-hydrophobic photo-thermal suppression ice applies Layer surface has good micro-nano structure.The average grain diameter of single nanoparticle is 30nm~40nm, due to being added to hexadecane Base trimethoxy silane is cross-linked with each other between particle, to construct higher surface roughness.
Fig. 4 is the electromicroscopic photograph that the solar energy optical-thermal powder of one step 1 of embodiment preparation amplifies 60000 times;Fig. 5 is real The solar energy optical-thermal powder for applying the preparation of one step 1 of example amplifies 80000 times of electromicroscopic photograph;It can be seen that solar energy optical-thermal powder Partial size average out to 80nm~100nm, it was demonstrated that powder made from present implementation has reached nano-scale particle size, to possess bigger Specific surface area so that photothermal conversion efficiency is higher.
Fig. 6 is the X-ray diffraction spectrogram of the solar energy optical-thermal powder of one step 1 of embodiment preparation;The present embodiment method can Purer iron copper manganese ternary metal oxide is prepared, the crystal form of powder is cubic spinel type.
Fig. 7 is the contact angle photo that super-hydrophobic photo-thermal prepared by embodiment one presses down ice coating and water;It is manufactured in the present embodiment Super-hydrophobic photo-thermal suppression ice coating is 157 ° to the contact angle of water, and it is super-hydrophobic that spherical shape, which is presented, in water droplet on sample.And it is contacting It is 2 ° that roll angle is measured in the experimentation of angle.
It is 2000mW/cm using power in room temperature2Xenon lamp, the super-hydrophobic photo-thermal of the xenon lamp 10cm that adjusts the distance presses down ice coating 180s is irradiated, test xenon lamp irradiates the ramp case of super-hydrophobic photo-thermal suppression ice coating, as shown in Figure 8.Fig. 8 is the preparation of embodiment one Super-hydrophobic photo-thermal suppression ice coating xenon lamp irradiation under heating curve;As seen from the figure, the photo-thermal powder of present embodiment preparation It can be warming up to 185 DEG C in the time of 180s, there is good temperature rise effect.
The simulated experiment of photo-thermal sleet is carried out to super-hydrophobic photo-thermal suppression ice coating: making row's drip nozzle, injection with 5 syringes Device is connect with deionized water container, and control water droplet sinking speed is about 2.1m/s, and drop speed is maintained at 180 drops/minute, often the amount of dripping Be maintained at 0.05mL, the temperature of deionized water container is about 0 DEG C, syringe nozzle and super-hydrophobic photo-thermal suppression ice coating between away from From for 30cm.Super-hydrophobic photo-thermal suppression ice coating is placed on sloping platform, with respect to the horizontal plane with 30 ° of inclination angle, and With xenon lamp (400mW/cm2) irradiation.Meanwhile xenon lamp presses down ice coating 50cm, vertical irradiation surface away from super-hydrophobic photo-thermal.By sample It is previously positioned in chamber, is then -15 DEG C by chamber temperature setting, after twenty minutes, opens xenon lamp, opened in drip process Surface is irradiated when the beginning.With infrared thermoviewer recording surface temperature, it is real that the simulation of photo-thermal sleet is carried out to super-hydrophobic photo-thermal suppression ice coating It tests.Fig. 9 is the ice condition figure that aluminium sheet continues simulation sleet experiment in 25 minutes at low temperature.Figure 10 is the super of the preparation of embodiment one Hydrophobic photo-thermal suppression ice coating continues the ice condition figure of simulation sleet experiment in 25 minutes at low temperature.As seen from the figure, embodiment one For the super-hydrophobic photo-thermal suppression ice coating coating of preparation in simulation sleet experiment in 25 minutes, surface does not form ice crystal;In xenon lamp It can achieve complete suppression ice effect under irradiation.
And under the conditions of above-mentioned frost rain simulated experiment, heating test is carried out to super-hydrophobic photo-thermal suppression ice coating surface ,- 15 DEG C of low temperature environment and certain Power Xenon Light (400mW/cm2) under irradiation, coating shows excellent super-hydrophobicity, increasing extent of temperature Up to 40 DEG C or more, and keep stable, to reach suppression ice effect;
Adhesive force test is carried out to super-hydrophobic photo-thermal suppression ice coating: firstly, being by 1.5mL deionized water injection diameter In the glass column of 1.2cm, it is placed on coating.Then, it places it in the insulating box that temperature is -25 DEG C, in coating surface Form complete icicle.Glass column is removed after 2h, sample is placed in the trial zone equipped with tension sensor, by trial zone temperature Degree is maintained at -20 DEG C, and the probe for being 0.7cm with diameter is measured in tension sensor with the constant speed of 1mm/s from coating table The power of the icicle of face separation.The fracture maximum, force of measurement is recorded, and measures 5 parallel samples, to obtain average value (Fp).By Fp Divided by contact area s, the adhesion strength of ice is calculated, contact area is 1.1304 × 10-4m2.Coating known to test shines in xenon lamp The lower adhesion strength to ice is penetrated down to 2.1KPa.

Claims (10)

1. a kind of preparation method for pressing down ice coating using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material, It is characterized in that it is to sequentially include the following steps:
One, solar energy optical-thermal powder is prepared:
Nine water ferric nitrates, nitrate trihydrate copper, tetrahydrate manganese chloride and water are mixed, mixed solution is obtained, then by mass percent Sodium hydroxide solution for 3%~8% is instilled in container simultaneously and is stirred with mixed solution, obtains mixture, and process is added dropwise Controlling rate of addition and keeping mixture pH is 10.5~11.5, then mixture is stood 1h~4h at room temperature, discarded supernatant Liquid simultaneously filters, and is precipitated, and under conditions of temperature is 50 DEG C~120 DEG C, will precipitate dry 1h~3h, then grinds, finally With heating rate for 5 DEG C/min~20 DEG C/min, temperature is warming up to 600 DEG C~800 DEG C, and be 600 DEG C~800 DEG C in temperature And under air atmosphere, 1h~2h is calcined, solar energy optical-thermal powder is obtained;
The quality of the nine water ferric nitrates and the volume ratio of water are 1g:(10~20) mL;Iron in the nine water ferric nitrates The molar ratio of copper ion in ion and nitrate trihydrate copper is 1:(0.9~2);Iron ion and four in the nine water ferric nitrates The molar ratio of manganese ion in water manganese chloride is 1:(0.9~2);The sodium hydroxide that the mass percent is 3%~8% is molten Hydroxyl molal quantity in liquid is identical as the anion mol number in mixed solution;
Two, nanoparticles solution is prepared:
By gas phase SiO2Nano particle is added in hexamethylene, obtains gas phase SiO2Nanoparticles solution, by gas phase SiO2Nanometer Grain solution ultrasonic disperse 5min~30min, obtains uniform SiO2Suspension, under room temperature and stirring condition, by cetyl Trimethoxy silane and glacial acetic acid are added dropwise to uniform SiO2In suspension, stirs 1 day~2 days, it is molten to obtain nano particle Liquid;
The gas phase SiO2The concentration of nanoparticles solution is 5mg/mL~25mg/mL;The gas phase SiO2Nano particle with The mass ratio of hexadecyl trimethoxy silane is 1:(2~4);The gas phase SiO2The mass ratio of nano particle and glacial acetic acid For 1:(0.5~1);
Three, solar heat matrix is prepared:
The curing agent of solar energy optical-thermal powder, dimethyl silicone polymer and dimethyl silicone polymer is mixed, then in ball mill Middle grinding 1h~3h, obtains coating, under conditions of being 100 μm~600 μm with coating thickness, coating is coated in substrate, is obtained To solar heat matrix;
The mass ratio of the solar energy optical-thermal powder and dimethyl silicone polymer is 1:(5~15);
Four, it sprays:
1., using nanoparticles solution as spray coating liquor, in spray gun air pressure be 0.4MPa~0.7MPa and distance is 15cm~20cm's Under the conditions of, 15 layers~50 layers nanoparticle coating are sprayed in solar heat substrate upper surface, are then 100 DEG C~135 in temperature Under conditions of DEG C, 10min~20min is heated, obtains the matrix after spraying for the first time;
2., using nanoparticles solution as spray coating liquor, in spray gun air pressure be 0.4MPa~0.7MPa and distance is 15cm~20cm's Under the conditions of, the substrate upper surface after first time sprays continues to spray 15 layers~50 layers nanoparticle coating, is then in temperature Under conditions of 100 DEG C~135 DEG C, 20min~30min, the matrix after obtaining second of spraying are heated;
3., using nanoparticles solution as spray coating liquor, in spray gun air pressure be 0.4MPa~0.7MPa and distance is 15cm~20cm's Under the conditions of, the substrate upper surface after spraying at second continues to spray 15 layers~50 layers nanoparticle coating, is then in temperature Under conditions of 100 DEG C~135 DEG C, 30min~50min is heated, obtains the matrix after third time sprays;
4., using nanoparticles solution as spray coating liquor, in spray gun air pressure be 0.4MPa~0.7MPa and distance is 15cm~20cm's Under the conditions of, the substrate upper surface after third time sprays continues to spray 15 layers~50 layers nanoparticle coating, is then in temperature Under conditions of 100 DEG C~135 DEG C, solidify 1h~3h, obtains super-hydrophobic photo-thermal suppression ice coating.
2. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that gas phase SiO described in step 22The average grain diameter of nano particle be 200nm~ 300nm。
3. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that the solidification of dimethyl silicone polymer described in step 3 and dimethyl silicone polymer The mass ratio of agent is 10:1.
4. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that in step 1 under conditions of temperature is 80 DEG C~120 DEG C, dry 1.5h will be precipitated ~3h, then grinds, and finally with heating rate for 10 DEG C/min~20 DEG C/min, temperature is warming up to 700 DEG C~800 DEG C, and In the case where temperature is 700 DEG C~800 DEG C and air atmosphere, 1h~2h is calcined, solar energy optical-thermal powder is obtained.
5. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that the quality of nine water ferric nitrate described in step 1 and the volume ratio of water are 1g:(16 ~20) mL;The molar ratio of the copper ion in iron ion and nitrate trihydrate copper in nine water ferric nitrate described in step 1 is 1: (1~2);The molar ratio of the manganese ion in iron ion and tetrahydrate manganese chloride in nine water ferric nitrate described in step 1 is 1:(1 ~2).
6. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that gas phase SiO described in step 22The concentration of nanoparticles solution be 7mg/mL~ 25mg/mL;Gas phase SiO described in step 22The mass ratio of nano particle and hexadecyl trimethoxy silane be 1:(2~ 3.5);Gas phase SiO described in step 22The mass ratio of nano particle and glacial acetic acid is 1:(0.6~1).
7. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that by solar energy optical-thermal powder, dimethyl silicone polymer and poly dimethyl in step 3 The curing agent of siloxanes mixes, and then grinds 1h~2h in the ball mill, obtains coating, with coating thickness for 200 μm~600 μm Under conditions of, coating is coated in substrate, solar heat matrix is obtained.
8. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that the quality of solar energy optical-thermal powder and dimethyl silicone polymer described in step 3 Than for 1:(9~15).
9. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the suppression of the super-hydrophobic photo-thermal of raw material The preparation method of ice coating, it is characterised in that by gas phase SiO in step 22Nano particle is added in hexamethylene, obtains gas phase SiO2Nanoparticles solution, by gas phase SiO2Nanoparticles solution ultrasonic disperse 5min~20min, obtains uniform SiO2It suspends Hexadecyl trimethoxy silane and glacial acetic acid are added dropwise to uniform SiO under room temperature and stirring condition by liquid2It suspends In liquid, stirs 1 day~1.5 days, obtain nanoparticles solution.
10. according to claim 1 a kind of using iron copper manganese Metal salt and nano silica as the super-hydrophobic photo-thermal of raw material Press down the preparation method of ice coating, it is characterised in that step 4 is 1. middle to heat 10min;Step 4 is 2. middle to heat 20min;Step 4 is 3. Middle heating 30min;Step 4 is 4. middle to solidify 1.5h.
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