CN109627905A - It is a kind of with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings and preparation method thereof - Google Patents
It is a kind of with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings and preparation method thereof Download PDFInfo
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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Abstract
It is a kind of with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings, belong to coating technology field, it can solve existing relatively low with absorption coating absorbing property, and cannot achieve automatically cleaning and anti-freeze problem, the present invention includes the following steps: the nanoparticle oily dispersion for being respectively synthesized low-surface-energy and Fe3O4/ rGO/PANI/ resin compounded coating, successively sprays Fe in substrate3O4The nanoparticle oily dispersion of/rGO/PANI/ resin compounded coating and low-surface-energy, obtain automatically cleaning and anti-freeze absorption coating, relative to traditional absorption coating, absorbent properties are more excellent, also there is excellent automatically cleaning and deicing properties, and can big face controllable preparation, be all with a wide range of applications in two fields of the army and the people.
Description
Technical field
The invention belongs to coating technology fields, and in particular to it is a kind of with automatically cleaning, anti-freeze and microwave absorption more function
Energy coating and preparation method thereof.
Background technique
With stealth technology and microwave weapon, the effect of radar, electronic countermeasure in military struggle increases, microwave absorption
The research and application of material are increasingly taken seriously.On modern battlefield, the aircraft and guided missile of different model have used microwave suction
Receiving material can make its effective reflecting surface reduce by 90%, this makes radar power decline to a great extent.Terrestrial weapon such as tank, panzer with
And cannon is carried out stealthy using absorbing material, makes enemy's electronic reconnaissance, including satellite reconaissance and Ground Electronic scouting cannot all have
Effect plays a role.It develops Wide band high performance and lightweight Thin-Layer Radar Absorbing Materials and by this material and improves military weapon
The performance of equipment is combined closely, and will generate significant impact to the fight for improving army；Develop electromagnetic parameter temperature stability
Good high power absorbing material and design and manufacture by this material applied to microwave terminal, microwave weapon function with absorption characteristic
Rate detection system is all significant to the standby performance of active service Jia is improved.
In recent years, there are many report about nanometer microwave absorbing material, and the nanometer for also obtaining Wide band high performance is micro-
Wave absorbs powder body material, and still, substance application is seldom.Main contributor is, existing to absorb the micro- of powder based on nanometer microwave
There is also bandwidths and thickness to be difficult to the problem of optimizing simultaneously for wave absorber coatings.In addition, being easy on existing absorption coating surface
It freezes and falls dust, the performance of absorption coating can be reduced.These problems greatly limit the work of nanometer microwave absorber coatings
The maintenance cost of coating is applied and increased to journeyization.
Super-hydrophobic coat in water, is easy to form one layer of vaporization membrane with aqueous medium interface at it, can prevent dust from falling in painting
Entering due to the random motion of molecule coat inside after layer surface influences the microwave absorbing property of coating, and excellent super thin
It is aqueous can make coating have self-cleaning performance, dust fall in coating surface after wind and rain drop erosion still as before, so,
Super-hydrophobic coat and absorption coating is compound, it is expected that being made has automatically cleaning, anti-freeze and microwave absorption multi-functional painting
Layer.But there is automatically cleaning, anti-freeze and microwave absorption multi-functional coatings to be rarely reported, the preparation of this difunctional coating
Middle key technology is how to assign the superhydrophobic characteristic of absorption coating, while not influencing microwave absorbing property again.Building applies
Layer surface micro-nano structure is to realize super-hydrophobic most effective approach, such as using aque-chemical method, chemistry or laser ablation method,
Hydro-thermal method, anodizing process, electrochemical deposition method, sol-gel method, nano-composite coating method and template etc. are in metal surface
Construct porous or array structure.The study found that this porous or array structure possesses excellent superhydrophobic characteristic, still, because
Porous or array structure roughness is big, and mechanical strength is not high, when by external influence, it is easy to be deteriorated, lead to it
Hydrophobic performance decline.In addition, there is equipment mostly in the preparation method of early period either super-hydrophobic coat or absorption coating
It expensive, the defects of poor repeatability or technique are cumbersome, is only applicable to experimental study and is unable to large scale preparation.Therefore, how to develop one
Have automatically cleaning, anti-freeze and microwave absorption multi-functional painting while planting easy to operate, energy large-scale application and stable performance
The preparation method of layer just seems with important value and meaning.
Summary of the invention
The present invention has microwave absorbing property, the composite coating preparation side of self-cleaning function and icing protection for existing
The problem that method is complicated and performance is unstable, provide it is a kind of with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings and
Preparation method.
The present invention adopts the following technical scheme:
It is a kind of with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings, including be successively sprayed at Metal Substrate from outside to inside
External coating and inner coating on bottom, wherein external coating is the nanoparticle assembling film with low-surface-energy, inner coating Fe3O4/
RGO/PANI/ resin doped and compounded film.
It is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings, include the following steps:
The first step, the preparation of the nanoparticle oily dispersion of low-surface-energy
A. the NaOH for weighing 4 ~ 6g is dissolved in the deionized water of 92.5mL, and preparation NaOH solution is spare, weighs 2.86 ~ 4.29g respectively
FeCl2·4H2The FeCl of O and 4.864 ~ 7.296g3·6H2O is dissolved in 70 ~ 110mL deionized water, and ultrasonic disperse is uniform
Solution after, be transferred in flask and heat, when temperature rises to 40 ~ 60 DEG C, start to drip into flask according to 1 drop/sec of rate
Add NaOH solution, after being added dropwise to complete, continue under the conditions of 40 ~ 60 DEG C, reaction 1.5h is cooled to 25 DEG C, spends after reaction
Ionized water supersound washing several times, obtains magnetic particle, is 1:4 by the volume ratio of magnetic particle ultrasonic disperse to 250 ~ 350mL
Water/ethanol solution in, obtain stable Fe3O4Dispersion liquid；
B. the Fe of 250mL is taken3O4Dispersion liquid, thereto be added 10ml ammonium hydroxide, be dispersed with stirring 1h, in whipping process, dropwise plus
Enter 4ml silester, then stir 6h at 25 DEG C again, precipitated by magnetic suck, with ethyl alcohol and distillation water washing, obtains Fe3O4@
SiO2Core-shell structure composite nanoparticle, by Fe3O4@SiO2Core-shell structure composite nanoparticle ultrasonic disperse is in 150ml deionization
In water, Fe is obtained3O4@SiO2Core-shell structure composite nanoparticle dispersion liquid；
C. the Fe of 120mL is taken3O4@SiO2Core-shell structure composite nanoparticle dispersion liquid, sequentially add thereto 1 ~ 4g urea,
The cationic surfactant of 2 ~ 6g, the 1- amylalcohol of 4 ~ 10mL, 100 ~ 150mL hexamethylene and 10g silester, at 25 DEG C
0.5-6h is stirred, mixed solution is obtained, mixed solution is transferred in reaction kettle, after reacting 5h at 110 ~ 150 DEG C, is cooled to
It after 25 DEG C, is precipitated by magnetic suck, after carrying out washing drying with water and ethyl alcohol, obtains Fe3O4@SiO2/ organic composite nanoparticle
Son, by Fe3O4@SiO2/ organic composite nanoparticle is scattered in 150ml toluene solution, obtains Fe3O4@SiO2/ organic composite is received
Rice corpuscles toluene dispersion liquid；
D. the Fe of 100mL is weighed3O4@SiO2The l of 30 ~ 50mL is being added just thereto in/organic composite nanoparticle toluene dispersion liquid
Octyl trimethoxy siloxane, 20 ~ 48h of back flow reaction under the conditions of 120 DEG C, is precipitated using magnetic suck, with toluene and dimethylbenzene
It is washed, obtains Fe3O4@H-SiO2/ organic composite nanoparticle, by Fe3O4@H-SiO2/ organic composite nanoparticle ultrasound
It is scattered in solvent, obtains the nanoparticle oily dispersion for the low-surface-energy that solid content is 10.0 ~ 25.0wt%；
Second step, Fe3O4The preparation of/rGO/PANI/ resin compounded coating
A. the aniline of 0.01M being dissolved in the hydrochloric acid solution that 10mL concentration is 1M, ultrasonic disperse 15min obtains mixed solution A,
The ammonium persulfate of 0.01M is dissolved in the hydrochloric acid solution that 10mL concentration is 1M, ultrasonic disperse 15min obtains mixed solution B, will
Mixed solution B pours into mixed solution A, and under the conditions of 20 DEG C, stirring 2h obtains blackish green solution after the reaction was completed, will be blackish green
Solution filtering, obtain filtrate, with water and methanol wash several times to washing lotion be it is colourless, the filtrate after washing is dissolved in
The PANI solution that mass fraction is 1wt%-3wt% is obtained in ionized water；
B. the hydrazine hydrate that the concentration for measuring 10mL is 80% is uniformly mixed with the dehydrated alcohol of 20mL, obtains hydrazine hydrate mixed solution
It is spare；It measures the graphene oxide water solution of 2.5mg/mL of 400mL respectively and the polyvinylpyrrolidone of 0.5g is added to burning
It after ultrasonic disperse is uniform in cup, is transferred in flask and begins to warm up, when temperature reaches 80 DEG C, start that hydration is added dropwise into flask
Hydrazine mixed solution, after being added dropwise to complete, reaction 3h is cooled to 25 DEG C after reaction, obtains rGO dispersion liquid；In 100 ~ 150ml
RGO dispersion liquid in be separately added into the Fe of 20 ~ 40ml3O4The PANI solution of dispersion liquid and 30 ~ 60ml, under the conditions of 50 ~ 85 DEG C,
After adding coating material, 2 ~ 6h is reacted, Fe is obtained3O4The aqueous solution of/rGO/PANI composite magnetic particle；
C. Fe is adsorbed with magnet3O4The aqueous solution of/rGO/PANI composite magnetic particle, makes Fe3O4/ rGO/PANI composite magnetic grain
Son sedimentation, is then washed 3 ~ 5 times with dehydrated alcohol, obtains Fe3O4/ rGO/PANI magnetic particle slurry, by Fe3O4/rGO/PANI
Magnetic particle slurry is added in resin, 1000 ~ 1500 revs/min revolving speeds stirring under, disperse 1.0h, obtain concentration 5 ~
The Fe of 35wt%3O4/ rGO/PANI/ resin compounded coating；
Third step has automatically cleaning, anti-freeze and microwave absorption multi-functional coatings preparation
By Fe3O4/ rGO/PANI/ resin compounded coating even application, as inner coating, is put into 60 DEG C of bakings in metal substrate surface
30 ~ 120min in case, when inner coating surface is not fully cured, by the nanoparticle oily dispersion even application of low-surface-energy
It is obtained further after solidification with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings in external coating.
Cationic surfactant described in the step c of the first step is cetyl trimethylammonium bromide, dodecyl three
In methyl bromide ammonium, tetradecyltrimethylammonium bromide, Cetyltrimethylammonium bromide and cetyl pyridinium ammonium bromide
Any one.
Solvent described in the step d of the first step is ethyl acetate or dimethylbenzene.
Coating material described in the step b of second step is KH550, KH560, KH570, dodecyl sodium sulfate, 12
Any one in sodium alkyl benzene sulfonate and cetyl trimethylammonium bromide.
Resin described in the step c of second step is epoxylite, polyurethane based resin and the tetrafluoro of 30.0 ~ 45.0wt%
Any one in vinyl resins.
In third step, internally coated spray pressure is the MPa of 0.1MPa ~ 0.25, the spray pressure of external coating be 0.25MPa ~
0.35MPa。
Further curing mode described in third step is to solidify at 4.0h ~ 8.0h or 25 DEG C of solidification in 60.0 DEG C of baking ovens
20.0h。
In the present invention, the key technology of low-surface-energy nanoparticle oily dispersion preparation is that acquisition structural stability is good
Low-surface-energy nanoparticle, while having both good stability and dispersibility in nonpolar solvent.For above-mentioned requirements, originally
In application, relatively traditional low-surface-energy nanoparticle preparation process has done some corresponding innovations and raising in the following aspects:
In particle preparation process, control particle size, surfactant structure and dosage and dispersion concentration, to improve it non-
Stability and dispersibility in polar solvent；Secondly, using wet process transfer method, carrying out the purification of particle in whole preparation process
And dispersion, it preventing in drying process, particle forms secondary agglomeration, its stability and dispersibility in nonpolar solvent is influenced, and
It is unfavorable for modifying again for particle；In addition, control synthesis technology and the suitable low-surface-energy organic molecule of selection, using generalization
Graft Method is learned, organic molecule is modified in nanoparticle surface, to obtain low-surface-energy and stable nanoparticle.
Fe3O4The key technology of the preparation of/rGO/PANI/ resin compounded coating is how to obtain good dispersion
Fe3O4/ rGO/PANI magnetic particle avoids the secondary agglomeration of magnetic particle in the drying process.For above-mentioned requirements, the application
In, by Fe3O4Magnetic nano-particle and rodlike PANI are supported on the surface of the graphene oxide layer of reductive modification, Fe3O4With
The load of PANI, which avoids to be formed between graphene sheet layer, reunites, and is difficult to redisperse and opens.
Key technology with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings preparation is to obtain stable structure
Property super hydrophobic surface, while and can area stable preparation.Conventional nano doping method, using highly concentrated nano particle in coating
The Gao Cu Unfeigned degree of surface construction is super-hydrophobic to realize, although this method can be prepared using spray coating method large area, repeats
It prepares that stability is poor, and coating and the poor , Cu Unfeigned structure of the adhesive force of substrate are easily destroyed, loses super-hydrophobic, limit significantly
It is applied.In view of the above-mentioned problems, this patent develops a kind of new structural super-hydrophobic coat, not only possess excellent super thin
Water, mechanics and stable repetition preparation, and the preparation of spray coating method large area can also be used.
Beneficial effects of the present invention are as follows:
1. what the present invention designed is a kind of with automatically cleaning, the multi-functional composite coating of anti-freeze and microwave absorption, possess more excellent
Different superhydrophobic characteristic, contact angle are greater than 169 °, and roll angle is less than 2 °.
2. the present invention is designed and prepared with automatically cleaning, the multi-functional composite coating of anti-freeze and microwave absorption, can adopt
It is prepared with spray coating method large area, and the super-hydrophobic low-surface-energy for mostling come from nano surface particle, surface roughness is relied on
Smaller, it is preferable that coating repeats preparation stability.
3. present invention preparation has automatically cleaning, the multi-functional composite coating of anti-freeze and microwave absorption, coating cure conditions
It is required that being easier to control, can both having solidified in a heated condition or being solidified under room temperature (25 DEG C), more it is applicable in
Large scale preparation under outdoor true environment.
4. present invention preparation has automatically cleaning, the multi-functional composite coating of anti-freeze and microwave absorption, nanoparticle is direct
It is sprayed on the coating surface not being fully cured, as coating further solidifies, is embedded in coating surface, nanoparticle particle-stabilisedly
It is bonded by absorption coating, and surface particle stable structure, loads 100g counterweight, move in parallel 10cm, recycled 100 times, connect
Feeler is still greater than 165 °, has excellent mechanical stability.
5. prepared by the present invention have automatically cleaning, the multi-functional composite coating of anti-freeze and microwave absorption, coating layer thickness is
It is at 9.47GHz in frequency, the minimal reflection loss of composite coating has reached -32.5dB when 2mm.Its effective [RL < -10
DB] wave frequency width is inhaled for 13.93GHz [4.07-18].
Detailed description of the invention
Fig. 1 is high dispersive Fe prepared by the embodiment of the present invention 13O4And Fe3O4@H-SiO2The XRD diagram of/CTAB nanoparticle, a
For high dispersive Fe3O4XRD diagram, b Fe3O4@H-SiO2The XRD diagram of/CTAB nanoparticle；
Fig. 2 is coating pictorial diagram prepared by the embodiment of the present invention 2；
Fig. 3 is the Fe of preparation of the embodiment of the present invention3O4@H-SiO2The SEM of/CTAB nanoparticle schemes, wherein A is embodiment 1
The Fe of silane-modified fibrous nucleocapsid structure3O4@H-SiO2The SEM of/CTAB nanoparticle schemes, and B is that the silane of embodiment 2 changes
The Fe of the fibrous nucleocapsid structure of property3O4@H-SiO2The SEM of/CTAB nanoparticle schemes；
Fig. 4 is that the microwave absorption of coating prepared by the embodiment of the present invention 3 can scheme；
Fig. 5 is the mechanical stability phenogram of coating prepared by the embodiment of the present invention 3；
Fig. 6 is the self-cleaning performance characterization of coating prepared by the embodiment of the present invention 4；
Fig. 7 is the deicing properties phenogram of coating prepared by the embodiment of the present invention 4；
Fig. 8 is the structural schematic diagram of automatically cleaning of the present invention and the difunctional coating of microwave absorption, in which: 1- metallic substrates；2- resin；
3-Fe3O4/ rGO/PANI compound particle；The nanoparticle of 4- low-surface-energy.
Specific embodiment
Embodiment 1
It is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings, include the following steps:
The first step, the preparation of the nanoparticle oily dispersion of low-surface-energy
A. the NaOH for weighing 5g is dissolved in the deionized water of 92.5mL, and it is spare to be made into homogeneous solution.Weigh the four hydration chlorine of 3.5g
Change ferrous iron (FeCl2·4H2) and 6.5g ferric chloride hexahydrate (FeCl O3·6H2O), it is dissolved in deionized water, ultrasonic disperse is equal
It is transferred in flask after even solution, starts that NaOH solution is added dropwise when temperature reaches 65 DEG C, the rate of dropwise addition is 1 drop/sec, drop
1.5h is reacted after complete, reaction terminates to be cooled to room temperature, and it is multiple with deionized water supersound washing, finally by magnetic particle ultrasonic disperse
Yu Shui/ethanol solution (VWater/VEthyl alcohol=1:4) in, stable Fe is prepared3O4Dispersion liquid (8.0mg/ml)；
B. in 250.0ml Fe3O410ml ammonium hydroxide is added in dispersion liquid, is dispersed with stirring 1h, 4ml is added dropwise in whipping process
Then reaction 6h is stirred at room temperature in silester, precipitate removal reaction solution by magnetic absorption, washed with ethyl alcohol and distillation
It washs clean.Obtain Fe3O4@SiO2Core-shell structure composite nanoparticle, by Fe3O4@SiO2Core-shell structure composite nanoparticle ultrasound
It is scattered in aqueous solution, obtains Fe3O4@SiO2Core-shell structure composite nanoparticle dispersion liquid (16.7mg/ml)；
C. in 120ml Fe3O4@SiO2It is sequentially added in core-shell structure composite nanoparticle dispersion liquid: 2.5g urea, 4g 16
Alkyl trimethyl ammonium bromide, 7ml 1- amylalcohol, 100ml hexamethylene and 10g silester, are dispersed with stirring 2h, then at 25 DEG C
Mixed solution is transferred to 130 DEG C of reaction 5h in reaction kettle, room temperature is cooled to, is filled by magnetic suck precipitating with water and ethyl alcohol
Divide washing, by Fe after drying3O4@SiO2/ organic composite nanoparticle is scattered in toluene solution, and Fe is prepared3O4@SiO2/
Organic composite nanoparticle toluene dispersion liquid (0.2g/ml)；
D. in 100ml Fe3O4@SiO235ml n-octyl trimethoxy silicon is added in/organic composite nanoparticle toluene dispersion liquid
Oxygen alkane is precipitated then in 120 DEG C of back flow reaction 30h using magnetic suck, is sufficiently washed with toluene and dimethylbenzene.By Fe3O4@
H-SiO2The nanoparticle oily dispersion of low-surface-energy can be obtained in dimethylbenzene in/organic composite nanoparticle ultrasonic disperse,
Solid content is 15.0wt%；
Second step, Fe3O4The preparation of/rGO/PANI/ resin compounded coating
A. the aniline of 0.01 M(931mg) is dissolved in the hydrochloric acid solution of 10ml 1M, ultrasonic disperse 15min is formed it into uniformly
Mixed solution (being denoted as A)；The ammonium persulfate of 0.01 M(2.282g) is equally dissolved in the hydrochloric acid solution of 10ml 1M, ultrasound
Dispersion forms it into uniform mixed solution (being denoted as B).B solution is poured into 20 DEG C of magnetic force in solution A and is vigorously stirred 2h.It has reacted
Cheng Hou filters obtained blackish green solution, and is washed with water and methanol until filtrate becomes colorless, to remove extra over cure
Sour ammonium and oligomer of phenylamine.Sample after washing is dissolved in the PANI for obtaining that mass fraction is 1.62wt% in deionized water later
Solution；
B. GO (graphene oxide) aqueous solution for measuring the 2.5mg/mL of 400mL, weighs 0.5gPVP(polyvinylpyrrolidone)
It is added to after ultrasonic disperse is uniform in the beaker of clean 500mL and is transferred in three-necked flask, heating water bath, stirring.It measures
The hydrazine hydrate (80%) of 10mL, is uniformly mixed spare with 20mL dehydrated alcohol.Reach 80 DEG C to bath temperature to start that hydrazine hydrate is added dropwise
Mixed solution, reacts 3h after dripping off, be cooled to 25 DEG C after reaction, is transferred in bottle and saves.150mlrGO is taken to disperse
The homemade Fe of 25ml is added in liquid3O4The rodlike stable PANI of dispersion liquid (8.0mg/ml) and the preparation of the 30ml above method
Dispersion liquid, temperature be 50 DEG C at, be added coating material react 3h, available Fe3O4/ rGO/PANI composite magnetic grain
The aqueous solution of son；
C. by Fe3O4The aqueous solution magnet absorption of/rGO/PANI composite magnetic particle makes Fe3O4/ rGO/PANI magnetic particle
Sedimentation, is then washed 3-5 times with dehydrated alcohol, obtains Fe3O4The slurry of/rGO/PANI magnetic particle high concentration, by above-mentioned slurry
It is added in epoxy resin (30wt%), under high speed electric stirring (1000 revs/min), disperses 1.0h, Fe can be obtained3O4/
RGO/PANI/ resin (15wt%) composite coating；
Third step, bilayer be mingled with structure have automatically cleaning, anti-freeze and microwave absorption multifunctional composite coating preparation
By deployed Fe3O4/ rGO/PANI/ cold coating equably sprays (spray pressure 0.1MPa) in metallic substrates table
Coating is placed in 60.0 DEG C of baking ovens and carries out solidification 1.0h by face, when layer surface to be coated is not fully cured, by deployed low surface
Energy nanoparticle coating equably sprays (spray pressure 0.25MPa) in coating surface, is put into 60.0 DEG C of baking ovens and continues to solidify
5h or at room temperature spontaneous curing 20.0h obtain bilayer and are mingled with the multi-functional multiple with automatically cleaning, anti-freeze and microwave absorption of structure
Close coating.
It is found that the characteristic diffraction peak of XRD appears in 2 from a of Fig. 1θ=18.2°、29.9°、35.4°、37.1°、43.0°、
53.3 °, 56.9 °, 62.6 ° and 74.1 ° their correspondence Fe3O4(111), (220), (311), (400), (422), (511),
(440) and (533) crystal face.(b) 2θ=21.5 ° there is SiO2Amorphous diffraction maximum, illustrate core-shell structure Fe3O4@well
The successful preparation of H-SiO2/CTAB nanoparticle.
Embodiment 2
By the first step in example 1,3.5g Iron dichloride tetrahydrate (FeCl24H2O) is changed to 4.0g Iron dichloride tetrahydrate
(FeCl24H2O).3g urea and 5g cetyl trimethylammonium bromide are changed to 2g urea and 4g tetradecyltrimethylammonium bromination
Ammonium, 35ml n-octyl trimethoxy siloxane are changed to 45ml n-octyl trimethoxy siloxane.
Remaining step is identical as example 1.
The size of nucleocapsid structure Fe3O4/H-SiO2/CTAB nanoparticle reduces as can be seen from Figure 3.
Embodiment 3
By Fe3O4/rGO/PANI magnetic particle/resin compounded coating preparation in the second step in example 1, by the rGO of 150ml
The dispersion liquid that dispersion liquid is changed to the rGO dispersion liquid of 200ml and the rodlike stable PANI of 30ml is changed to the rodlike steady of 20ml
The dispersion liquid of fixed PANI.Fe3O4/rGO/PANI composite magnetic particle content is changed to 20.0wt% by 15.0wt%.Remaining step
It is identical as example 1.
As can be known from Fig. 4, the double-deck coating for being mingled with structure has excellent microwave absorbing property.
Fig. 5 is that the counterweight of load 100g pulls coating on sand paper, moves 10cm every time, after recycling 10 overall length 100cm,
The contact angle of coating is still 168 °, and coating performance of coating after circulation friction does not change, and illustrates that coating has very
Good mechanical resistant performance.As can be known from Fig. 5, the double-deck composite coating for being mingled with structure shows good mechanical stability, is rubbing
Still there is very high ultra-hydrophobicity after wiping.
Embodiment 4
By in 1 third step of example, epoxy resin solid content 30wt% is changed to 40wt%, Fe3O4/rGO/PANI/ organic composite
0.1 MPa of coating spray pressure is changed to 0.2 MPa, 0.35 MPa of low-surface-energy nanoparticle spray pressure, and 60 DEG C of solidifications are changed to
Solidify under room temperature (25 DEG C).
Fig. 6 is coating load dust and the process that washes with water, and A figure is its surface of initial coating completely without any ash
Dirt and sundries, the coating surface in B figure load dust, the F figure floating coat table after C, D, E water droplet tumble and take away dust
Restore as before in face.The procedure declaration coating has excellent self-cleaning performance.As can be known from Fig. 6, double-deck to be mingled with the compound of structure
Coating has excellent self-cleaning performance.
It is mingled with the coating of structure and the surface spray of EP/CMP coating to bilayer manufactured in the present embodiment respectively, every
10min is 1 minute spraying to coating, after 15min, sees that the double-deck composite coating surface for being mingled with structure does not load from the A in Fig. 7
Small water droplet, the EP/CMP coating surface of B have uniformly loaded one layer of small water droplet；Under freezing conditions, bilayer is seen from the C in Fig. 7
The coating surface for being mingled with structure does not have ice, and the EP/CMP coating surface of D has uniformly loaded one layer of small frozen beads, therefore it can be concluded that
The composite coating that the bilayer of the application is mingled with structure has anti-freeze performance.As can be known from Fig. 7, double-deck to be mingled with the compound of structure
Coating has anti-freeze performance under freezing conditions to coating spraying treatment as the result is shown.
Claims (8)
1. it is a kind of with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings, it is characterised in that: including from outside to inside successively
The external coating and inner coating being sprayed in metallic substrates, wherein external coating is the nanoparticle assembling film with low-surface-energy, interior
Coating is Fe3O4/ rGO/PANI/ resin doped and compounded film.
2. a kind of preparation method with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings as described in claim 1,
It is characterized by comprising following steps:
The first step, the preparation of the nanoparticle oily dispersion of low-surface-energy
A. the NaOH for weighing 4 ~ 6g is dissolved in the deionized water of 92.5mL, and preparation NaOH solution is spare, weighs 2.86 ~ 4.29g respectively
FeCl2·4H2The FeCl of O and 4.864 ~ 7.296g3·6H2O is dissolved in 70 ~ 110mL deionized water, and ultrasonic disperse is uniform
Solution after, be transferred in flask and heat, when temperature rises to 40 ~ 60 DEG C, start to drip into flask according to 1 drop/sec of rate
Add NaOH solution, after being added dropwise to complete, continue under the conditions of 40 ~ 60 DEG C, reaction 1.5h is cooled to 25 DEG C, spends after reaction
Ionized water supersound washing several times, obtains magnetic particle, is 1:4 by the volume ratio of magnetic particle ultrasonic disperse to 250 ~ 350mL
Water/ethanol solution in, obtain stable Fe3O4Dispersion liquid；
B. the Fe of 250mL is taken3O4Dispersion liquid, thereto be added 10ml ammonium hydroxide, be dispersed with stirring 1h, in whipping process, dropwise plus
Enter 4ml silester, then stir 6h at 25 DEG C again, precipitated by magnetic suck, with ethyl alcohol and distillation water washing, obtains Fe3O4@
SiO2Core-shell structure composite nanoparticle, by Fe3O4@SiO2Core-shell structure composite nanoparticle ultrasonic disperse is in 150ml deionization
In water, Fe is obtained3O4@SiO2Core-shell structure composite nanoparticle dispersion liquid；
C. the Fe of 120mL is taken3O4@SiO2Core-shell structure composite nanoparticle dispersion liquid, sequentially add thereto 1 ~ 4g urea,
The cationic surfactant of 2 ~ 6g, the 1- amylalcohol of 4 ~ 10mL, 100 ~ 150mL hexamethylene and 10g silester, at 25 DEG C
0.5-6h is stirred, mixed solution is obtained, mixed solution is transferred in reaction kettle, after reacting 5h at 110 ~ 150 DEG C, is cooled to
It after 25 DEG C, is precipitated by magnetic suck, after carrying out washing drying with water and ethyl alcohol, obtains Fe3O4@SiO2/ organic composite nanoparticle
Son, by Fe3O4@SiO2/ organic composite nanoparticle is scattered in 150ml toluene solution, obtains Fe3O4@SiO2/ organic composite is received
Rice corpuscles toluene dispersion liquid；
D. the Fe of 100mL is weighed3O4@SiO2The l of 30 ~ 50mL is being added just thereto in/organic composite nanoparticle toluene dispersion liquid
Octyl trimethoxy siloxane, 20 ~ 48h of back flow reaction under the conditions of 120 DEG C, is precipitated using magnetic suck, with toluene and dimethylbenzene
It is washed, obtains Fe3O4@H-SiO2/ organic composite nanoparticle, by Fe3O4@H-SiO2/ organic composite nanoparticle ultrasound
It is scattered in solvent, obtains the nanoparticle oily dispersion for the low-surface-energy that solid content is 10.0 ~ 25.0wt%；
Second step, Fe3O4The preparation of/rGO/PANI/ resin compounded coating
A. the aniline of 0.01M being dissolved in the hydrochloric acid solution that 10mL concentration is 1M, ultrasonic disperse 15min obtains mixed solution A,
The ammonium persulfate of 0.01M is dissolved in the hydrochloric acid solution that 10mL concentration is 1M, ultrasonic disperse 15min obtains mixed solution B, will
Mixed solution B pours into mixed solution A, and under the conditions of 20 DEG C, stirring 2h obtains blackish green solution after the reaction was completed, will be blackish green
Solution filtering, obtain filtrate, with water and methanol wash several times to washing lotion be it is colourless, the filtrate after washing is dissolved in
The PANI solution that mass fraction is 1wt%-3wt% is obtained in ionized water；
B. the hydrazine hydrate that the concentration for measuring 10mL is 80% is uniformly mixed with the dehydrated alcohol of 20mL, obtains hydrazine hydrate mixed solution
It is spare；It measures the graphene oxide water solution of 2.5mg/mL of 400mL respectively and the polyvinylpyrrolidone of 0.5g is added to burning
It after ultrasonic disperse is uniform in cup, is transferred in flask and begins to warm up, when temperature reaches 80 DEG C, start that hydration is added dropwise into flask
Hydrazine mixed solution, after being added dropwise to complete, reaction 3h is cooled to 25 DEG C after reaction, obtains rGO dispersion liquid；In 100 ~ 150ml
RGO dispersion liquid in be separately added into the Fe of 20 ~ 40ml3O4The PANI solution of dispersion liquid and 30 ~ 60ml, under the conditions of 50 ~ 85 DEG C,
After adding coating material, 2 ~ 6h is reacted, Fe is obtained3O4The aqueous solution of/rGO/PANI composite magnetic particle；
C. Fe is adsorbed with magnet3O4The aqueous solution of/rGO/PANI composite magnetic particle, makes Fe3O4/ rGO/PANI composite magnetic grain
Son sedimentation, is then washed 3 ~ 5 times with dehydrated alcohol, obtains Fe3O4/ rGO/PANI magnetic particle slurry, by Fe3O4/rGO/PANI
Magnetic particle slurry is added in resin, 1000 ~ 1500 revs/min revolving speeds stirring under, disperse 1.0h, obtain concentration 5 ~
The Fe of 35wt%3O4/ rGO/PANI/ resin compounded coating；
Third step has automatically cleaning, anti-freeze and microwave absorption multi-functional coatings preparation
By Fe3O4/ rGO/PANI/ resin compounded coating even application, as inner coating, is put into 60 DEG C of baking ovens in metal substrate surface
In 30 ~ 120min the nanoparticle oily dispersion even application of low-surface-energy is existed when inner coating surface is not fully cured
External coating obtains further after solidification with automatically cleaning, anti-freeze and microwave absorption multi-functional coatings.
3. according to claim 2 it is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings,
It is characterized by: cationic surfactant described in the step c of the first step is cetyl trimethylammonium bromide, dodecyl
In trimethylammonium bromide, tetradecyltrimethylammonium bromide, Cetyltrimethylammonium bromide and cetyl pyridinium ammonium bromide
Any one.
4. according to claim 2 it is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings,
It is characterized by: solvent described in the step d of the first step is ethyl acetate or dimethylbenzene.
5. according to claim 2 it is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings,
It is characterized by: coating material described in the step b of second step is KH550, KH560, KH570, dodecyl sodium sulfate, ten
Any one in dialkyl benzene sulfonic acids sodium and cetyl trimethylammonium bromide.
6. according to claim 2 it is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings,
It is characterized by: resin described in the step c of second step is epoxylite, the polyurethane based resin and four of 30.0 ~ 45.0wt%
Any one in vinyl fluoride resinoid.
7. according to claim 2 it is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings,
It is characterized by: internally coated spray pressure is 0.1MPa ~ 0.25MPa in third step, the spray pressure of external coating is
0.25MPa~0.35MPa。
8. according to claim 2 it is a kind of with automatically cleaning, the preparation method of anti-freeze and microwave absorption multi-functional coatings,
It is characterized by: further curing mode described in third step is to solidify at 4.0h ~ 8.0h or 25 DEG C of solidification in 60.0 DEG C of baking ovens
20.0h。
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| CN110467830A (en) * | 2019-07-23 | 2019-11-19 | 北京易净星科技有限公司 | Wear-resisting hydrophobic coating and the method for preparing wear-resisting hydrophobic coating |
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| CN115537024B (en) * | 2022-08-26 | 2024-04-09 | 奇遇新材料科技(佛山)有限公司 | Hydrophobic self-cleaning wave-absorbing electromagnetic film and preparation method thereof |
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