CN109704347A - A kind of hollow silica ball nanocomposite and preparation and application - Google Patents
A kind of hollow silica ball nanocomposite and preparation and application Download PDFInfo
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- CN109704347A CN109704347A CN201910090159.XA CN201910090159A CN109704347A CN 109704347 A CN109704347 A CN 109704347A CN 201910090159 A CN201910090159 A CN 201910090159A CN 109704347 A CN109704347 A CN 109704347A
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Abstract
The present invention relates to a kind of hollow silica ball nanocomposite and preparations and application, are related to field of nanometer material technology.The preparation method of the hollow silica ball nanocomposite specifically includes: preparing the hollow silica ball suspension and the nano silica acidic sol respectively；Hollow silica ball suspension is mixed with nano silica acidic sol by stirring, then stands, obtains hollow silica ball nanocomposite.There is good anti-reflection, automatically cleaning and anti-fog effect using silica nanometer composite coating prepared by silicon dioxide nano composite material of the invention, coating also has good mechanical endurance and weatherability simultaneously, fastness between substrate is good, coating preparation does not need high-temperature calcination or other post processing modes, it can play a role outdoors for a long time, it is applied widely.
Description
Technical field
The present invention relates to field of nanometer material technology, and in particular to hollow silica ball nanocomposite and preparation and answers
With.
Background technique
With the development of science and technology, the development of Multi-function self-cleaning glass is very urgent.So-called more function
Can glass refer to while having anti-reflection, the mechanical strength of automatically cleaning (super hydrophilic antifog or super-hydrophobic) performance and superelevation and resistance to
The glass of time property.Meanwhile also requiring that preparation method is simple and preparation cost is cheap.
Self-cleaning glass (Self-cleaning glass) refers to that simple glass is special either physically or chemically in process
After processing, its surface is made to generate unique physicochemical characteristics, so that glass be made to be not necessarily to through traditional artificial scrubbing method just
It can achieve the glass of cleaning effect.The atomization of glass refers to that moisture or steam are condensate in glass article surface and form minute water
Drop.And antifog glass (Anti-fogging glass) just refers to that simple glass after by specially treated, has surface
Super hydrophilic characteristic, paves the small water droplet formed due to atomization rapidly, thus reach do not influence mirror image, visibility and
The effect of the light transmittance of glass.Self-cleaning glass is broadly divided into two major classes from preparation method: superhydrophilic self-cleaning glass；It is super thin
Water self-cleaning glass.Common preparation method is to coat one layer of inorganic material coating in glass article surface.
If the inorganic material coating is Superhydrophilic substance, the contact angle of small water droplet on the glass surface can be made to level off to
Zero degree rapidly in its surface spreading, forms uniform moisture film, shows super hydrophilic property when water touches glass surface,
It will not influence mirror image, while water layer is thin, the influence to light transmittance also greatly reduces, and passes through the gravity fall band of uniform water film
Spot is walked, most of spot can be removed in the inorganic material coating of glass surface coating Superhydrophilic.Simultaneously using super hydrophilic
Principle, be also possible to prevent the formation of small water droplet, achieve the effect that antifog.
Foreign countries have just had begun glass automatically cleaning and antifog research, in terms of basic research, mesh in the 1960s
Before, developed country Jun You renowned company is in the research and development and production for specializing in self-cleaning glass, such as Britain in the world
Pilkington company, TOTO company, Japan, PPG company, the U.S., GEA company, Germany, VTA company, UIC company etc.；It is applying
Exploitation aspect, Japan take the lead in that exploitation is unfolded, promote, using TiO2Photocatalytic self-cleaning glass, Pilkington company, Britain, beauty
The glass quotient such as PPG company, state also have an optimistic view of the big market of exploitation, processing, production and the popularization and application of this product.Britain
Pilkington glass company is in development and application TiO2It has been walked before Europe, the United States' glass manufacturer in terms of photocatalytic self-cleaning glass
Column, and the product promotion to Europe and other countries (such as U.S.) glass market will be carried out open batch before the end of the year 2002
Sale, then release in North America, Oceanian Australia, the area such as Japan in Asia and country (Chen Libin, building glass with
Industrial glass 2004, No.6,12~15)；The transparent composite self-cleaning antifog glass (W.L. that U.S. W.L.Tonar et al. is developed
Tonareta1.ElectrochromicDeviceHavingASelf-cleaning HydrophilicCoating.United
StatesPatentApplication PublicationUS2001/00210066A1,2001-09-13；K.Toru.Vehic
leMirror.UnitedStatesPatentUS5594585:1997-01-14；K.Toru.Anti-
fogElement.US5854708:1998-12-29；K.Takahamaeta1.MethodofFormingHydrophilicIno
rganic CoatingFilmAndInorganicCoatingComposition.United StatesPatentApplicat
IonPublicationUS2001/008696A1,2001-07-13), it is to be formed that there is catalytic action on the surface of glass baseplate
Photochemical catalyst clear coat, then photochemical catalyst clear coat surface formed have hydrophilic transparent porous inorganic oxide
Object (SiO2And Al2O3) coating.However TiO is all utilized in these technologies2Photocatalysis characteristic promotes surface to reach super hydrophilic, is applicable in
Condition will receive limitation, since it is desired that there is the environment of illumination just to can be carried out catalytic action；Though and this cavernous structure surface can
To improve hydrophily, but the substance for the volatilization that is easy to be killed in a disaster or nanometer dust block aperture, and durability is undesirable.
Although domestic research is started late, but also achieve significant progress, is had in relation to patent and technological achievement up to a hundred
, and constantly have the release of glass antidimmer product.Cause to be atomized in order to avoid forming small water droplet on glassware, transparency drop
It is low, generally use following measures: (1) spraying layer of surface activating agent in glass surface, with remove the water droplet that is deposited thereon and
Dust；(2) one layer of organic water suction nano coating is coated in glass surface；(3) heating device is installed, heating evaporation glass table is passed through
Face water droplet；(4) dispersion of installation ultrasonic wave and heating device are dispersed and are heated simultaneously to glass surface water droplet, reach quick
The purpose of evaporation.However these methods have respective limitation: method (1) needs periodically spary surfactant repeatedly and seems
It is not convenient；Method (2) is due to using organic substance to cause glassware wearability and heat resistance bad；Due to adding in method (3)
Thermal evaporation water droplet usually requires 7~10 minutes, poor in timeliness, and needs external energy, and energy consumption is big, thus impracticable；Side
The device of method (4) is more complex, and element is more, and at high cost (Liu Fu Shengcong, Li Yu put down national building materials technical journal-" glass " 2002
The 3rd phase 16~19 of year).The normal temperature cure nanometer of Zhongke Nano Tech Engineering Center Co., Ltd (section's nanometer company in abbreviation) is certainly
Cleaning glass technology obtains remarkable break-throughs and completes the production of big plate face self-cleaning glass in conjunction with glass post-processing technique, be applied to
The construction projects such as Grand National Theatre and car show Room glass.The standby self-cleaning glass of middle section's nanometer corporation, water is in glass table
The contact angle in face is 6.5 degree, and the self-cleaning glass of external certain leading company preparation, water is 17 degree in the contact angle of glass surface,
As it can be seen that the hydrophily of the standby self-cleaning glass of middle section nanometer corporation far better than certain external leading company product (Chen Libin,
Building glass and industrial glass 2004, No6,12~15).Unfortunately the technology will utilize TiO2Photocatalysis characteristic improve
The hydrophily of stromal surface, it is necessary to good hydrophilicity is just shown in the environment for having ultraviolet light, in dark ring
It is extremely difficult to this effect in border, therefore limits its scope of application.Generally speaking, the automatically cleaning of these current technologies
It is also undesirable with anti-fog effect and durability.
In view of this, the present invention is specifically proposed.
Summary of the invention
The purpose of the present invention is to provide a kind of hollow silica ball nanocomposite and preparations and application, utilize this
The hollow silica ball nano coating of hollow silica ball nanocomposite preparation, with good anti-reflection, certainly
Cleaning and anti-fog effect, while coating also has the fastness between good mechanical endurance and weatherability, with substrate good, makes
With unrestricted, can play a role outdoors for a long time, it is applied widely.
According to the first aspect of the invention, a kind of preparation method of hollow silica ball nanocomposite, institute are provided
Hollow silica ball nanocomposite is stated to be answered by silicon dioxide nano hollow sphere suspension and nano silica acidic sol
Close, the method specifically includes the following steps:
The hollow silica ball suspension and the nano silica acidic sol are prepared respectively；
The hollow silica ball suspension is uniformly mixed with the nano silica acidic sol by stirring, with
After stand,
Wherein, temperature when control is stood is 4-30 DEG C, more preferably 20-25 DEG C；
Wherein, time of repose >=48h is controlled.
Further, the partial size of hollow silica ball is 20-120nm, shell in the hollow silica ball suspension
With a thickness of 5-15nm；
The nano silica acidic sol has chain nano silica, and the nano silica acidity is molten
The condensation degree of glue is 70~90% or so, and the average length of chain nano silica is 5nm or so.
Further, the hollow silica ball suspension by forming two for hollow silica ball dispersion in a solvent
Silica hollow sphere suspension,
Wherein, the solvent is selected from least one of ethyl alcohol, methanol, isopropanol, propylene glycol and n-butanol.
Further, the preparation process of the nano silica acidic sol is as follows:
By carrying out condensation polymerization reaction to alkoxy silane under acidic catalysis conditions, the chain for forming non-particle shape is received
Rice silica species, constitute the nano silica acidic sol.
According to the second aspect of the invention, a kind of hollow silica ball nanocomposite, the silica are provided
Hollow sphere nanocomposite uses the method according in terms of any of the above to be prepared.
According to the third aspect of the invention we, a kind of preparation method of hollow silica ball nano coating, the system are provided
Preparation Method uses the silicon dioxide nano composite material according to the above, is grasped by carrying out lifting at least once to substrate
Make, to prepare nano coating on the surface of the substrate,
Wherein, the hollow silica ball nano coating with a thickness of 50-200nm；
Wherein, light transmittance >=95% of the hollow silica ball nano coating, preferably >=97.8%；
Wherein, contact angle≤8 degree of the hollow silica ball nano coating, preferably 3.8 degree；
Wherein, hardness >=3H of the hollow silica ball nano coating.
Further, the substrate is glass, and the glass is acrylic glass, solar energy glass, window-glass, mirror
Glass or vehicle glass.
Further, it is described at least once lifting operation specifically includes the following steps:
The substrate is immersed in the hollow silica ball nanocomposite, is then lifted, then stand,
It wherein, is 20-200mm/min to the pull rate of substrate when control submergence；Control Immersion time is 5-50s；Often
5~60 seconds are stood after secondary pull-out indoors.
According to the fourth aspect of the invention, a kind of hollow silica ball nano coating, the silicon dioxide hollow are provided
Ball nano coating uses the preparation method according in terms of any of the above to be made.
According to the fifth aspect of the invention, a kind of film covered glass is provided, is covered in the substrate of glass according to top
Hollow silica ball nano coating described in face,
Wherein, the substrate of glass is acrylic glass, solar energy glass, window-glass, mirror glass or vehicle glass.
Compared with prior art, beneficial effects of the present invention include at least:
1, the present invention is compounded to form silica using hollow silica ball suspension and nano silica acidic sol
Hollow sphere nanocomposite, the residual alkoxy in nano silica acidic sol being capable of self-crosslinking in recombination process
Crosslinking is carried out to form tridimensional network, without handing over to the hollow silica ball in hollow silica ball suspension simultaneously
Connection agent is the properties for being remarkably improved hollow silica ball nano coating.
2, preparation method of the invention is easy to operate, at low cost, reproducible, being capable of large-scale industrial production；Meanwhile
The stability for the hollow silica ball nanocomposite being prepared is good, can long-term preservation at room temperature, can be by more
Kind usual manner is filmed, and the process operability of film is good, is convenient for practical operation and application.
3, hollow silica ball nano coating of the invention has good anti-reflection, automatically cleaning and anti-fog effect,
Light transmittance >=97%, contact angle≤8 degree；Meanwhile the coating also has good mechanical endurance, weatherability and fastness,
Hardness >=3H, use is unrestricted, can play a role outdoors for a long time, applied widely.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 shows the preparation method flow chart of the hollow silica ball nanocomposite according to invention；
Fig. 2 shows the scanning electron microscope (SEM) photographs (a) of silicon dioxide nano hollow sphere according to an embodiment of the invention and transmission
Electron microscope (b)；
Fig. 3 shows the transmission plot of hollow silica ball nanocomposite according to another embodiment of the present invention；
Fig. 4 a to Fig. 4 f shows the nanometer that is covered with prepared under the conditions of the differential responses of different embodiments according to the present invention and applies
The light transmittance curve figure of the sheet glass of layer；
Fig. 5 a to Fig. 5 f shows sweeping for the nano coating constructed under the conditions of the differential responses of different embodiments according to the present invention
Retouch electron microscope；
Fig. 6 shows the reaction effect figure under the conditions of the differential responses of different embodiments according to the present invention；
Fig. 7 shows the anti-of the glass sheet surface of the nano coating under the conditions of differential responses according to an embodiment of the invention
Fog effect comparison diagram；
Fig. 8 shows the pencil hardness test knot of the nano coating under the conditions of differential responses according to an embodiment of the invention
Fruit.
Specific embodiment
Technical scheme is described further combined with specific embodiments below.
Hollow silica ball nanocomposite according to the present invention, mainly by hollow silica ball suspension and nanometer
Silica acidic sol is combined；Wherein: the partial size of hollow silica ball is in the hollow silica ball suspension
20-120nm, shell thickness 5-15nm；The nano silica acidic sol has chain nano silica, and described
The condensation degree of nano silica acidic sol is 70-90%, and the average length of chain nano silica is 5nm or so.
In the present invention, hollow silica ball suspension refers to mainly being formed by hollow silica ball and solvent mixed
Close liquid；More specifically, hollow silica ball dispersion is in a solvent, to form suspension.To in hollow silica ball suspension
Solvent do not limit strictly, such as can be excellent at least one of selected from ethyl alcohol, methanol, isopropanol, propylene glycol and n-butanol
It is selected as ethyl alcohol.In addition, the generation type to hollow silica ball suspension does not limit strictly, it can be by hollow silica ball
It is directly dispersing in solvent and forms the suspension, it can also be anti-by that will be carried out containing the raw material of solvent, lye and alkoxy silane
The suspension should be prepared.
In the present invention, nano silica acidic sol refers to the nanometer titanium dioxide prepared under acidic catalysis conditions
Silica solution；More specifically, by carrying out condensation polymerization reaction (abbreviation polycondensation) to alkoxy silane under acidic catalysis conditions, shape
At the chain nanometer titanium dioxide silicon species of non-particle shape, and then constitute the nano silica acidic sol.Wherein, condensation degree
Refer to the extent of reaction that monomer (i.e. alkoxy silane) is condensed in nano silica acidic sol；The nano silica
The condensation degree of acidic sol is 70-90%, that is, refers to that polycondensation occurs for the alkoxy of 70-90% in alkoxy silane, to make nanometer
Silica acidic sol has the residual alkoxy of 10-30%.
The complex form of hollow silica ball suspension of the invention and nano silica acidic sol can for example lead to
Cross the modes such as mixing, standing formed it is described compound；In particular, time of repose >=48h, as shown in Figure 1.In above-mentioned recombination process
In, the residual alkoxy in nano silica acidic sol can be to the silicon dioxide hollow in hollow silica ball suspension
Ball carries out crosslinking to form tridimensional network；More specifically, the residual alkoxy in nano silica acidic sol was both
Energy self-crosslinking forms Si-O-Si key, while can also be cross-linked to form Si-O-Si key with the Si-OH of hollow silica ball, from
And the performances such as the wearability, weatherability, fastness of hollow silica ball nanocomposite can be significantly improved.
Hollow silica ball nanocomposite of the invention, by above-mentioned specific hollow silica ball suspension and
Nano silica acidic sol is compounded to form tridimensional network, so as to which anti-reflection is prepared, automatically cleaning, prevents
The hollow silica ball nano coating that mist, mechanical endurance, weatherability, fastness etc. are had excellent performance；Its reason may is that
The size of hollow silica ball is smaller, and accumulation is capable of forming enough holes, while coating surface being made to have enough tables
Surface roughness to reduce the refractive index of coating, and then makes coating have good anti-reflection, hydrophilic antifogging and automatically cleaning
Performance, furthermore nano silica acidic sol being capable of self-crosslinking cross-linked silica hollow sphere, and fill part two simultaneously
Gap between silica hollow sphere, and then the performances such as mechanical strength, wearability, weatherability and fastness for improving coating.
The study found that the condensation degree of nano silica acidic sol is too high or too low to be unfavorable for hollow silica ball
Crosslinking and composite property raising；Specifically, when the condensation degree of nano silica acidic sol is excessively high, titanium dioxide
Silicon hollow sphere can not form full cross-linked, thereby reduce intensity, wearability, fastness of coating etc., and nano silica
It will lead to when the condensation degree of acidic sol is too low in silicon dioxide nano composite material and there is residual alkoxy, and then will lead to painting
The contact angle of layer surface improves, and is unfavorable for the raising of the performances such as coating anti-reflection, hydrophilic antifogging and automatically cleaning, therefore, is suitable for
Condensation degree be 70-90%, preferably 75-85%, more preferably 80-85%.Furthermore, in the present invention it is possible to pass through acid
Dosage adjusts the condensation degree of nano silica acidic sol, and sour dosage is bigger, then condensation degree is higher.
The present invention does not limit hollow silica ball strictly, preferably non-porous silicas hollow sphere；This non-porous two
Silica hollow sphere refers in hollow silica ball shell substantially without hole.The study found that porous silica is hollow
Ball contains large-sized cavity, provides effective porosity, so as to reduce the refractive index of coating, to reach anti-reflection increasing
Saturating performance.
In the present invention, above-mentioned hollow silica ball suspension and nanometer two can be prepared using the conventional method of this field
Silica acidic sol, as long as being conducive to the suspension that the correlated quality requirement for having the present invention above-mentioned is prepared and acidic sol i.e.
It can；That is, the preparation method of hollow silica ball suspension should at least make the partial size 20- of hollow silica ball in suspension
120nm, shell thickness 5-15nm, the preparation method of nano silica acidic sol should at least make nanometer titanium dioxide silicic acid
Property colloidal sol condensation degree be 70-90%, the average length of chain nano silica is 5nm or so.
More specifically, the preparation method of the silicon dioxide nano hollow sphere suspension may include: that will contain solvent, alkali
The raw material of liquid, polyacrylic acid and alkoxy silane is reacted.The condition of above-mentioned reaction is not limited strictly, as long as convenient for system
It is standby to obtain the hollow silica ball suspension with the above-mentioned quality requirement of the present invention.The molecular weight control of polyacrylic acid exists
2000~1000；Specifically, can control volume ratio between solvent, lye, polyacrylic acid and alkoxy silane be 90:3~
6:0.4~0.8:1~3, the ratio range are conducive to that above-mentioned specific hollow silica ball is prepared.
Hollow sphere is washed by water repeatedly, to remove polyacrylic acid, ammonium hydroxide in hollow sphere suspension etc..Washing is dry
Net hollow sphere disperses in ethanol, to be ready for configuration hollow sphere composite nano materials.
The study found that the stability of above-mentioned preparation method and reproducible, is not strict with the scale of reaction system,
Even if good repeatability can also be had by being prepared under the conditions of extensive, therefore particularly suitable large-scale industrial production.Tool
The reaction volume of body can be determined rationally according to actual needs, such as can be 0.4-20L.
In the present invention, the preparation method of the nano silica acidic sol may include: that will contain solvent, acid solution
It is reacted with the raw material of alkoxy silane；Wherein it is possible to control the volume ratio between water, ethyl alcohol, acid solution and alkoxy silane
For 5~20:200~300:0.05~0.2:10~40.Said ratio range is conducive to the chain that above-mentioned specific dimensions are prepared
Shape nano silica.
The study found that the stability of above-mentioned nano silica acidic sol preparation method and reproducible, to reactant
The scale of system is not strict with, even if good repeatability can also be had by being prepared under the conditions of extensive, therefore especially
It is applicable in large-scale industrial production.Specific reaction volume can be determined rationally according to actual needs, such as can be 0.2-5L.
In the present invention, it stands for realizing the above-mentioned of hollow silica ball suspension and nano silica acidic sol
It is compound；That is, realizing the self-crosslinking of the residual alkoxy in nano silica acidic sol and to hollow silica ball
The crosslinked action of hollow silica ball in suspension.Static conditions are not limited strictly；For example, when can control standing
Temperature is 4-30 DEG C, preferably 20-25 DEG C, furthermore can control time of repose >=48h.The study found that dwell temperature is 20-25
DEG C when be conducive to further decrease the contact angle of coating, contact angle can be reduced to 4-6 degree；In addition, time of repose is 48h or more base
Originally can be realized integral system stablizes crosslinking, and product can be stored for a long time, and quality is stablized.
In the present invention, the mass percentage of hollow sphere is 0.5~5% in the hollow silica ball suspension of configuration,
The volume ratio range of hollow sphere suspension and acidic sol liquid are as follows: 8:50~24:50.
The present invention provides a kind of preparation method of silicon dioxide nano hollow sphere nano coating, empty using above-mentioned silica
Bulbus cordis composite material carries out preparation nanometer painting according to hollow silica ball nanocomposite prepared by above-mentioned preparation method
Layer.The present invention does not limit method used by the film strictly, can use the conventional film-forming method of this field, such as
Czochralski method, spray coating method etc.；In addition, the present invention does not limit strictly used substrate is film-made, substrate can use glass, example
Such as acrylic glass, solar energy glass, window-glass, mirror glass, vehicle glass.
The preparation method of silica nanometer laminated film of the invention may include lifting step or extremely at least once
A few spraying process；Wherein, the lifting step may include: that substrate is immersed in the silicon dioxide nano composite material
In, it then lifts, then stand.In the lifting step, the decrease speed of substrate is 20-200mm/min when can control submergence；
Control Immersion time is 5-50s；The rate of climb of substrate is 20-200mm/min when control lifting；Control time of repose is 60-
120s；5~60 seconds are stood indoors after pulling out every time.
The present invention provides a kind of hollow silica ball nano coating, is made according to above-mentioned preparation method.Wherein, described two
Silica hollow sphere with a thickness of 50-200nm；Light transmittance >=95%, preferably >=97.8%；Contact angle≤8 degree, preferably 3.8
Degree；Hardness >=3H.
The present invention also provides a kind of film covered glass, are covered with above-mentioned hollow silica ball nano coating in substrate surface；It is right
Substrate does not limit strictly, can be acrylic glass, solar energy glass, window-glass, mirror glass, vehicle glass etc..This
The concrete application field of invention film covered glass without stringent limitation, can be widely applied to daily life, industry, astronomy, military science,
The related fieldss such as electronics especially can be applied to the solar battery etc. of long-term outdoor work.
The present invention also provides a kind of hydrophilic antifogging automatically cleaning silica with high mechanical strength and anti-reflection performance
The preparation process of nano coating, it is characterised in that: the technique is by acidic sol liquid and silicon dioxide nano hollow sphere suspension
Mixing is deposited in substrate using lifting and spraying method, makes to have enough in coating containing enough porosity and coating surface
Rough surface, to reach anti-reflection and hydrophilic antifogging performance；The purpose that acidic sol liquid is added is to be crosslinked titanium dioxide
Silicon nano-hollow ball, while the gap between fill part silicon dioxide nano hollow sphere, to increase the mechanical endurance of coating.It is logical
The proportion for crossing regulation acidic sol liquid and nano-hollow ball suspension promotes the combination of the two, to make the nanometer constructed
Coating has the hydrophilic antifogging self-cleaning performance of high mechanical strength, anti-reflection performance simultaneously.
Technical solution of the present invention is clearly and completely described below in conjunction with embodiment, it is clear that described reality
Applying example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The raw material and equipment that each embodiment uses are as follows:
Ethyl alcohol: density is 0.789g/mL or so；Concentrated ammonia liquor: concentration 25-28%, density are 0.913g/mL or so；It is dense
Hydrochloric acid: concentration is 37% or so；Tetraethoxysilane: molecular weight 208.33g/mol, density are 0.93g/mL or so；Lifting
Plated film instrument: Science and Technology Ltd. is ground purchased from Shanghai three.
Embodiment 1
Particle size is the preparation of the silicon dioxide nano hollow sphere of 20~120nm:
(1) polyacrylic acid solution (the wherein quality percentage of polyacrylic acid for being 5000 by 0.4~0.8 milliliter of molecular weight
Content is 50%) to be added in 3~6 milliliters of ammonium hydroxide, in 25 degrees Celsius of lower stirring in water bath；
(2) 90 milliliters of ethyl alcohol are added in 500 milliliters of flasks, the mixed solution in (1) are added in flask, 25
Degree Celsius lower stirring in water bath；
(3) under 25 degrees Celsius, 1~3 milliliter of tetraethoxysilane is added in the mixed solution in (2), continues to stir
It mixes 10~20 hours, obtains the silicon dioxide nano hollow sphere.
(4) by the method for centrifugation, the precipitating of silicon dioxide nano hollow sphere is obtained, 500 milliliters of water are added, be ultrasonically treated
30 minutes, then be centrifuged, it is therefore an objective to polyacrylic acid is removed, this water-washing process repeats twice.Finally by the sky of acquisition
Bulbus cordis is dispersed in 90 milliliters of ethyl alcohol, prepares hollow sphere alcohol suspending liquid.
Fig. 2 is the transmission plot of the silicon dioxide hollow nanosphere of above-mentioned preparation；As shown in Figure 2, manufactured in the present embodiment outstanding
The partial size of silicon dioxide nano hollow sphere is 20-120nm, shell thickness 5-15nm in liquid.
Embodiment 2
Prepare nano silica acidic sol:
Under room temperature (25 DEG C), 0.05~0.2mL concentrated hydrochloric acid (37%) is added in 5~20mL water, dilute hydrochloric acid is made
Solution；Then, above-mentioned dilute hydrochloric acid solution is added in 200~300mL ethyl alcohol, is stirred and evenly mixed.
10~40mL tetraethoxysilane is add to the above mixed solution, after reaction 4h is stirred at room temperature, then room temperature is quiet
It only reacts 4 days, obtains nano silica acidic sol, can be saved in 4 DEG C.
It is detected using solid-state nuclear magnetic resonance, the results showed that the contracting of the nano silica acidic sol of above-mentioned preparation
Right is 70~90% or so, and the average length of chain nano silica is 5nm or so.
Embodiment 3
The configuration of the mixed liquor of hollow silica ball and acidic sol liquid:
The mass concentration of hollow sphere is configured by the way that ethyl alcohol is added using the hollow sphere alcohol suspending liquid prepared in embodiment 1
The alcohol suspending liquid of respectively 0.5%, 1% and 5%.
The low concentration (0.5%) or high concentration (1%) hollow silica ball alcohol suspending liquid for taking 50 milliliters, are constantly being stirred
In the case where mixing, acidic sol liquid obtained in the embodiment 2 of different volumes is added thereto, mixed liquor is made into.Regulation is added
Acidic sol liquid volume, respectively 8,10,12,14,16,18,20,22 and 24 milliliters, so that it is outstanding to configure different hollow spheres
The mixed liquor of turbid and acidic sol liquid volume ratio.Then, it is placed under room temperature (25 DEG C) and stands more than 48h, silica is made
Hollow sphere nanocomposite.
Fig. 3 is outstanding above by the hollow silica ball ethyl alcohol using 8 milliliters of acidic sol liquid and low concentration (0.5%)
The mixed liquor that turbid is constituted, and the transmission plot of the hollow silica ball nanocomposite prepared；As seen from the figure, the titanium dioxide
Silicon dioxide nano hollow sphere is cross-linked with each other to form tridimensional network by acidic sol liquid in silicon hollow sphere nanocomposite,
In addition the chain species in acidic sol liquid are also cross-linked with each other together, form tridimensional network, internal to form many rulers
The very little gap in 3~100nm.
Embodiment 4
Nano coating is prepared by czochralski method, preparation method includes the following steps:
(1) sheet glass is cleaned by ultrasonic in ethanol 5~30 minutes.
(2) sheet glass for cleaning up step (1) in embodiment 3 " 8 milliliters of+50 milliliters of acidic sol liquid are low dense
Spend (0.5%) hollow sphere ethanol solution mixed liquor " in lift respectively 1,2,3,4,5 times, pull rate be 20~200 millimeters/
Minute, it is impregnated 5~50 seconds in suspension, stands 5~60 seconds indoors after pulling out every time.
Fig. 4 (a) shows to be deposited on the glass sheet in embodiment 4 has lifted 1,2,3,4,5 " 8 milliliters of acidity respectively
The light transmittance curve figure of the sheet glass of the mixed liquor of+50 milliliters of low concentration hollow sphere ethanol solutions of sol solutions ", can therefrom send out
Existing: cover cated glass has apparent anti-reflection phenomenon within the scope of visible light and near-infrared wavelength, has and passes through
Lifting 4 times and formed nano coating glass have highest light transmittance, average transmittance increases 5% or more, in 555nm
There is highest light transmittance at wavelength, reach 97%.
It is deposited on sheet glass in Fig. 5 (a) embodiment of the present invention 4 by 4 lifting " 8 milliliters of+50 milliliters of acidic sol liquid
The mixed liquor of low concentration hollow sphere ethanol solution " and prepare nano coating scanning electron microscope (SEM) photograph, it can be seen that coating be by
Hollow sphere, which is accumulated, to be formed, coating surface be it is smooth, between hollow ball inside and hollow sphere there are many gaps, these gaps
Refractive index is caused to reduce, to make to cover cated glass light transmittance with higher, in addition, these gaps are also beneficial to water
It the infiltration of drop and sprawls.
Embodiment 5
The method for preparing nano coating referring to 4 method of embodiment.
(1) sheet glass is cleaned by ultrasonic in ethanol 5~30 minutes.
(2) sheet glass for cleaning up step (1) in embodiment 3 " 10 milliliters of+50 milliliters of acidic sol liquid are low dense
The mixed liquor of degree (0.5%) hollow sphere ethanol solution ", " 12 milliliters of acidic sol liquid+50 milliliters of low concentrations (0.5%) hollow sphere
The mixed liquor of ethanol solution ", " mixing of 14 milliliters of acidic sol liquid+50 milliliters of low concentrations (0.5%) hollow sphere ethanol solution
Liquid ", " mixed liquor of 16 milliliters of acidic sol liquid+50 milliliters of low concentrations (0.5%) hollow sphere ethanol solution ", " 18 milliliters of acidity
The mixed liquor of+50 milliliters of low concentrations of sol solutions (0.5%) hollow sphere ethanol solution ", " 20 milliliters of+50 milliliters of acidic sol liquid are low
The mixed liquor of concentration (0.5%) hollow sphere ethanol solution ", "+50 milliliters of low concentrations of 22 milliliters of acidic sol liquid (0.5%) are hollow
The mixed liquor of ball ethanol solution ", " mixing of 24 milliliters of acidic sol liquid+50 milliliters of low concentrations (0.5%) hollow sphere ethanol solution
Liquid ", " mixed liquor of 8 milliliters of acidic sol liquid+50 milliliters of high concentrations (1%) hollow sphere ethanol solution ", " 10 milliliters of acidic sols
The mixed liquor of+50 milliliters of high concentrations of liquid (1%) hollow sphere ethanol solution ", "+50 milliliters of high concentrations of 12 milliliters of acidic sol liquid
(1%) mixed liquor of hollow sphere ethanol solution ", " 14 milliliters of acidic sol liquid+50 milliliters of high concentrations (1%) hollow sphere ethyl alcohol is molten
The mixed liquor of liquid ", " mixed liquor of 16 milliliters of acidic sol liquid+50 milliliters of high concentrations (1%) hollow sphere ethanol solution ", " 18 millis
The mixed liquor of liter+50 milliliters of high concentrations of acidic sol liquid (1%) hollow sphere ethanol solution ", " 20 milliliters of+50 millis of acidic sol liquid
The mixed liquor of elevated concentrations (1%) hollow sphere ethanol solution ", "+50 milliliters of high concentrations of 22 milliliters of acidic sol liquid (1%) are hollow
The mixed liquor of ball ethanol solution ", " mixing of 24 milliliters of acidic sol liquid+50 milliliters of high concentrations (1%) hollow sphere ethanol solution
It is lifted respectively in liquid " 1,2,3,4,5 times, pull rate is 20~200 mm/mins, impregnates 5~50 seconds in suspension, often
5~60 seconds are stood after secondary pull-out indoors.
Fig. 4 (b) shows to be deposited on the glass sheet in embodiment 5 has lifted 1,2,3,4,5 " 10 milliliters of acidity respectively
The light transmittance curve figure of the sheet glass of the mixed liquor of+50 milliliters of low concentrations of sol solutions (0.5%) hollow sphere ethanol solution ", therefrom
It can be found that: cover cated glass has apparent anti-reflection phenomenon within the scope of visible light and near-infrared wavelength, tool
There is the glass of the nano coating formed by lifting 4 times that there is highest light transmittance, average transmittance increases 5% or more,
There is highest light transmittance at 550nm wavelength, reach 97%.
Fig. 4 (c) shows to be deposited on the glass sheet in embodiment 5 has lifted 1,2,3,4,5 " 12 milliliters of acidity respectively
The light transmittance curve figure of the sheet glass of the mixed liquor of+50 milliliters of low concentrations of sol solutions (0.5%) hollow sphere ethanol solution ", therefrom
It can be found that: cover cated glass has apparent anti-reflection phenomenon within the scope of visible light and near-infrared wavelength, tool
There is the glass of the nano coating formed by lifting 3 times that there is highest light transmittance, average transmittance increases 5% or more,
There is highest light transmittance at 520nm wavelength, reach 97%.
Fig. 4 (d) shows to be deposited on the glass sheet in embodiment 5 has lifted 1,2,3,4,5 " 8 milliliters of acidity respectively
The light transmittance curve figure of the sheet glass of the mixed liquor of+50 milliliters of high concentrations of sol solutions (1%) hollow sphere ethanol solution ", Cong Zhongke
With discovery: cover cated glass has apparent anti-reflection phenomenon within the scope of visible light and near-infrared wavelength, has
The glass of the nano coating formed by lifting 2 times has highest light transmittance, and average transmittance increases 5.8% or more,
There is highest light transmittance at 520nm wavelength, reach 97.8%.
Fig. 4 (e) shows to be deposited on the glass sheet in embodiment 5 has lifted 1,2,3,4,5 " 10 milliliters of acidity respectively
The light transmittance curve figure of the sheet glass of the mixed liquor of+50 milliliters of high concentrations of sol solutions (1%) hollow sphere ethanol solution ", Cong Zhongke
With discovery: cover cated glass has apparent anti-reflection phenomenon within the scope of visible light and near-infrared wavelength, has
The glass of the nano coating formed by lifting 2 times has highest light transmittance, and average transmittance increases 5.8% or more,
There is highest light transmittance at 540nm wavelength, reach 97.8%.
Fig. 4 (f) shows to be deposited on the glass sheet in embodiment 5 has lifted 1,2,3,4,5 " 12 milliliters of acidity respectively
The light transmittance curve figure of the sheet glass of the mixed liquor of+50 milliliters of high concentrations of sol solutions (1%) hollow sphere ethanol solution ", Cong Zhongke
With discovery: cover cated glass has apparent anti-reflection phenomenon within the scope of visible light and near-infrared wavelength, has
The glass of the nano coating formed by lifting 2 times has highest light transmittance, and average transmittance increases 5.4% or more,
There is highest light transmittance at 540nm wavelength, reach 97.4%.
Fig. 5 (b) and Fig. 5 (c) is respectively to be deposited on sheet glass in the embodiment of the present invention 5 by 4 lifting " 10 milliliters of acid
Property+50 milliliters of low concentrations of sol solutions (0.5%) hollow sphere ethanol solution mixed liquor " and by 3 times lifting " 12 milliliters of acidity are molten
The mixed liquor of+50 milliliters of low concentrations of glue (0.5%) hollow sphere ethanol solution, and the scanning electron microscope (SEM) photograph of the nano coating prepared,
It can be seen that coating is to be accumulated to be formed by hollow sphere, coating surface be it is smooth, deposited between hollow sphere cavity and hollow sphere
In many gaps, these gaps cause refractive index to reduce, to make to cover cated glass light transmittance with higher, separately
Outside, as the additional amount of acidic sol liquid increases, cloud components content is accordingly increased in coating.
Fig. 5 (d), Fig. 5 (e) and Fig. 5 (f) are respectively to be deposited on sheet glass in the embodiment of the present invention 5 by 2 liftings " 8
Milliliter acidic sol+50 milliliters of high concentrations of liquid (1%) hollow sphere ethanol solution mixed liquor ", by 2 lifting " 10 milliliters of acid
Property+50 milliliters of high concentrations of sol solutions (1%) hollow sphere ethanol solution mixed liquor " and pass through 2 lifting " 12 milliliters of acidic sols
The mixed liquor of+50 milliliters of high concentrations of liquid (1%) hollow sphere ethanol solution ", and the scanning electron microscope (SEM) photograph of the nano coating prepared, from figure
In as it can be seen that the hollow sphere of high concentration causes the ratio of hollow sphere in coating to obviously increase, coating surface almost has hollow sphere close
What accumulation was formed, acidic sol liquid is crosslinked together by hollow sphere, cotton-shaped in coating as the additional amount of acidic sol liquid increases
Constituent content accordingly increases.
Fig. 6 shows 3 microlitres of water droplets, and deposition " is mixed by 2 times or 3 times liftings on sheet glass in embodiment 4 and 5 respectively
Liquid " and contact angle size and acidic sol liquid of the glass sheet surface for being covered with nano coating prepared when sprawling 0.5 second
Long-pending relation curve.As shown, the contact angle of water droplet is both less than 8 degree.It is deposited with and has lifted 2 " 12 milliliters of acidic sol liquid
With the mixed solution of 50 milliliters of high concentration hollow spheres " the glass sheet surface of nano coating contact angle when sprawling 0.5 second
Digital photograph shows that its contact angle is 3.8 degree, has reached super hydrophilic.
Fig. 7, which shows to be deposited in blank glass and embodiment 5, has lifted 2 " 12 milliliters of acidic sol liquid and 50 milliliters
The antifog effect contrast figure of the glass sheet surface of the nano coating of the mixed solution of high concentration hollow sphere ".Cated part can
Effectively to inhibit the formation of mist.
It is detected using " GB/T6739-1996 hardness of film pencil measuring method ".Fig. 8 shows in embodiment 5 and deposits
There is the pencil for the nano coating for having lifted 2 times " mixed solution of 12 milliliters of acidic sol liquid and 50 milliliters of high concentration hollow spheres " hard
Spend test result.After the test of 3H pencil, coating does not have any damage, shows that coating has reached the industrial requirements of 3H.
Embodiment 6
The method for preparing nano coating referring to 4 method of embodiment.
(1) sheet glass is cleaned by ultrasonic in ethanol 5~30 minutes.
(2) sheet glass for cleaning up step (1) in embodiment 3 " 12 milliliters+50 milliliter 5% of acidic sol liquid
It is lifted respectively in the mixed liquor of hollow sphere ethanol solution " 1,2,3,4,5 times, pull rate is 20~200 mm/mins, outstanding
It is impregnated 5~50 seconds in supernatant liquid, stands 5~60 seconds indoors after pulling out every time.
The light transmittance of the coating of preparation is reduced to 93%, and it is anti-reflection to show that ultrahigh concentration hollow sphere is unfavorable for.
Claims (10)
1. a kind of preparation method of hollow silica ball nanocomposite, which is characterized in that the hollow silica ball
Nanocomposite is combined by silicon dioxide nano hollow sphere suspension and nano silica acidic sol, the method tool
Body the following steps are included:
The hollow silica ball suspension and the nano silica acidic sol are prepared respectively；
The hollow silica ball suspension is uniformly mixed with the nano silica acidic sol by stirring, it is then quiet
It sets, obtains hollow silica ball nanocomposite,
Wherein, temperature when control is stood is 4-30 DEG C, more preferably 20-25 DEG C；
Wherein, time of repose >=48h is controlled.
2. preparation method according to claim 1, which is characterized in that
The partial size of hollow silica ball is 20-120nm, shell thickness 5-15nm in the hollow silica ball suspension；
The nano silica acidic sol has chain nano silica, and the nano silica acidic sol
Condensation degree is 70~90%, and the average length of chain nano silica is 5nm.
3. preparation method according to claim 2, which is characterized in that the hollow silica ball suspension is by by dioxy
The dispersion of SiClx hollow sphere forms hollow silica ball suspension in a solvent,
Wherein, the solvent is selected from least one of ethyl alcohol, methanol, isopropanol, propylene glycol and n-butanol.
4. preparation method according to claim 2, which is characterized in that the preparation of the nano silica acidic sol
Journey is as follows:
By carrying out condensation polymerization reaction to alkoxy silane under acidic catalysis conditions, the chain nanometer two of non-particle shape is formed
Silicon species are aoxidized, the nano silica acidic sol is constituted.
5. a kind of hollow silica ball nanocomposite, which is characterized in that the nano combined material of hollow silica ball
Material is prepared using method according to claim 1 to 4.
6. a kind of preparation method of hollow silica ball nano coating, which is characterized in that the preparation method is used according to power
Benefit require 5 described in silicon dioxide nano composite material, by substrate carry out at least once lifting operate, in substrate surface
On prepare nano coating,
Wherein, the hollow silica ball nano coating with a thickness of 50-200nm；
Wherein, light transmittance >=95% of the hollow silica ball nano coating；
Wherein, contact angle≤8 degree of the hollow silica ball nano coating；
Wherein, hardness >=3H of the hollow silica ball nano coating.
7. preparation method according to claim 6, which is characterized in that the substrate is glass, and the glass is acrylic
Glass, solar energy glass, window-glass, mirror glass or vehicle glass.
8. preparation method according to claim 6, which is characterized in that the operation of lifting at least once specifically includes following
Step:
The substrate is immersed in the hollow silica ball nanocomposite, is then lifted, then stand,
It wherein, is 20-200mm/min to the pull rate of substrate when control submergence；Control Immersion time is 5-50s；It draws every time
5~60s is stood after out indoors.
9. a kind of hollow silica ball nano coating, which is characterized in that the hollow silica ball nano coating uses root
It is made according to preparation method described in any one of claim 6 to 8.
10. a kind of film covered glass, which is characterized in that be covered with silica according to claim 8 in the substrate of glass
Hollow sphere nano coating,
Wherein, the substrate of glass is acrylic glass, solar energy glass, window-glass, mirror glass or vehicle glass.
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| CN110982325A (en) * | 2019-12-31 | 2020-04-10 | 上海特栎材料科技有限公司 | Antireflection, antistatic and super-hydrophilic coating composition, coating and product |
| CN113754308A (en) * | 2021-09-30 | 2021-12-07 | 常州大学 | Preparation method of super-amphiphobic antifouling transparent coating |
| CN114716153A (en) * | 2022-04-14 | 2022-07-08 | 常州亚玛顿股份有限公司 | Anti-reflection anti-dazzle coated glass |
| CN115404003A (en) * | 2022-09-13 | 2022-11-29 | 厦门威亮光学涂层技术有限公司 | Coating with antireflection, dustproof, antifogging and antistatic functions and preparation method thereof |
| CN115536286A (en) * | 2022-06-29 | 2022-12-30 | 北京科技大学 | TiO 2 And SiO 2 Composite nano coating, preparation and application |
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| CN115536286B (en) * | 2022-06-29 | 2024-04-26 | 北京科技大学 | TiO2And SiO2Composite nano coating, preparation and application |
| CN115404003A (en) * | 2022-09-13 | 2022-11-29 | 厦门威亮光学涂层技术有限公司 | Coating with antireflection, dustproof, antifogging and antistatic functions and preparation method thereof |
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