CN107445487A - A kind of super hydrophilic dose, preparation method and super hydrophilic glass for vehicle window - Google Patents

A kind of super hydrophilic dose, preparation method and super hydrophilic glass for vehicle window Download PDF

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Publication number
CN107445487A
CN107445487A CN201710738847.3A CN201710738847A CN107445487A CN 107445487 A CN107445487 A CN 107445487A CN 201710738847 A CN201710738847 A CN 201710738847A CN 107445487 A CN107445487 A CN 107445487A
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super
super hydrophilic
hydrophilic
zinc oxide
glass
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林军
张胜君
朱振兴
陈绍木
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Fuyao Glass Industry Group Co Ltd
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Fuyao Glass Industry Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/29—Mixtures
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

It is particularly a kind of super hydrophilic dose, it is characterised in that to be made up of following component the present invention relates to hydrophilic glass technical field：0.1~0.45wt% zinc oxide nano rod, 1.5~5wt% carbon nanotube dust, 12~18wt% N, N dimethylformamides, surplus are dispersion liquid；The carbon nanotube dust is the single wall or multi-walled carbon nanotube of powder shaped, and the CNT is attached to the surface of zinc oxide nano rod.The present invention also provides a kind of super hydrophilic dose of preparation method and is provided with the super hydrophilic glass for vehicle window of super-hydrophilic coating simultaneously.Advantage is：Visible light transmissivity is high, can absorb infrared and ultraviolet radioactive and still has good super hydrophilic characteristic under non-illumination condition.

Description

A kind of super hydrophilic dose, preparation method and super hydrophilic glass for vehicle window
Technical field：
It is particularly a kind of super hydrophilic dose the present invention relates to hydrophilic glass technical field, super hydrophilic dose of preparation method and set It is equipped with the super hydrophilic glass for vehicle window of super-hydrophilic coating.
Background technology：
The wetability of material surface is always the focus of academic and industrial circle concern, super hydrophilic and super-hydrophobic be used as two kinds of poles Special wetting phenomena is held, has attracted the widely studied of domestic and foreign scholars in recent years.In general, super hydrophobic surface refers to solid-liquid Contact angle is more than 150 ° of surface.On the contrary, ultra-hydrophilic surface refers to that liquid can spread completely, and cause contact angle be equal to or Close to 0 ° of surface.With it is super-hydrophobic research compared with, super hydrophilic aspect research it is less, but due to ultra-hydrophilic surface uniqueness wetting Feature so that ultra-hydrophilic surface has the advantages that automatically cleaning, high heat transfer.Earliest it is found out that super hydrophilic characteristic is to be based on two The photocatalysis characteristic of titanium oxide, after by ultraviolet light, water and titanium dioxide semiconductor film contacts, contact angle are decreased to rapidly 0±1°.Its principle generates active oxygen radical for the bridge location oxygen of titanium dioxide surface after by ultraviolet excitation, react and give birth to hole Into epoxide hole, water absorption turns into chemical absorbed water in epoxide hole, so as to form equally distributed nanoscale on surface Hydrophilic microcell.This super hydrophilic property has important application in terms of antifog glass, self-cleaning glass.
However, the significant drawback that titanium deoxid film is used for self-cleaning glass embodies both ways：First, can be by illumination Conditionality, that is, it must have the super hydrophilic characteristic of competence exertion under conditions of light irradiation；Second, the printing opacity of coating of titanium dioxide Property is poor, is not appropriate for being directly used in glass coating.
By comparison, the shield effectiveness of zinc oxide and titanium dioxide both when wavelength is less than 350 nanometers is close, but When between 350~400nm, the shield effectiveness of zinc oxide is apparently higher than titanium dioxide.Simultaneous oxidation zinc is 1.9 to the refractive index of light Refractive index 2.6 less than titanium dioxide to light, diffusing reflection of the zinc oxide to light is relatively low, and it can improve the printing opacity of transparent article Rate.In addition, it also has good chemical stability in water environment, the super hydrophilic painting of transparent glass surface is highly suitable as Layer.But the contact angle due to nano zine oxide in itself is about 60 ° or so, wants to play its super hydrophilicity, need also exist for It could be realized under illumination condition.
On the other hand, now widely used glass, such as vehicle glass, building glass use silicate material system Into especially, sandwich-type silicate glass typically being used to improve glass impact strength for the windshield of automobile.So And this kind of silicate interlayer glass light is high according to transmitance, especially in Summer High-Temperature Times, high intensity visible light-transmissive automotive front baffle folder Layer glass, not only hinders driver's sight, causes visual fatigue, cause binocular dizzy, and increase drives risk, moreover, strong Infrared emanation can also improve vehicle interior temperature, the living load that increase on-board air conditioner is brought, be unfavorable for automobile to energy-saving and environmental protection side To sustainable development.
In view of the above problems, it is special to propose this invention.
The content of the invention：
The technical problems to be solved by the invention are to be directed to above-mentioned technical problem existing for existing hydrophilic glass, there is provided a kind of It is that use condition is not limited by illumination, have good super hydrophilic characteristic, visible light transmissivity high and can absorb infrared and ultraviolet Super hydrophilic dose of radiation.The present invention also provides a kind of super hydrophilic dose of preparation method, and inner surface coated with super hydrophilic simultaneously The super hydrophilic glass for vehicle window of coating.
The technical scheme adopted by the invention to solve the technical problem is that：It is a kind of super hydrophilic dose, it is characterised in that by following Component forms：0.1~0.45wt% zinc oxide nano rod, 1.5~5wt% carbon nanotube dust, 12~18wt% N, Dinethylformamide, surplus are dispersion liquid；The carbon nanotube dust is the single wall or multi-walled carbon nanotube of powder shaped, described CNT is attached to the surface of zinc oxide nano rod.
Further, the length of the zinc oxide nano rod is 10~20um, a diameter of 100~1000nm.
Further, the length of the CNT is 0.1~5um, a diameter of 1~3nm.
Further, the wall number of the CNT is 1~5.
Further, the dispersion liquid is 5~8 by volume ratio:1 dispersant and concentrated acid solution composition.
Further, the dispersant is at least one of ethanol, isopropanol and n-hexyl alcohol.
Further, the concentrated acid solution is 3~5 by volume ratio:1 concentrated sulfuric acid solution and concentrated nitric acid solution composition.
Further, the Solute mass fraction of the concentrated sulfuric acid solution is more than 90%, the solute matter of the concentrated nitric acid solution Measure fraction and be more than 60%.
Further, the CNT is attached to the surface formation Wolf tooth bar structure of the zinc oxide nano rod, institute Stating Wolf tooth bar structure includes the trunk portion formed by the zinc oxide nano rod and the spine formed by the CNT Part.
The present invention also provides super hydrophilic dose of preparation method described in any of the above simultaneously, it is characterised in that including as follows Step：Step 10：Prepare zinc oxide nano rod；Step 20：0.1~0.45wt% zinc oxide nano rod is dissolved into 12~ In 18wt% DMF, zinc oxide colloidal sol is made；Step 30：It is 5~8 by volume ratio:1 dispersant and strong Acid solution is mixed to form dispersion liquid, then adds 1.5~5wt% carbon nanotube dust, and the pH value for making solution is 2~4, then 1~3h is stirred at 25~30 DEG C, it is well mixed to obtain carbon nano tube dispersion liquid；Step 40：By carbon nanometer made from step 30 Pipe dispersion liquid is gradually added into zinc oxide colloidal sol made from the step 20 being stirred continuously, and is then aged 10~24h, is formed super hydrophilic Agent.
Further, the preparation method of zinc oxide nano rod described in step 10 comprises the following steps：Step 11：By two water Close zinc acetate and triammonium citrate is added in absolute ethyl alcohol, in temperature T1Lower condensing reflux is simultaneously stirred continuously and makes its dissolving, then In temperature T after cooling2Under it is stored refrigerated, be made precursor solution；Step 12：Sodium hydroxide is added in absolute ethyl alcohol, room temperature Lower ultrasonic dissolution t for a period of time1, obtain the ethanol solution of sodium hydroxide；Step 13：Then by sodium hydroxide made from step 12 Ethanol solution add into precursor solution made from step 11, the ethanol solution of the sodium hydroxide and the presoma are molten The volume ratio of liquid is 1~1.2:2.4~3.6, in temperature T3Water bath in sustained response t for a period of time2, through ultrasound, from The heart, after cleaning 3~5 times, dry at room temperature, zinc oxide nano rod is made.
Further, the T1For 80~100 DEG C, T2For 2~5 DEG C, T3For 60~80 DEG C, t1For 30~60min, t2For 180~300min.
Further, in a step 11, the mass ratio of the Zinc diacetate dihydrate, Triammonium citrate and absolute ethyl alcohol is 10 ~15:0.8~1.2:110~150；In step 12, the mass ratio of the sodium hydroxide and absolute ethyl alcohol is 1~1.5:200 ~400.
The present invention also provides a kind of super hydrophilic glass for vehicle window, it is characterised in that：Including glass substrate and by above-mentioned super hydrophilic Dosage form into super-hydrophilic coating, the super-hydrophilic coating is arranged on the in-car inner surface of direction of the glass substrate.
Further, the thickness of the super-hydrophilic coating is 10~40um.
Further, the super hydrophilic dosage form is into the method for super-hydrophilic coating, by being sprayed on the glass substrate table Super-hydrophilic coating is coated on face, the spraying temperature is 20~27 DEG C, and spraying humidity is 36~52%；Then infrared surface drying is used And drying, surface drying temperature are 20~70 DEG C, surface drying time is 20~50min, and drying temperature is 125~130 DEG C, and drying time is 80~120min.
Further, the super hydrophilic dosage form is into the method for super-hydrophilic coating, by being sprayed on the glass substrate table Super-hydrophilic coating is coated on face, the spraying temperature is 20~27 DEG C, and spraying humidity is 36~52%；Then infrared surface drying is used And drying, surface drying temperature are 20~70 DEG C, surface drying time is 20~50min, and drying temperature is 125~130 DEG C, and drying time is 80~120min；Then put it into heating furnace, be warming up to 125 DEG C and be incubated, the heating-up time is 30~60min, during insulation Between be 100min；Then 480 DEG C are warming up to again, heating-up time 150min；It is finally cooled to room temperature.
Due to taking above-mentioned technical proposal, it has the advantages that the present invention：
1) present invention for zinc oxide be used as coating material face by illumination conditionality, by CNT and zinc oxide Nanometer rods are compound, are prepared for a kind of super hydrophilic dose with mace microstructure, improve coating asperity, make oxidation Zinc equally has water-wet behavior under non-illumination condition；
2) combining CNT and zinc oxide itself has the strong absorbability of good infrared and ultraviolet radiation, in addition carbon nanometer Pipe also has excellent electric conductivity, this super-hydrophilic coating can also realize it is conductive, through visible ray and absorb the special work(of radiation Energy；
3) in the inner surface of super hydrophilic glass for vehicle window of the present invention, steam is concentrated according to the position of zinc oxide nano rod to be divided Cloth, it can be achieved according to the internal and external environment temperature difference, automatic adjusument visible light-transmissive intensity；And with good infrared absorption, corrosion resistant Erosion, chemical-resistance；
4) manufacture craft of this super hydrophilic dose and glass for vehicle window is simple, can scale processing, in future feature type glass Field has broad application prospects.
Brief description of the drawings：
Fig. 1 is a kind of partial schematic diagram of super hydrophilic glass for vehicle window of the present invention；
Fig. 2 is a kind of close-up schematic view of super-hydrophilic coating of the present invention；
Label declaration in accompanying drawing：1 is glass substrate, and 2 be super-hydrophilic coating, and 3 be CNT, and 4 be zinc oxide nano rod.
Embodiment：
Present disclosure is described further below in conjunction with accompanying drawing.
Super hydrophilic dose of one kind of the present invention, it is characterised in that be made up of following component：0.1~0.45wt% oxygen Change zinc nanometer rods, 1.5~5wt% carbon nanotube dust, 12~18wt% DMF, surplus is scattered Liquid；The carbon nanotube dust is the single wall or multi-walled carbon nanotube of powder shaped, and the CNT is preferably less wall carbon nano-tube Pipe, wall number is preferably 1~5, and the CNT 3 is attached to the surface of zinc oxide nano rod 4, preferably forms Wolf tooth bar knot Structure, the trunk portion of mace is zinc oxide nano rod, and the sharp portion of mace is divided into CNT, as shown in Figure 2.
Zinc oxide has excellent photocatalysis characteristic and transmitance, and has good heat endurance, absorbs infrared and ultraviolet Effect, it is highly suitable for being used as glass surface coating material, makes glass that there is excellent light transmittance, it is conductive, super hydrophilic and every purple The function such as outer.Because illumination condition limits, single Zinc oxide coating is difficult to realize super hydrophilic effect under conditions of non-illumination. Therefore the present invention is carried out compound using CNT with zinc oxide nano rod, by improving former cated asperity, with Improve hydrophilic ability of the coating under conditions of non-illumination.
According to Cassie-Baxter models, contact of the liquid with substrate surface is composite contact, i.e. drop and groove solid Between retention liquid or air be present, just easily produce capillarity when material has preferable hydrophilicity, adsorb in water wetted material Surface.Here we are compound with zinc oxide nano rod by carbon nano tube dispersion liquid, and then obtain wolf's fang rod type structure to strengthen oxygen Change the microscopic surface roughness of spelter coating.And CNT has very strong hydrophobic property in itself, zinc oxide has stronger parent It is water-based can, so extraneous moisture will be sent to around zinc oxide nano rod and concentrate certainly in the case where high potential energy acts on driving, and can be with Do not limited by illumination condition, expand the application scenario of zinc oxide super-hydrophilic coating and using duration.
On the other hand, there is the strong absorbability of good infrared and ultraviolet radiation with reference to CNT and zinc oxide itself, this Outer CNT also has excellent electric conductivity, this super-hydrophilic coating can also realize it is conductive, through visible ray and absorb radiation Specific function.
Further, the length of the zinc oxide nano rod is 10~20um, a diameter of 100~1000nm.The carbon is received The length of mitron is 0.1~5um, a diameter of 1~3nm.
Further, the dispersion liquid is 5~8 by volume ratio:1 dispersant and concentrated acid solution composition.The dispersant Preferably at least one of ethanol, isopropanol and n-hexyl alcohol.The concentrated acid solution is preferably that volume ratio is 3~5:1 dense sulphur Acid solution and concentrated nitric acid solution mixed liquor, the Solute mass fraction of the concentrated sulfuric acid solution are more than 90%, the concentrated nitric acid solution Solute mass fraction be more than 60%.
The present invention also provides super hydrophilic dose of preparation method described in more than one simultaneously, it is characterised in that including as follows Step：
Step 10：Prepare zinc oxide nano rod；
Step 20：0.1~0.45wt% zinc oxide nano rod is dissolved into 12~18wt% N, N- dimethyl formyls In amine, zinc oxide colloidal sol is made；
Step 30：It is 5~8 by volume ratio:1 dispersant and strong acid solution is mixed to form dispersion liquid, then add 1.5~ 5wt% carbon nanotube dust, the pH value for making solution are 2~4, and 1~3h is then stirred at 25~30 DEG C, well mixed to obtain Carbon nano tube dispersion liquid；
Step 40：Carbon nano tube dispersion liquid made from step 30 is gradually added into the obtained oxidation of the step 20 being stirred continuously In zinc colloidal sol, 10~24h is then aged, forms super hydrophilic dose.Wherein, wt% is weight percentage, and h is hour, described above The percentage by weight of each component refer to that it is accounted for super hydrophilic dose of part by weight be finally made.
Further, the preparation method of zinc oxide nano rod described in step 10 comprises the following steps：
Step 11：By Zinc diacetate dihydrate (Zn (OAc)2·2H2) and triammonium citrate ((NH4) O3C6H5O7) add it is anhydrous In ethanol, in temperature T1Lower condensing reflux is simultaneously stirred continuously and makes its dissolving, in temperature T after then cooling down2Under it is stored refrigerated, be made Precursor solution；Wherein, the mass ratio of Zinc diacetate dihydrate, Triammonium citrate and absolute ethyl alcohol is preferably 10~15:0.8~ 1.2:110~150, T1Preferably 80~100 DEG C, T2Preferably 2~5 DEG C,
Step 12：Sodium hydroxide is added in absolute ethyl alcohol, at room temperature ultrasonic dissolution t for a period of time1, obtain sodium hydroxide Ethanol solution；Wherein, t1The mass ratio of preferably 30~60min, sodium hydroxide and absolute ethyl alcohol is preferably 1~1.5:200 ~400.
Step 13：Then the ethanol solution of the sodium hydroxide is added into the precursor solution, the hydroxide The volume ratio of the ethanol solution of sodium and the precursor solution is 1~1.2:2.4~3.6, in temperature T3Water bath in hold Continuous reaction a period of time t2, after ultrasound, centrifugation, cleaning 3~5 times, dry at room temperature, zinc oxide nano rod be made.Wherein, T3Preferably 60~80 DEG C, t2Preferably 180~300min.
As shown in figure 1, the present invention also provides a kind of super hydrophilic glass for vehicle window simultaneously, it is characterised in that：Including glass substrate 1 With above-described super hydrophilic dosage form into super-hydrophilic coating 2, the super-hydrophilic coating 2 is arranged on the court of the glass substrate 1 To on the inner surface of in-car, the thickness of the super-hydrophilic coating is preferably 10~40um.The super-hydrophilic coating is by high transparency, conduction And the super hydrophilic dosage form of the ultraviolet infrared function of isolation is into making this glass have good heating defrosting-defogging and automatically cleaning work( Can, visual impact caused by easy accumulated snow frosting gives people under extreme climate so as to solving the problems, such as general glass, further Improve the driving safety performance of the transit equipments such as automobile.
In the present invention, the glass for vehicle window can be monolithic glass, laminated glass, vacuum glass, double glazing or its With reference to.The material of the glass for vehicle window is chosen as plate glass, float glass, quartz glass, borosilicate glass, calcium soda-lime glass Or plastics, it is special rigid plastics, preferably polyethylene, polypropylene, makrolon, polymethyl methacrylate, polystyrene, poly- Acid amides, polyester, polyvinyl chloride and/or their mixture.
The present invention is larger for nano zine oxide coating contact angle, and zinc oxide and CNT is compound, is prepared for one kind Super hydrophilic dose of wolf's fang rod type microstructure, it can make zinc oxide that equally there is super hydrophilic characteristic under non-illumination, due to carbon nanometer Pipe has hydrophobic oleophilic oil performance, and zinc oxide nano rod has hydrophilicity, so steam integrated distribution is on zinc oxide nano rod. This super-hydrophilic coating is applied into the inner surface in vehicle glass, the dirty separation of water can be realized by producing one kind, while be had concurrently good The functional glass of infrared absorption well, corrosion-resistant, chemically-resistant and anti-fog performance.This super hydrophilic dose and its functional glass system Preparation Method is simple, easily operated, easily realizes industrialized production, has in the antifog defrosting field of vehicle glass and building glass Wide application prospect.
The present invention can use spraying method, make described super hydrophilic dose to be atomized by pressure, be dispersed into uniform and thin Small droplet, the surface coated in substrate of glass.The spraying process humiture requirement：20~27 DEG C, (38~50) ± 2%. Then infrared surface drying and drying, surface drying temperature are used：20~70 DEG C, surface drying time about 20~50min, drying temperature 125~130 DEG C, drying time about 80~120min.
In order to further enhance the adhesion between super-hydrophilic coating 2 and glass substrate 1, it is necessary to continue to carry out hot place to it Reason.Heat treatment concretely comprises the following steps：The glass substrate 1 for being coated with super-hydrophilic coating 2 is put into heating furnace, is warming up to 125 DEG C And be incubated, the heating-up time is 30~60min, soaking time 100min；Then 480 DEG C are warming up to again, and the heating-up time is 150min；Room temperature is finally cooled to, super hydrophilic glass for vehicle window is made.Wherein, min is minute.
This glazing construction coated with super-hydrophilic coating is highly suitable as automobile front windshield, and it is except possessing Outside transparent, conductive, automatically cleaning, anti-infrared radiation function, it is strong also visible light-transmissive can adaptively to be adjusted according to vehicle internal-external temperature difference Degree.Its operation principle is to have benefited from the special microstructure of inner side coating Wolf tooth bar, and steam is concentrated along zinc oxide nano rod to be divided Cloth.In summer high temperature weather, in-car opens air-conditioning, and internal-external temperature difference is big, causes internal layer surface moisture content high, such visible ray exists It can repeatedly reflect, will greatly weaken through intensity of illumination through steam via during internal layer surface；And in the winter time or under overcast sky, Car internal-external temperature difference is relatively low, and inner surface moisture content is low, and such visible ray maintains normally to pass through intensity substantially, does not interfere with driver Member's normal driving.
The present invention is more at large illustrated below in conjunction with specific embodiment.
Embodiment 1：Super hydrophilic dose of preparation method
(1) preparation of nano zine oxide：By 1g Zinc diacetate dihydrates (Zn (OAc)2·2H2) and 0.1g triammonium citrates O ((NH4)3C6H5O7) add in 120ml absolute ethyl alcohols, condensing reflux and it is stirred continuously at a temperature of 90 DEG C and makes its dissolving, it is obtained The refrigerator that temperature is 3 DEG C is put in after solution cooling to preserve, and precursor solution is made；0.1g sodium hydroxides (NaOH) are added into 30ml In absolute ethyl alcohol, ultrasonic dissolution 40min (minute) for a period of time at room temperature, then by the ethanol of prepared 20ml sodium hydroxides Solution is added into the 60ml precursor solutions of preparation, the sustained response 4h for a period of time in temperature is 70 DEG C of water bath (hour), after ultrasound, centrifugation, cleaning 3~5 times, dry at room temperature, zinc oxide nano rod is made.
In the preparation method of zinc oxide nanometer rods described above, document may be referred to【The preparation of Korea Spro's cosmos nano zine oxides And application study [D] the Beijing Institute of Technology in terms of biology and photocatalysis, 2015】(Chinese master thesis full-text data Storehouse).To meet the needs of of the invention, the present invention carries out verification experimental verification on the basis of above-mentioned document announcement method, and to parameter and Reagent optimizes, and obtains the higher zinc oxide nano rod of surface-active.To save space, this is only incorporated in, but above-mentioned document All technologies disclose the part that also should be regarded as the exposure of the present patent application technology.
(2) prepared by nano-zinc oxide sol：Zinc oxide nano rod described in 0.1g is added to 16ml N, N- dimethyl formyls In amine, dissolving 45min is continuously stirred, zinc oxide colloidal sol is made.
(3) super hydrophilic dose of preparation：3g CNTs are added into the 3ml concentrated sulfuric acids/concentrated nitric acid mixed acid solution, and (volume ratio is 3：1) in, regulation pH value is 3~4, is then added into 50ml alcohol dispersants and forms carbon nano tube dispersion liquid, finally by carbon Nanotube dispersion liquid is gradually added into the zinc oxide colloidal sol being stirred continuously, and is then aged 20h.
Then spraying method is used, makes described super hydrophilic dose to be atomized by pressure, is dispersed into uniform and tiny mist Drop, the surface coated in substrate of glass.The spraying process humiture requirement：20~27 DEG C, (38~50) ± 2%.Then adopt With infrared surface drying and drying, surface drying temperature：20~70 DEG C, surface drying time about 20~50min, 125~130 DEG C of drying temperature, dry About 80~120min of dry time.
In preparation method described above, in order to further enhance the adhesion between super-hydrophilic coating 2 and glass substrate 1, Need to continue to be heat-treated it.Heat treatment concretely comprises the following steps：The glass substrate 1 for being coated with super-hydrophilic coating 2 is put into In heating furnace, it is warming up to 125 DEG C and is incubated, the heating-up time is 30~60min, soaking time 100min；Then it is warming up to again 480 DEG C, heating-up time 150min；Room temperature is finally cooled to, super hydrophilic glass for vehicle window is made.On the super hydrophilic glass for vehicle window The contact angle of water droplet is 5 °, light transmittance 89%.
Above content has been carried out specifically to super hydrophilic dose of one kind, preparation method and super hydrophilic glass for vehicle window of the present invention Description, but the present invention is not limited to by specific embodiments described above content, so all technologies according to the present invention will Any improvement, equivalent modifications and replacement that point is carried out etc., belongs to the scope of protection of the invention.

Claims (17)

  1. It is 1. a kind of super hydrophilic dose, it is characterised in that to be made up of following component：0.1~0.45wt% zinc oxide nano rod, 1.5 ~5wt% carbon nanotube dust, 12~18wt% DMF, surplus are dispersion liquid；The CNT Powder is the single wall or multi-walled carbon nanotube of powder shaped, and the CNT is attached to the surface of zinc oxide nano rod.
  2. 2. super hydrophilic dose according to claim 1, it is characterised in that：The length of the zinc oxide nano rod be 10~ 20um, a diameter of 100~1000nm.
  3. 3. super hydrophilic dose according to claim 1, it is characterised in that：The length of the CNT is 0.1~5um, directly Footpath is 1~3nm.
  4. 4. super hydrophilic dose according to claim 1, it is characterised in that：The wall number of the CNT is 1~5.
  5. 5. super hydrophilic dose according to claim 1, it is characterised in that：The dispersion liquid is 5~8 by volume ratio:1 it is scattered Agent and concentrated acid solution composition.
  6. 6. super hydrophilic dose according to claim 5, it is characterised in that：The dispersant is ethanol, isopropanol and n-hexyl alcohol At least one of.
  7. 7. super hydrophilic dose according to claim 5, it is characterised in that：The concentrated acid solution is 3~5 by volume ratio:1 it is dense Sulfuric acid solution and concentrated nitric acid solution composition.
  8. 8. super hydrophilic dose according to claim 7, it is characterised in that：The Solute mass fraction of the concentrated sulfuric acid solution is more than 90%, the Solute mass fraction of the concentrated nitric acid solution is more than 60%.
  9. 9. super hydrophilic dose according to claim 1, it is characterised in that：The CNT is attached to the zinc-oxide nano The surface of rod forms Wolf tooth bar structure, the Wolf tooth bar structure include the trunk formed by the zinc oxide nano rod and by The spine that the CNT is formed.
  10. 10. any super hydrophilic dose described of the preparation method of a kind of claim 1~9, it is characterised in that comprise the following steps：
    Step 10：Prepare zinc oxide nano rod；
    Step 20：0.1~0.45wt% zinc oxide nano rod is dissolved into 12~18wt% DMF, Zinc oxide colloidal sol is made；
    Step 30：It is 5~8 by volume ratio:1 dispersant and strong acid solution is mixed to form dispersion liquid, then add 1.5~ 5wt% carbon nanotube dust, the pH value for making solution are 2~4, and 1~3h is then stirred at 25~30 DEG C, well mixed to obtain Carbon nano tube dispersion liquid；
    Step 40：It is molten that carbon nano tube dispersion liquid made from step 30 is gradually added into zinc oxide made from the step 20 being stirred continuously In glue, 10~24h is then aged, forms super hydrophilic dose.
  11. 11. preparation method according to claim 10, it is characterised in that the preparation of zinc oxide nano rod described in step 10 Method comprises the following steps：
    Step 11：Zinc diacetate dihydrate and triammonium citrate are added in absolute ethyl alcohol, in temperature T1Lower condensing reflux simultaneously constantly stirs Mixing makes its dissolving, in temperature T after then cooling down2Under it is stored refrigerated, be made precursor solution；
    Step 12：Sodium hydroxide is added in absolute ethyl alcohol, at room temperature ultrasonic dissolution t for a period of time1, obtain the second of sodium hydroxide Alcoholic solution；
    Step 13：Then the ethanol solution of sodium hydroxide made from step 12 is added to precursor solution made from step 11 In, the volume ratio of the ethanol solution of the sodium hydroxide and the precursor solution is 1~1.2:2.4~3.6, in temperature T3's Sustained response t for a period of time in water bath2, after ultrasound, centrifugation, cleaning 3~5 times, dry at room temperature, zinc oxide be made Nanometer rods.
  12. 12. preparation method according to claim 11, it is characterised in that：The T1For 80~100 DEG C, T2For 2~5 DEG C, T3 For 60~80 DEG C, t1For 30~60min, t2For 180~300min.
  13. 13. preparation method according to claim 11, it is characterised in that：In a step 11, the Zinc diacetate dihydrate, lemon The mass ratio of lemon three ammoniums of acid and absolute ethyl alcohol is 10~15:0.8~1.2:110~150；In step 12, the sodium hydroxide Mass ratio with absolute ethyl alcohol is 1~1.5:200~400.
  14. A kind of 14. super hydrophilic glass for vehicle window, it is characterised in that：Surpass including glass substrate and by claim 1~9 is any described The super-hydrophilic coating that hydrophilizing agent is formed, the super-hydrophilic coating are arranged on the inner surface of direction in-car of the glass substrate.
  15. 15. super hydrophilic glass for vehicle window according to claim 14, it is characterised in that：The thickness of the super-hydrophilic coating is 10 ~40um.
  16. 16. super hydrophilic glass for vehicle window according to claim 14, it is characterised in that：The super hydrophilic dosage form is into super hydrophilic painting The method of layer is to coat super-hydrophilic coating by being sprayed on the glass baseplate surface, and the spraying temperature is 20~27 DEG C, It is 36~52% to spray humidity；Then infrared surface drying and drying are used, surface drying temperature is 20~70 DEG C, surface drying time is 20~ 50min, drying temperature are 125~130 DEG C, and drying time is 80~120min.
  17. 17. super hydrophilic glass for vehicle window according to claim 14, it is characterised in that：The super hydrophilic dosage form is into super hydrophilic painting The method of layer is to coat super-hydrophilic coating by being sprayed on the glass baseplate surface, and the spraying temperature is 20~27 DEG C, It is 36~52% to spray humidity；Then infrared surface drying and drying are used, surface drying temperature is 20~70 DEG C, surface drying time is 20~ 50min, drying temperature are 125~130 DEG C, and drying time is 80~120min；Then put it into heating furnace, be warming up to 125 DEG C and it is incubated, the heating-up time is 30~60min, soaking time 100min；Then 480 DEG C are warming up to again, and the heating-up time is 150min；It is finally cooled to room temperature.
CN201710738847.3A 2017-08-25 2017-08-25 A kind of super hydrophilic dose, preparation method and super hydrophilic glass for vehicle window Pending CN107445487A (en)

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Application publication date: 20171208