A kind of super-hydrophobic glass coating and preparation method thereof
Technical field
The present invention relates to glass surface masking technique field, specifically a kind of super-hydrophobic glass coating and preparation method thereof.
Background technology
Water contact angle has a hydrophobicity more than 90 ° of body surface, and water contact angle more than 150 ° when body surface
With super-hydrophobicity, super hydrophobic surface not only hydrophobic also oleophobic.With the progress of modern science and technology, increasing electronical display is produced
Product use touch-screen, and at present, capacitive touch screen turns into the touch screen technology of global main flow, the outermost lid of capacitive touch screen
Glass sheet then turns into one of critical material of touch-screen.Fingerprint, greasy dirt when regrettably, using product on hand, sweat
Screen surface can be remained in unavoidably, the rapid decline of readability of touch panel is not only resulted in, vision is influenceed, and also reduce equipment
Availability.
To solve this problem, presently mainly using the technology in glass surface coating anti-fingerprint paint, the master of coating
Want the fluorosilicone compound that composition is mostly low-surface-energy.It is residual on glass that this method can reduce fingerprint, water stain, greasy dirt
Stay, the spot of adhesion and fingerprint is easily cleared up, because coating property and operating procedure are limited, coating is not durable and effect is inadequate
Significantly.《Anti-fingerprint film and preparation method thereof》(Patent No. ZL201310300953.5)Existed using magnetron sputtering and vacuum evaporation
Substrate surface is sequentially depositing silicon oxide layer and fluoride layer, and film layer is about 110 °, product appearance is easy to clear with the contact angle of water
Clean greasy dirt, fingerprint.
The content of the invention
It is an object of the invention to provide a kind of super-hydrophobic glass coating and preparation method thereof, the contact angle of the coating and water
More than 150 °, anti-fingerprint, oil-stain-preventing and hydrophobic effect are improved, and translucency and scratch resistance can be strengthened.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of super-hydrophobic glass coating and preparation method thereof, including the nanoporous glass of glass surface is in turn attached to from the inside to the outside
Glass film and low-surface-energy hydrophobic membrane, the thickness of nano-porous glass film is 150~1000nm, the hole chi of nano-porous glass film
Very little is 1~100nm;Low-surface-energy hydrophobic membrane is the siloxanes or fluorinated siloxane of 1~20nm of thickness, low-surface-energy hydrophobic membrane
Surface can be less than 40mN/m, and low-surface-energy hydrophobic membrane is attached to outer surface and the nano-porous glass film of nano-porous glass film
The inwall of hole.
Further, amorphous silicon oxide, 0~12% of the nano-porous glass film comprising molar fraction 80~100%
Boron oxide and 0~8% sodium oxide molybdena.
Further, the amorphous silicon oxide of the nano-porous glass film comprising molar fraction 86~98%, 0~8%
Boron oxide and 0~6% sodium oxide molybdena;The thickness of nano-porous glass film is 200~800nm, the hole chi of nano-porous glass film
Very little is 1~60nm;Low-surface-energy hydrophobic membrane is the siloxanes or fluorinated siloxane of 1~15nm of thickness, low-surface-energy hydrophobic membrane
Surface can be less than 30mN/m.
Further, the amorphous silicon oxide of the nano-porous glass film comprising molar fraction 90~95%, 0~5%
Boron oxide and 0~5% sodium oxide molybdena;The thickness of nano-porous glass film is 300~500nm, the hole chi of nano-porous glass film
Very little is 5~60nm;Low-surface-energy hydrophobic membrane is the siloxanes or fluorinated siloxane of 5~10nm of thickness, low-surface-energy hydrophobic membrane
Surface can be less than 20mN/m.
The present invention also provides a kind of preparation method of super-hydrophobic glass coating, comprises the following steps:
S1, cleaning glass substrate;
S2, it is coated with glass film on the glass substrate using vacuum radio frequency magnetron sputtering technique, sputtering target material uses quality percentage
The mixing target that silica, 9~14% sodium oxide molybdena and 18~24% boron oxide than 65~78% are constituted;
S3, the glass film that will be obtained are heat-treated, and make the abundant split-phase of glass film;
S4, by the glass film after split-phase by obtaining nano-porous glass film after pickling;
S5, nano-porous glass film is dried into 1~2h in 120~200 DEG C of air, then less than 5 × 10-2The air pressure of Pa
Under vacuumize 5~20min, nano-porous glass film is immersed in low-surface-energy 15~30min of organic solution under negative pressure afterwards,
It is last to dry 30~60min at 60~120 DEG C, obtain super-hydrophobic glass coating of the invention;The low-surface-energy organic solution
It is siloxane solution or fluorinated siloxane solution.
Further, then the step S1 uses body using ethanol and deionized water successively ultrasonic glass cleaning substrate
Product compares 3:1 98% concentrated sulfuric acid and 30% hydrogen peroxide mixed solution treatment glass substrate, make glass substrate have cleaning, be easy to deposition
With the surface being bonded.
Further, 300~400 DEG C of vacuum chamber depositing temperature in the step S2 vacuum radio frequency magnetron sputtering techniques.
Further, 500~700 DEG C of the step S3 heat treatment temperatures, 30~360min of heat treatment time.
Further, the acid that the step S4 is mixed in equal volume using 0.5mol/L hydrofluoric acid with 0.1mol/L ammonium fluorides
Solution carries out pickling to glass film, using supersonic oscillations and heating water bath as subsidiary conditions, water bath heating temperature during pickling
To 70 DEG C, supersonic oscillations frequency 40KHz, time 15min.
Further, the step S4 is using 0.1mol/L nitric acid, 0.5mol/L hydrofluoric acid and 0.1mol/L ammonium fluorides etc.
The acid solution of volume mixture carries out pickling to glass film, using supersonic oscillations and heating water bath as subsidiary conditions during pickling,
Water bath heating temperature is to 90 DEG C, supersonic oscillations frequency 40KHz, time 20min.
The beneficial effects of the invention are as follows, low-surface energy substance is coated on nano level rough porous glass-film surface, make water
Contact angle reaches more than 150 °, such that it is able to obtain super hydrophobic surface, improves anti-fingerprint, oil-stain-preventing and hydrophobic effect;Low surface
Whole volumetric spaces of the energy material full of cellular glass membrane pores, even if top layer abrasion still has same ultra-hydrophobicity.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples:
Fig. 1 is structural representation of the invention.
Specific embodiment
As shown in figure 1, the present invention provides a kind of super-hydrophobic glass coating and preparation method thereof, including it is attached successively from the inside to the outside
The nano-porous glass film 2 and low-surface-energy hydrophobic membrane 3 on the surface of glass 1, the thickness of nano-porous glass film 2 for 150~
1000nm, the pore-size of nano-porous glass film 2 is 1~100nm;Low-surface-energy hydrophobic membrane 3 is the silica of 1~20nm of thickness
Alkane or fluorinated siloxane, the surface of low-surface-energy hydrophobic membrane 3 can be less than 40mN/m, and siloxanes or fluorinated siloxane are attached to nanometer
The outer surface of SPG membrane 2 and the inwall of nano-porous glass membrane pores 2a;As preferred, nano-porous glass film 2
Amorphous silicon oxide comprising molar fraction 80~100%, 0~12% boron oxide and 0~8% sodium oxide molybdena.
On the basis of more than, nano-porous glass film 2 can also be the amorphous comprising molar fraction 86~98%
Silicon, 0~8% boron oxide and 0~6% sodium oxide molybdena;The thickness of nano-porous glass film 2 is 200~800nm, nanoporous glass
The pore-size of glass film 2 is 1~60nm;Low-surface-energy hydrophobic membrane 3 is the siloxanes or fluorinated siloxane of 1~15nm of thickness, low
The surface of surface energy hydrophobic membrane 3 can be less than 30mN/m.
Used as further preferred scheme, nano-porous glass film 2 can be that the nothing comprising molar fraction 90~95% is determined
Conformal silicon oxide, 0~5% boron oxide and 0~5% sodium oxide molybdena;The thickness of nano-porous glass film 2 is 300~500nm, nanometer
The pore-size of SPG membrane 2 is 5~60nm;Low-surface-energy hydrophobic membrane 3 is the siloxanes or fluorination silica of 5~10nm of thickness
Alkane, the surface of low-surface-energy hydrophobic membrane can be less than 20mN/m.
The present invention also provides a kind of preparation method of super-hydrophobic glass coating, is specifically shown in following examples:
Embodiment one
A kind of preparation method of super-hydrophobic glass coating, comprises the following steps:
S1, using ethanol and deionized water successively ultrasonic wave clean aluminosilicate glass substrates 10min, then with volume ratio 3:1
98% concentrated sulfuric acid and 30% hydrogen peroxide mixed solution treatment glass substrate 15min, make glass substrate 1 have it is clean, be easy to deposition
With the surface being bonded;
S2, it is coated with glass film on the glass substrate using vacuum radio frequency magnetron sputtering technique, sputtering target material uses quality percentage
The mixing target that silica, 9~14% sodium oxide molybdena and 18~24% boron oxide than 65~78% are constituted;Vacuumized before sputtering
To 4 × 10-4Pa, glass substrate is heated to 350 DEG C, argon flow amount 50sccm, sputtering power 450W, sputtering time 15min;
S3, the glass film that will be obtained 500 DEG C of 1 h of heat treatment in chamber type electric resistance furnace, make the abundant split-phase of glass film;
S4, the acid solution mixed in equal volume with 0.1mol/L ammonium fluorides using 0.5mol/L hydrofluoric acid are to the glass thin after split-phase
Film carries out pickling, using supersonic oscillations and heating water bath as subsidiary conditions, water bath heating temperature to 70 DEG C, ultrasonic wave during pickling
Frequency of oscillation 40KHz, time 15min, obtain nano-porous glass film 2;
S5, nano-porous glass film is dried into 1~2h in 120~200 DEG C of air, then less than 5 × 10-2The air pressure of Pa
Under vacuumize 20min, nano-porous glass film is immersed in low-surface-energy organic solution 15min, low surface under negative pressure afterwards
Energy organic solution is the dimethyl silicone polymer solution that mass concentration is 4%, finally dries 60min at 80 DEG C, obtains of the invention
Super-hydrophobic glass coating.
Nano-porous glass thicknesses of layers is 300nm, 5~50nm of pore size, silicon in obtained super-hydrophobic glass coating
Siloxane film thickness is 8nm;Draining test is done with 5 microlitres of water, three measurement average values of water droplet contact angle are 161 °, it is seen that light printing opacity
Rate is 94%.
Embodiment two
A kind of preparation method of super-hydrophobic glass coating, comprises the following steps:
S1, using ethanol and deionized water successively ultrasonic wave clean quartz glass substrate 15min, then with volume ratio 3:The 98% of 1
The concentrated sulfuric acid and 30% hydrogen peroxide mixed solution treatment glass substrate 20min, make glass substrate 1 have cleaning, are easy to deposition and are bonded
Surface;
S2, it is coated with glass film on the glass substrate using vacuum radio frequency magnetron sputtering technique, sputtering target material uses quality percentage
The mixing target that silica, 9~14% sodium oxide molybdena and 18~24% boron oxide than 65~78% are constituted;Vacuumized before sputtering
To 4 × 10-4Pa, glass substrate is heated to 200 DEG C, argon flow amount 40sccm, sputtering power 400W, sputtering time 10min;
S3, the glass film that will be obtained 700 DEG C of heat treatment 3h in chamber type electric resistance furnace, make the abundant split-phase of glass film;
S4, the acid solution pair mixed in equal volume with 0.1mol/L ammonium fluorides using 0.1mol/L nitric acid, 0.5mol/L hydrofluoric acid
Glass film after split-phase carries out pickling, using supersonic oscillations and heating water bath as subsidiary conditions, heating water bath temperature during pickling
To 90 DEG C, supersonic oscillations frequency 40KHz, time 20min obtain nano-porous glass film 2 to degree;
S5, nano-porous glass film is dried into 1~2h in 120~200 DEG C of air, then less than 5 × 10-2The air pressure of Pa
Under vacuumize 15min, nano-porous glass film is immersed in low-surface-energy organic solution 20min, low surface under negative pressure afterwards
Energy organic solution is the ten trifluoro octyl group triethyl group siloxane solutions that mass concentration is 2%, finally dries 40min at 100 DEG C, is obtained
To super-hydrophobic glass coating of the invention.
Nano-porous glass thicknesses of layers is 500nm, 15~30nm of pore size, silicon in obtained super-hydrophobic glass coating
Siloxane film thickness is 10nm;Draining test is done with 5 microlitres of water, three measurement average values of water droplet contact angle are 168 °, it is seen that light is saturating
Light rate is 95%.
The above, is only presently preferred embodiments of the present invention, and any formal limitation is not made to the present invention;Appoint
What those of ordinary skill in the art, in the case where technical solution of the present invention ambit is not departed from, all using the side of the disclosure above
Method and technology contents make many possible variations and modification, or the equivalent reality for being revised as equivalent variations to technical solution of the present invention
Apply example.Therefore, every content without departing from technical solution of the present invention, is done according to technical spirit of the invention to above example
Any simple modification, equivalent, equivalence changes and modification, still fall within the range of technical solution of the present invention protection.