CN102951850B - Preparation method of chemical toughened glass product with wearing-resisting film - Google Patents
Preparation method of chemical toughened glass product with wearing-resisting film Download PDFInfo
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- CN102951850B CN102951850B CN201210484873.5A CN201210484873A CN102951850B CN 102951850 B CN102951850 B CN 102951850B CN 201210484873 A CN201210484873 A CN 201210484873A CN 102951850 B CN102951850 B CN 102951850B
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- glass
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- wear
- toughened glass
- thin film
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- 239000005341 toughened glass Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000126 substance Substances 0.000 title abstract description 15
- 239000011521 glass Substances 0.000 claims abstract description 40
- 238000005342 ion exchange Methods 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000001816 cooling Methods 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000010409 thin film Substances 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims description 10
- 238000004140 cleaning Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910001414 potassium ion Inorganic materials 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000006123 lithium glass Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 3
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 21
- 238000005496 tempering Methods 0.000 abstract description 13
- 238000005452 bending Methods 0.000 abstract description 4
- 238000007747 plating Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 238000007373 indentation Methods 0.000 description 12
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 11
- 239000010410 layer Substances 0.000 description 10
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 9
- 239000005357 flat glass Substances 0.000 description 9
- 230000035882 stress Effects 0.000 description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000005361 soda-lime glass Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 238000013001 point bending Methods 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000004323 potassium nitrate Substances 0.000 description 5
- 238000007669 thermal treatment Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 235000010344 sodium nitrate Nutrition 0.000 description 4
- 239000004317 sodium nitrate Substances 0.000 description 4
- 229940001516 sodium nitrate Drugs 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000006018 Li-aluminosilicate Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- VEUACKUBDLVUAC-UHFFFAOYSA-N [Na].[Ca] Chemical compound [Na].[Ca] VEUACKUBDLVUAC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- -1 tetraethoxy Chemical compound 0.000 description 1
- 238000009997 thermal pre-treatment Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Abstract
The invention discloses a preparation method of a chemical toughened glass product with a wearing-resisting film. The preparation method comprises the following steps of: (1), plating an oxide film on the surface of the clean glass product so as to obtain the glass product with a wearing-resisting coating; and (2), putting the glass product (obtained in the first step) with the wearing-resisting coating into molten salt, carrying out ion exchange to be strengthened for 8-18 hours at 400-500 DEG C, and subsequently cooling to the room temperature and washing so as to obtain the chemical toughened glass product. According to the method, the particularly prepared molten salt is adopted for ion exchange and tempering, the wearing-resisting coating with high hardness is combined with the surface of the glass product more tightly, and a part of surface crack can also be healed, so that the surface hardness and the anti-bending strength of the product are improved, and the application field of the chemical toughened glass product is expanded.
Description
Technical field
The invention belongs to glass surface treatment technical field, be specifically related to a kind of preparation method with the chemically toughened glass goods of wear-resistance thin film.
Background technology
The actual working strength of simple glass is very low, is slightly collided and impacts, and just cracks or fragmentation.For this hard brittle material of glass, bending strength can reflect its mechanical property level.Test result shows: the average bending strength of normal silicate glass is lower than 100Mpa.But calculate according to the chemical bond strength of glass, at least high several order of magnitude of its theoretical bending strength.Current research thinks this mainly because a large amount of Griffith flaw existed of surface damage and its surface produced at glasswork, transport and produce in storage process causes.
Chemically toughened glass by carrying out ion-exchange, the K that namely fused salt Ionic Radius is larger in fused salt
+or Na
+the Na less with the radius of surface layer of glass
+or Li
+carry out ion-exchange and form bearing stress layer on top layer generation " jammed effect ", thus reduce the impact of surface crack, make the intensity of glasswork improve 3 ~ 6 times, higher than the increase rate of physical toughened 1 ~ 2 times.But in use, because chemically toughened glass compressive stress layer is thinner, be usually less than 50 μm, its Surface stress layer is easily rubbed or is impacted the scar destruction producing and run through, and causes the intensity of chemically toughened glass significantly to reduce.
For obtaining the strong chemically toughened glass goods of damage resistant ability, be currently suggested some ways: first method uses ion-exchange speed glass kind and the fused salt mated (as: lithium aluminosilicate glass and SODIUMNITRATE fused salt) faster, the ion-exchange of short period just obtains the product of the stressor layers degree of depth more than 200 μm, and this just avoids the 40-50 μm of degree of depth of the usual easy damaged of glass surface.Publication number is the toughened glass that the Chinese patent application of CN1886348B discloses a kind of Lithia-alumina-silica containing, carries out the ion exchange depth that more than ion-exchange 8h can obtain more than 150 μm in SODIUMNITRATE fused salt.This is because lithium ion radius is 60pm, and the radius of sodium ion is 95pm, and potassium ion radius is 133pm.The radius of sodium ion is less than the radius of potassium ion, and sodium ion is less than potassium ion the energy that lithium ion cements out needs and displaces energy required for sodium ion from glass, therefore can obtain thicker tempering layer at a lower temperature quickly.But relative to being most commonly used to the soda-lime glass of chemical tempering, this method needs to use expensive lithium glass, limits range of application.
Second method is the glass surface covered with protective film after chemical tempering; this method is very wide in range in the application of simple glass; and the film of high hardness covered can not only improve wear resistance; repair owing to having carried out part to the Griffith flaw of glass article surface simultaneously; also improve the intensity of glass, decrease the dispersiveness of intensity.But due to chemically toughened glass goods can not be in for a long time wear-resistance thin film solidification required for the high temperature of more than 300 DEG C, limit wear-resistance thin film kind performance and process of preparing.
Muneo Watanabe etc. discloses the another kind of method (US Patent:4021218) preparing scrape resistant glasswork for 1975.Different from above-mentioned second method, the method first will by certain thin film preparation process by wear-resisting oxide-coated at soda-lime glass product surface, and then by KCl-KNO
3or K
2sO
4-KNO
3highly concentrated solution be sprayed on the surface of glasswork and carry out thermal pretreatment at about 130 DEG C, afterwards glasswork is placed in and carries out ion-exchange enhancing a little less than at glass softening point temperature, after cooling cleaning, the product surface stress of final acquisition can reach 110Mpa, and ion exchange depth can reach about 16 μm.But when adopting the method, the thickness of film is restricted, very poor more than ion-exchange effect after 15nm, and tempering layer thickness reduces rapidly, and the strength enhancing limited extent of glass after chemical tempering.
Summary of the invention
The invention provides a kind of preparation method with the chemically toughened glass goods of wear-resistance thin film, the chemically toughened glass product surface hardness that this preparation method obtains and flexural strength high, it is large that surface ion exchanges the degree of depth, has excellent wear resisting property.
There is a preparation method for the chemically toughened glass goods of wear-resistance thin film, comprise the steps:
(1) sull is plated at glass article surface;
(2) on plated surface step (1) obtained, the glasswork of sull is placed in metal fused salt, after carrying out ion-exchange strengthening 8-18h at 400-500 DEG C, cooling, takes out cleaning, obtains the described chemically toughened glass goods with wear-resistance thin film;
The weight percent of the metal fused salt described in step (2) is composed as follows:
The present invention first prepares wear-resistant coating at simple glass product surface, then the fused salt of special preparation is used to carry out ion-exchange tempering, this can make the wear-resistant coating of high rigidity be combined finer and close with glass article surface, and can also heal part surface crackle, improves the dispersiveness of product strength.Simultaneously, coated glass article carries out chemical tempering in the fused salt of particular design can make the motivating force of ion-exchange larger, even if time the thickness of wear-resistant coating reaches 1 μm, still larger ion exchange depth can be obtained, therefore the chemically toughened glass goods obtained have higher surface hardness and flexural strength simultaneously, and wear resisting property is excellent.
In described fused salt, saltpetre and SODIUMNITRATE are as the ion source of ion-exchange, salt of wormwood and sodium carbonate are fused to fused salt, its carbanion and the high price foreign ion affecting velocity of ion exchange formed not fusant by Alpha-alumina and diatomite adsorb, sodium hydroxide and potassium hydroxide cut off the passage that surface portion siloxane bond forms more ion-exchange, accelerate whole ion exchange process.
As preferably, described glasswork for containing lithium glass, carries out lithium sodium ion exchange with fused salt and strengthens;
The weight percent of described metal fused salt is composed as follows:
described contains lithium glass more preferably lithium aluminosilicate glass.
Now, containing lithium ion in described glasswork, dominant cation composition in described fused salt is sodium ion, the magnitude difference of the ionic radius of sodium ion and lithium ion is suitable, " jammed effect " can be produced by ion-exchange and form Surface stress layer, and required energy is less, larger surface stress can be obtained at a lower temperature.
As other preferred, described glasswork for containing soda glass, carries out sodium potassium ion with fused salt and exchanges and strengthen;
The weight percent of described metal fused salt is composed as follows:
described contains soda glass more preferably soda-lime glass or soda-alumina-silica glass.
Now, containing sodium ion in described glasswork, the dominant cation composition in described fused salt is potassium ion, and the magnitude difference of the ionic radius of potassium ion and sodium ion is suitable, also can be produced " jammed effect " by ion-exchange and forms Surface stress layer.
In the present invention, the method that described glass article surface plates sull comprises chemistry or physical vapor deposition, magnetron sputtering, molecular-layer deposition, spray pyrolysis, pulsed laser deposition or sol-gel method.As preferably, the method that described glass article surface plates sull is sol-gel method, adopt sol-gel method can obtain even flawless sull, and the method preparation condition is gentle, raw material sources are extensive, with low cost, the surface coating of the glasswork of suitable different shape.
Described glass article surface plates thickness≤1 μm of sull, and thickness is excessive, affects the efficiency of ion-exchange.
As preferably, the concrete steps of described sol-gel method are as follows:
A oxide precursor dissolves with solvent by (), add auxiliary agent, and be hydrolyzed polyreaction, after having reacted, obtains oxide sol;
B oxide sol that step (a) obtains by () is coated in glass article surface, then dry 0.5-2 hour at 50 ~ 200 DEG C of temperature, and 2-4 hour is heat-treated at lower than glass softening point temperature, obtain the glasswork of sull on plated surface;
First described glass article surface uses method well known to those skilled in the art to carry out clean;
In step (b), described oxide sol can add dust technology before coating to stablize its viscosity.
As preferably, in step (a), described solvent is water and/or ethanol.
In step (a), described oxide precursor is the mineral compound generating oxide compound by hydrolytic-polymeric reaction, described oxide compound is the oxide compound of transition metal, III, IV and/or V main group element, the coating obtained can be unitary sull or multicomponents oxide thin film, described oxide sol more preferably ZrO
2, SnO
2, Al
2o
3, Cr
2o
3, SiO
2and V
2o
5colloidal sol at least one, these oxide sols formed coating there is good wear resisting property and good light transmission.
As preferably, in step (a), described auxiliary agent is ammoniacal liquor, and hydrogen peroxide or propylene oxide can participate in the hydrolytic-polymeric reaction of oxide precursor and go, the carrying out of facilitation of hydrolysis polyreaction.
In step (a), the temperature of described hydrolytic-polymeric reaction is room temperature.
In step (b), the method for described coating is spray method, roller painting, crystal pulling method or spin-coating method.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) glass article surface prepared by preparation method of the present invention has one deck damage resistant film, the hardness of glass surface can be increased to more than 18Gpa, improves the opposing frictionally damage of goods in routine use and the ability scratched;
(2) glass article surface of the sodium calcium matrix prepared by can obtain more than 30 μm compressive stress layers (ion exchange depth), and bearing stress > 300Mpa, the dispersiveness of intensity is also improved.This extends the Application Areas of chemically toughened glass goods, extends the work-ing life of this based article, when particularly as touch Panel and windshield apron.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of the embodiment of the present invention 1 gained film;
Fig. 2 is the embodiment of the present invention 1 gained glass article surface nano-indentation hardness;
Fig. 3 is the embodiment of the present invention 1 gained glasswork visible light transmissivity.
Embodiment
Illustrate the present invention further by the following examples.(each starting material are commercially available, are chemical pure or analytical pure grade without special instruction)
Embodiment 1: prepare plated surface ZrO
2wear-resistance thin film chemical tempering flat soda lime glass
With zirconium oxychloride, deionized water, ethanol, hydrogen peroxide for raw material, wherein deionized water is 1: 4 with ethanol contend ratio, and zirconium oxychloride is 2% of deionized water+total ethanol quality by zirconium oxide gauge, and the mol ratio of hydrogen peroxide and zirconium oxychloride is 4: 1.At room temperature, abundant stirring adds each material successively after about 4 hours, forms water white transparency colloidal sol.Ageing after 6 hours dissolved adhesiveness reach plated film requirement, enter the viscosity of 0.5% dust technology stable sol by the minim of every 100ml colloidal sol 0.5ml.By crystal pulling method by after on colloidal sol coating surface of plate glass after the cleaning, product transfers to the saltpetre fused salt (KNO of 450 DEG C in 60 DEG C of baking ovens after the dry retort furnace thermal treatment 2h be placed in again for 30 minutes under 550 DEG C of air atmospheres
395.5%, K
2cO
32%, α-Al
2o
31%, diatomite 1%, KOH0.5%) carry out the ion-exchange of 15h.Product carries out cooling after taking out and cleans.Tested by the nano-indentation hardness of nano-indentation hardness meter to its surface, measured result is more than 18Gpa, three-point bending resistance strength test is carried out to double-sided coating sheet glass sample simultaneously, on average reach more than 380Mpa, now ion exchange depth is more than 15 μm, and visible light transmissivity is greater than 80%.The XRD figure spectrum of surface film is shown in Fig. 1, and surface film nano-indentation hardness is shown in Fig. 2, and sample visible light transmissivity is shown in Fig. 3.
Embodiment 2: prepare plated surface SnO
2wear-resistance thin film chemical tempering flat soda lime glass
With tin chloride, deionized water, ethanol, hydrogen peroxide for raw material, wherein deionized water is 1: 4 with ethanol contend ratio, and tin chloride counts 5% of water+total ethanol quality by stannic oxide quality, and hydrogen peroxide adds the amount of tin chloride mol ratio 4.At room temperature, abundant stirring adds each material successively after about 4 hours, forms water white transparency colloidal sol.Ageing after 6 hours dissolved adhesiveness reach plated film requirement, enter the viscosity of 0.5% dust technology stable sol by the minim of every 100ml colloidal sol 0.5ml.By crystal pulling method by after on colloidal sol coating surface of plate glass after the cleaning, product transfers to the saltpetre fused salt (KNO of 450 DEG C in 60 DEG C of baking ovens after the dry retort furnace thermal treatment 2h be placed in again for 30 minutes under 550 DEG C of air atmospheres
395.5%, K
2cO
32%, α-Al
2o
31%, diatomite 1%, KOH0.5%) carry out the ion-exchange of 13h.Product carries out cooling after taking out and cleans.Tested by the nano-indentation hardness of nano-indentation hardness meter to its surface film, measured result is more than 17Gpa, three-point bending resistance strength test is carried out to double-sided coating sheet glass sample simultaneously, on average reach more than 380Mpa, now ion exchange depth is more than 17 μm, and visible light transmissivity is greater than 85%.
Embodiment 3: prepare plated surface Al
2o
3wear-resistance thin film chemical tempering flat soda lime glass
With aluminum chloride, deionized water, ethanol, propylene oxide for raw material, wherein deionized water is 1: 4 with ethanol contend ratio, and aluminum chloride counts 2% of water+total ethanol quality by quality of alumina, and propylene oxide adds the amount of aluminum chloride mol ratio 6.At room temperature, abundant stirring adds each material successively after about 7 hours, forms water white transparency colloidal sol.Ageing after 15 hours dissolved adhesiveness reach plated film requirement, enter the viscosity of 0.5% dust technology stable sol by the minim of every 100ml colloidal sol 0.5ml.By crystal pulling method by after on colloidal sol coating surface of plate glass after the cleaning, product transfers to the saltpetre fused salt (KNO of 450 DEG C in 60 DEG C of baking ovens after the dry retort furnace thermal treatment 2h be placed in again for 30 minutes under 550 DEG C of air atmospheres
395.5%, K
2cO
32%, α-Al
2o
31%, diatomite 1%, KOH0.5%) carry out the ion-exchange of 13h.Product carries out cooling after taking out and cleans.Tested by the nano-indentation hardness of nano-indentation hardness meter to its surface film, measured result is more than 19Gpa, three-point bending resistance strength test is carried out to double-sided coating sheet glass sample simultaneously, on average reach more than 400Mpa, now ion exchange depth is more than 18 μm, and visible light transmissivity is greater than 85%.
Embodiment 4: prepare plated surface ZrO
2-SiO
2the dull and stereotyped lithium aluminosilicate glass of wear-resistance thin film chemical tempering
With zirconium oxychloride, tetraethoxy, deionized water, ethanol, ammoniacal liquor for raw material, wherein deionized water is 1: 7 with ethanol contend ratio, zirconium oxychloride and tetraethoxy mol ratio are 1: 1, both add up to 2% of water+total ethanol quality by oxide mass at total amount, strong aqua is for subsequent use after diluting 10 times, with NH
4 +measure its add-on and be about zirconium oxychloride molar weight 3 times.At room temperature, add ethanol successively, tetraethoxy, deionized water, fully stir after zirconium oxychloride, more slowly instilled the ammoniacal liquor after dilution, uninterruptedly stir after about 2 hours, form ZrO
2-SiO
2water white transparency colloidal sol.After ageing 5, dissolved adhesiveness reaches plated film requirement, enters the viscosity of 0.5% dust technology stable sol by the minim of every 100ml colloidal sol 1ml.By crystal pulling method by after on colloidal sol coating surface of plate glass after the cleaning, product transfers to the SODIUMNITRATE fused salt (NaNO of 400 DEG C in 60 DEG C of baking ovens after the dry retort furnace thermal treatment 2h be placed in again for 30 minutes under 550 DEG C of air atmospheres
395.5%, Na
2cO
32%, α-Al
2o
31%, diatomite 1%, NaOH0.5%) carry out the ion-exchange of 10h.Product carries out cooling after taking out and cleans.Tested by the nano-indentation hardness of nano-indentation hardness meter to its surface, measured result is more than 18Gpa, three-point bending resistance strength test is carried out to double-sided coating sheet glass sample simultaneously, on average reach more than 580Mpa, now ion exchange depth is more than 45 μm, and visible light transmissivity is greater than 85%.
Embodiment 5: prepare plated surface ZrO
2-SnO
2-Al
2o
3ternary wear-resistance thin film chemical tempering ultrathin plate soda-alumina-silica glass
With zirconium oxychloride, aluminum chloride, tin tetrachloride, deionized water, ethanol, PEG1000, ammoniacal liquor for raw material, wherein deionized water is 1: 1 with ethanol contend ratio, zirconium oxychloride: aluminum chloride: the mol ratio of tin tetrachloride is 2: 1: 2, three's total amount adds up to 1% of water+total ethanol quality by oxide mass, strong aqua is for subsequent use after diluting 10 times, and its add-on is with NH
4 +metering is about zirconium oxychloride molar weight 5-15 doubly, and PEG1000 adds the 0.5wt% of solid content.Fully stir after adding zirconium oxychloride, aluminum chloride, tin tetrachloride, deionized water, ethanol, PEG1000 successively, dissolve and obtain mixing solutions, more slowly instilled the ammoniacal liquor after dilution, uninterruptedly stir after about 2 hours, form ZrO
2-SnO
2-Al
2o
3light blue vitreosol.After ageing 15h, dissolved adhesiveness reaches plated film requirement, enters the viscosity of 0.5% dust technology stable sol by the minim of every 100ml colloidal sol 1ml.By crystal pulling method by colloidal sol coating soda-alumina-silica glass after the cleaning on the surface after, product transfers to the saltpetre fused salt (KNO of 450 DEG C in 60 DEG C of baking ovens after the dry retort furnace thermal treatment 2h be placed in again for 30 minutes under 550 DEG C of air atmospheres
395.5%, K
2cO
32%, α-Al
2o
31%, diatomite 1%, KOH0.5%) carry out the ion-exchange of 15h.Product carries out cooling after taking out and cleans.Tested by the nano-indentation hardness of nano-indentation hardness meter to its surface, measured result is more than 19Gpa, three-point bending resistance strength test is carried out to double-sided coating sheet glass sample simultaneously, on average reach more than 420Mpa, now ion exchange depth is more than 25 μm, and visible light transmissivity is greater than 85%.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, and that can not assert specific embodiment of the invention is confined to these explanations.For those skilled in the technology concerned belonging to the present invention, without departing from the inventive concept of the premise, some simple deductions or replacement can also be made, all should be considered as protection scope of the present invention.
Claims (6)
1. there is a preparation method for the chemically toughened glass goods of wear-resistance thin film, it is characterized in that, comprise the steps:
(1) sull is plated at glass article surface;
(2) on plated surface step (1) obtained, the glasswork of sull is placed in metal fused salt, after carrying out ion-exchange strengthening 8-18h at 400-500 DEG C, cooling, takes out cleaning, obtains the described chemically toughened glass goods with wear-resistance thin film;
The weight percent of the metal fused salt described in step (2) is composed as follows:
Described glass article surface plates thickness≤1 μm of sull;
The method that described glass article surface plates sull is sol-gel method;
The step of described sol-gel method is as follows:
A oxide precursor dissolves with solvent by (), add auxiliary agent, and be hydrolyzed polyreaction, after having reacted, obtains oxide sol;
B oxide sol that step (a) obtains by () is coated in glass article surface, then dry 0.5-2 hour at 50 ~ 200 DEG C of temperature, and 2-4 hour is heat-treated at lower than glass softening point temperature, obtain the glasswork of sull on plated surface.
2. the preparation method with the chemically toughened glass goods of wear-resistance thin film according to claim 1, is characterized in that, described glasswork, for containing lithium glass, carries out lithium sodium ion exchange with fused salt and strengthens;
The weight percent of described metal fused salt is composed as follows:
3. the preparation method with the chemically toughened glass goods of wear-resistance thin film according to claim 1, is characterized in that, described glasswork for containing soda glass, carries out sodium potassium ion with fused salt and exchanges and strengthen;
The weight percent of described metal fused salt is composed as follows:
4. the preparation method with the chemically toughened glass goods of wear-resistance thin film according to claim 1, is characterized in that, in step (a), described solvent is water and/or ethanol.
5. the preparation method with the chemically toughened glass goods of wear-resistance thin film according to claim 1, is characterized in that, in step (a), described oxide sol is ZrO
2, SnO
2, Al
2o
3, Cr
2o
3, SiO
2and V
2o
5colloidal sol at least one.
6. the preparation method with the chemically toughened glass goods of wear-resistance thin film according to claim 1, is characterized in that, in step (a), described auxiliary agent is ammoniacal liquor, hydrogen peroxide or propylene oxide.
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Application publication date: 20130306 Assignee: ZHEJIANG JINLIHUA ELECTRIC JOINT-STOCK Ltd. Assignor: Zhejiang University Contract record no.: 2018330000027 Denomination of invention: Preparation method of chemical toughened glass product with wearing-resisting film Granted publication date: 20150429 License type: Common License Record date: 20180327 |
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