CN117720277B - Color glass ceramics and preparation method thereof - Google Patents
Color glass ceramics and preparation method thereof Download PDFInfo
- Publication number
- CN117720277B CN117720277B CN202311651319.6A CN202311651319A CN117720277B CN 117720277 B CN117720277 B CN 117720277B CN 202311651319 A CN202311651319 A CN 202311651319A CN 117720277 B CN117720277 B CN 117720277B
- Authority
- CN
- China
- Prior art keywords
- glass
- chitosan
- glass fiber
- aluminum
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002241 glass-ceramic Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000003365 glass fiber Substances 0.000 claims abstract description 91
- 229920001661 Chitosan Polymers 0.000 claims abstract description 90
- 239000011248 coating agent Substances 0.000 claims abstract description 54
- 238000000576 coating method Methods 0.000 claims abstract description 54
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 42
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 42
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 40
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 21
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 21
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 21
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 21
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 21
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 21
- 239000011787 zinc oxide Substances 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 51
- 239000011521 glass Substances 0.000 claims description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 41
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 19
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 19
- 235000012141 vanillin Nutrition 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 229960000583 acetic acid Drugs 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 9
- 239000006060 molten glass Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 230000006911 nucleation Effects 0.000 claims description 2
- 238000010899 nucleation Methods 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
Landscapes
- Glass Compositions (AREA)
Abstract
The invention relates to the technical field of glass ceramics, in particular to a colored glass ceramics and a preparation method thereof. The invention prepares a color glass-ceramic matrix by using silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide as raw materials. Then, a colored glass-ceramic vessel is obtained by coating a coating on the colored glass-ceramic substrate. According to the invention, silica sol is used as a main raw material, and chitosan modified glass fiber is added to improve the wear resistance and antibacterial property of the coating. The invention also loads nano aluminum on the glass fiber, further improves the wear resistance of the coating, and further enhances the wear resistance of the glass ceramics.
Description
Technical Field
The invention relates to the technical field of glass ceramics, in particular to a colored glass ceramics and a preparation method thereof.
Background
The glass ceramics is an inorganic nonmetallic material, has high mechanical strength, good chemical stability and excellent wear resistance, and can be widely used as functional materials and decorative materials in different technical fields of construction, chemical industry, electronics, machinery and the like.
However, there are limitations in some respects to the conventional glass-ceramic ware, which is susceptible to scratches and abrasion, reducing its aesthetic appearance and service life, and it is common to apply a coating to glass-ceramic ware to enhance its wear resistance. However, the coating of the wear-resistant coating also easily affects the light transmittance of the glass ceramics, and affects the aesthetic degree of the glass ceramics. Therefore, it becomes important to develop a colored glass-ceramic having abrasion resistance and high light transmittance.
In order to solve the problems, the invention provides a colored glass ceramics and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a colored glass ceramics and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
The preparation method of the color glass ceramics comprises the following steps:
step one: taking methyltriethoxysilane and ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking silica sol, glass fiber loaded with aluminum, water, acetic acid and hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2-3 hours, heating to 75-80 ℃, reacting for 2-3 hours, cooling to 25-35 ℃, adding KH-560 and isopropanol, and uniformly stirring to obtain the coating;
step two: grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 30-40min, and preserving heat at 1600-1650 ℃ for 3-4h to obtain molten glass liquid;
Step three: pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4-5 hours at 600-650 ℃, cooling to 30-35 ℃, nucleating for 4-6 hours, crystallizing for 2-3 hours, and cooling to 30-35 ℃ to obtain a microcrystalline glass matrix;
Step four: and (3) coating the coating on a microcrystalline glass substrate, and curing to obtain the color microcrystalline glass ware.
More optimally, the preparation method of the aluminum-loaded glass fiber comprises the following steps: taking chitosan modified glass fiber and aluminum chloride aqueous solution, uniformly stirring, heating to 160-165 ℃ for reaction for 3.5-4.5 hours, filtering, washing and drying to obtain the aluminum-loaded glass fiber.
More preferably, the concentration of the aluminum chloride aqueous solution is 0.45-0.55mol/L.
More optimally, the preparation method of the chitosan modified glass fiber comprises the following steps: taking glass fiber and ethanol, performing ultrasonic dispersion, adding modified chitosan, uniformly stirring, heating to 55-60 ℃ for reaction for 1-2h, filtering, washing and drying to obtain chitosan modified glass fiber;
More optimally, the preparation method of the modified chitosan comprises the following steps: taking chitosan and absolute ethyl alcohol, reacting for 40-45min, adding vanillin, heating to 55-65 ℃, stirring for 10-20min, adding glacial acetic acid, reacting for 9-12h, performing rotary evaporation, filtering and drying to obtain the modified chitosan.
More preferably, the mass ratio of the chitosan to the vanillin is (5.5-6.5): 9.
More preferably, in the first step, the particle size of the silica sol is 10-20nm.
More preferably, in the third step, the nucleation temperature is 710-740 ℃, and the crystallization temperature is 820-850 ℃.
More preferably, the microcrystalline glass matrix comprises the following components in percentage by mole: 18-22mol% of aluminum oxide, 6-12mol% of lithium oxide, 3-5mol% of zinc oxide, 2-3mol% of titanium dioxide, 0.5-1.0mol% of magnesium oxide, 0.5-0.8mol% of phosphorus pentoxide, 0.4-0.7mol% of zirconium dioxide, 0.1-0.2mol% of antimony trioxide and the balance of silicon dioxide.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention prepares a color glass-ceramic matrix by using silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide as raw materials. Then, a colored glass-ceramic vessel is obtained by coating a coating on the colored glass-ceramic substrate.
(2) The invention takes silica sol with the particle size of 10-20nm as a main raw material, and then prepares the coating coated on the surface of microcrystalline glass by adding tetraethoxysilane, and chitosan modified glass fiber is also added into the coating to improve the wear resistance and the antibacterial property of the coating.
The invention selects glass fiber with the diameter of 3-10 mu m, and loads nano aluminum on the glass fiber. Nanometer aluminum is loaded on glass fiber to form micro-nano structure, so that the wear resistance of the coating is further improved, and the wear resistance of the glass ceramics is further enhanced.
According to the invention, the chitosan is subjected to imine structure functionalization modification by adding vanillin, and the mass ratio of the chitosan to the vanillin is controlled to be (5.5-6.5): 9, the antibacterial property of the chitosan is improved. The modified chitosan is used for modifying the glass fiber, a layer of modified chitosan is coated on the surface of the glass fiber, then nano aluminum is loaded on the glass fiber, deposition of the nano aluminum on the glass fiber is promoted, the nano aluminum is uniformly loaded on the surface of the chitosan modified glass fiber, the dispersibility of the glass fiber is improved, the wear resistance of the glass fiber is enhanced, and the addition of the glass fiber loaded with aluminum enables the colored glass-ceramic to still have excellent light transmittance, and the wear resistance and the antibacterial property of the glass-ceramic ware are improved.
The invention limits the concentration of the aluminum chloride aqueous solution to 0.45-0.55mol/L, and needs to emphasize that the concentration of the aluminum chloride aqueous solution is reduced due to the existence of vanillin modified chitosan, nano aluminum is uniformly loaded on the surface of chitosan modified glass fiber, and finally, the requirements of the antibacterial property and the wear resistance of the microcrystalline glass vessel are met, and the cost is reduced.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The manufacturers of all the raw materials involved in the present invention are not particularly limited, and include, by way of example: silica sol: can be purchased from Qingdao ocean, particle size: 10-20nm, model: JA-25; methyltriethoxysilane: can be purchased from the North Chengfengfeng chemical industry; ethyl orthosilicate: available from ala Ding Shiji; chitosan: available from ala Ding Shiji, model: c434553; vanillin: commercially available from microphone; glass fiber diameter: 3-10 μm; silica: 5-100 μm; alumina: 5-100 μm; lithium oxide: 5-500 mu m, zinc oxide: 0.1-10 mu m, titanium dioxide: 10-200nm, magnesium oxide: 5-50 μm; 5-100 mu m of phosphorus pentoxide; zirconium dioxide: 5-100 μm; antimony trioxide: 5-100 μm.
Example 1: a color glass ceramics and a preparation method thereof comprise the following steps:
Step one: preparation of modified chitosan:
Taking 0.6g of chitosan and 50mL of absolute ethyl alcohol, reacting for 42min, adding 0.9g of vanillin, heating to 60 ℃, stirring for 15min, adding 3mL of glacial acetic acid, reacting for 11h, performing rotary evaporation, filtering and drying to obtain modified chitosan;
step two: preparation of chitosan modified glass fiber:
taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of modified chitosan, uniformly stirring, heating to 57 ℃ for reaction for 1.5 hours, filtering, washing and drying to obtain chitosan modified glass fiber;
step three: preparation of aluminum-loaded glass fibers:
taking 3g of chitosan modified glass fiber and 200mL of aluminum chloride aqueous solution with the concentration of 0.5mol/L, uniformly stirring, heating to 162 ℃ for reaction for 4 hours, filtering, washing and drying to obtain aluminum-loaded glass fiber;
Step four: preparation of the coating:
Taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of glass fiber loaded with aluminum, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2.5 hours at 28 ℃, heating to 78 ℃, reacting for 2.5 hours, cooling to 28 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 45 minutes to obtain the coating;
step five: preparation of a colored glass ceramics:
Grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 35min, and preserving heat at 1620 ℃ for 3.5h to obtain molten glass;
pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4.5 hours at 620 ℃, cooling to 32 ℃, then nucleating for 5 hours at 730 ℃, crystallizing for 2.5 hours at 830 ℃, and cooling to 32 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
20mol% of aluminum oxide, 10mol% of lithium oxide, 4mol% of zinc oxide, 2.5mol% of titanium dioxide, 0.8mol% of magnesium oxide, 0.7mol% of phosphorus pentoxide, 0.6mol% of zirconium dioxide, 0.1mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Example 2: a color glass ceramics and a preparation method thereof comprise the following steps:
Step one: preparation of modified chitosan:
Taking 0.6g of chitosan and 50mL of absolute ethyl alcohol, reacting for 40min, adding 0.9g of vanillin, heating to 55 ℃, stirring for 10min, adding 3mL of glacial acetic acid, reacting for 9h, performing rotary evaporation, filtering and drying to obtain modified chitosan;
step two: preparation of chitosan modified glass fiber:
Taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of modified chitosan, uniformly stirring, heating to 55 ℃ for reaction for 2 hours, filtering, washing and drying to obtain chitosan modified glass fiber;
step three: preparation of aluminum-loaded glass fibers:
Taking 3g of chitosan modified glass fiber and 200mL of aluminum chloride aqueous solution with the concentration of 0.45mol/L, uniformly stirring, heating to 160 ℃ for reaction for 4.5 hours, filtering, washing and drying to obtain aluminum-loaded glass fiber;
Step four: preparation of the coating:
Taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of chitosan modified glass fiber, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2 hours at 25 ℃, heating to 75 ℃, reacting for 2 hours, cooling to 25 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 40 minutes to obtain the coating;
step five: preparation of a colored glass ceramics:
grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 30min, and preserving heat at 1600 ℃ for 3h to obtain molten glass;
Pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4 hours at 600 ℃, cooling to 30 ℃, then nucleating for 4 hours at 710 ℃, crystallizing for 2 hours at 820 ℃, and cooling to 30 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
18mol% of aluminum oxide, 11mol% of lithium oxide, 3mol% of zinc oxide, 3mol% of titanium dioxide, 0.5mol% of magnesium oxide, 0.5mol% of phosphorus pentoxide, 0.4mol% of zirconium dioxide, 0.1mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Example 3: a color glass ceramics and a preparation method thereof comprise the following steps:
Step one: preparation of modified chitosan:
taking 0.6g of chitosan and 50mL of absolute ethyl alcohol, reacting for 45min, adding 0.9g of vanillin, heating to 65 ℃, stirring for 20min, adding 3mL of glacial acetic acid, reacting for 12h, performing rotary evaporation, filtering and drying to obtain modified chitosan;
step two: preparation of chitosan modified glass fiber:
Taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of modified chitosan, uniformly stirring, heating to 60 ℃ for reaction for 2 hours, filtering, washing and drying to obtain chitosan modified glass fiber;
step three: preparation of aluminum-loaded glass fibers:
Taking 3g of chitosan modified glass fiber and 200mL of aluminum chloride aqueous solution with the concentration of 0.55mol/L, uniformly stirring, heating to 165 ℃ for reaction for 4 hours, filtering, washing and drying to obtain aluminum-loaded glass fiber;
Step four: preparation of the coating:
Taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of chitosan modified glass fiber, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 3 hours at 35 ℃, heating to 80 ℃, reacting for 3 hours, cooling to 35 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 50 minutes to obtain the coating;
step five: preparation of a colored glass ceramics:
Grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 40min, and preserving heat at 1650 ℃ for 4h to obtain molten glass;
Pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 5 hours at 650 ℃, cooling to 35 ℃, then nucleating for 6 hours at 740 ℃, crystallizing for 3 hours at 850 ℃, and cooling to 35 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
22mol% of aluminum oxide, 10mol% of lithium oxide, 5mol% of zinc oxide, 3mol% of titanium dioxide, 1.0mol% of magnesium oxide, 0.5mol% of phosphorus pentoxide, 0.7mol% of zirconium dioxide, 0.2mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Comparative example 1: the procedure of example 1 was repeated except that vanillin was not used to modify the chitosan:
step one: preparation of chitosan modified glass fiber:
Taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of chitosan, uniformly stirring, heating to 57 ℃ for reaction for 1.5h, filtering, washing and drying to obtain chitosan modified glass fiber;
step two: preparation of aluminum-loaded glass fibers:
taking 3g of chitosan modified glass fiber and 200mL of aluminum chloride aqueous solution with the concentration of 0.5mol/L, uniformly stirring, heating to 162 ℃ for reaction for 4 hours, filtering, washing and drying to obtain aluminum-loaded glass fiber;
Step three: preparation of the coating:
taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of chitosan modified glass fiber, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2.5 hours at 28 ℃, heating to 78 ℃, reacting for 2.5 hours, cooling to 28 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 45 minutes to obtain the coating;
step four: preparation of a colored glass ceramics:
Grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 35min, and preserving heat at 1620 ℃ for 3.5h to obtain molten glass;
pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4.5 hours at 620 ℃, cooling to 32 ℃, then nucleating for 5 hours at 730 ℃, crystallizing for 2.5 hours at 830 ℃, and cooling to 32 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
20mol% of aluminum oxide, 10mol% of lithium oxide, 4mol% of zinc oxide, 2.5mol% of titanium dioxide, 0.8mol% of magnesium oxide, 0.7mol% of phosphorus pentoxide, 0.6mol% of zirconium dioxide, 0.1mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Comparative example 2: the procedure of example 1 was repeated except that the concentration of the aqueous aluminum chloride solution was increased to 0.6mol/L without modifying the chitosan with vanillin:
step one: preparation of chitosan modified glass fiber:
Taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of chitosan, uniformly stirring, heating to 57 ℃ for reaction for 1.5h, filtering, washing and drying to obtain chitosan modified glass fiber;
step two: preparation of aluminum-loaded glass fibers:
Taking 3g of chitosan modified glass fiber and 200mL of aluminum chloride aqueous solution with the concentration of 0.6mol/L, uniformly stirring, heating to 162 ℃ for reaction for 4 hours, filtering, washing and drying to obtain aluminum-loaded glass fiber;
Step three: preparation of the coating:
Taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of glass fiber loaded with aluminum, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2.5 hours at 28 ℃, heating to 78 ℃, reacting for 2.5 hours, cooling to 28 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 45 minutes to obtain the coating;
step four: preparation of a colored glass ceramics:
Grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 35min, and preserving heat at 1620 ℃ for 3.5h to obtain molten glass;
pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4.5 hours at 620 ℃, cooling to 32 ℃, then nucleating for 5 hours at 730 ℃, crystallizing for 2.5 hours at 830 ℃, and cooling to 32 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
20mol% of aluminum oxide, 10mol% of lithium oxide, 4mol% of zinc oxide, 2.5mol% of titanium dioxide, 0.8mol% of magnesium oxide, 0.7mol% of phosphorus pentoxide, 0.6mol% of zirconium dioxide, 0.1mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Comparative example 3: the concentration of the aqueous aluminum chloride solution was increased to 0.6mol/L, and the rest was the same as in example 1:
Step one: preparation of modified chitosan:
Taking 0.6g of chitosan and 50mL of absolute ethyl alcohol, reacting for 42min, adding 0.9g of vanillin, heating to 60 ℃, stirring for 15min, adding 3mL of glacial acetic acid, reacting for 11h, performing rotary evaporation, filtering and drying to obtain modified chitosan;
step two: preparation of chitosan modified glass fiber:
taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of modified chitosan, uniformly stirring, heating to 57 ℃ for reaction for 1.5 hours, filtering, washing and drying to obtain chitosan modified glass fiber;
step three: preparation of aluminum-loaded glass fibers:
Taking 3g of chitosan modified glass fiber and 200mL of aluminum chloride aqueous solution with the concentration of 0.6mol/L, uniformly stirring, heating to 162 ℃ for reaction for 4 hours, filtering, washing and drying to obtain aluminum-loaded glass fiber;
Step four: preparation of the coating:
Taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of glass fiber loaded with aluminum, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2.5 hours at 28 ℃, heating to 78 ℃, reacting for 2.5 hours, cooling to 28 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 45 minutes to obtain the coating;
step five: preparation of a colored glass ceramics:
Grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 35min, and preserving heat at 1620 ℃ for 3.5h to obtain molten glass;
pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4.5 hours at 620 ℃, cooling to 32 ℃, then nucleating for 5 hours at 730 ℃, crystallizing for 2.5 hours at 830 ℃, and cooling to 32 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
20mol% of aluminum oxide, 10mol% of lithium oxide, 4mol% of zinc oxide, 2.5mol% of titanium dioxide, 0.8mol% of magnesium oxide, 0.7mol% of phosphorus pentoxide, 0.6mol% of zirconium dioxide, 0.1mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Comparative example 4: the remainder was the same as in example 1, except that aluminum was not supported on the glass fiber:
Step one: preparation of modified chitosan:
Taking 0.6g of chitosan and 50mL of absolute ethyl alcohol, reacting for 42min, adding 0.9g of vanillin, heating to 60 ℃, stirring for 15min, adding 3mL of glacial acetic acid, reacting for 11h, performing rotary evaporation, filtering and drying to obtain modified chitosan;
step two: preparation of chitosan modified glass fiber:
taking 5.5g of glass fiber and 500mL of ethanol, performing ultrasonic dispersion, adding 2g of modified chitosan, uniformly stirring, heating to 57 ℃ for reaction for 1.5 hours, filtering, washing and drying to obtain chitosan modified glass fiber;
Step three: preparation of the coating:
taking 30g of methyltriethoxysilane and 5g of ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking 30g of silica sol, 7g of chitosan modified glass fiber, 100mL of water, 10g of acetic acid and 10g of hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2.5 hours at 28 ℃, heating to 78 ℃, reacting for 2.5 hours, cooling to 28 ℃, adding 3gKH-560 and 20g of isopropanol, and continuously stirring for 45 minutes to obtain the coating;
step four: preparation of a colored glass ceramics:
Grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 35min, and preserving heat at 1620 ℃ for 3.5h to obtain molten glass;
pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4.5 hours at 620 ℃, cooling to 32 ℃, then nucleating for 5 hours at 730 ℃, crystallizing for 2.5 hours at 830 ℃, and cooling to 32 ℃ to obtain a microcrystalline glass matrix;
the color glass ceramic matrix comprises the following components in percentage by mole:
20mol% of aluminum oxide, 10mol% of lithium oxide, 4mol% of zinc oxide, 2.5mol% of titanium dioxide, 0.8mol% of magnesium oxide, 0.7mol% of phosphorus pentoxide, 0.6mol% of zirconium dioxide, 0.1mol% of antimony trioxide and the balance of silicon dioxide;
Coating the coating on the microcrystalline glass substrate, wherein the coating thickness is 150nm, and curing to obtain the color microcrystalline glass ware.
Experiment:
The colored glass ceramics prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to a frictional wear test at 25℃using a HT-1000 type frictional wear tester using WC ceramic balls at a rotation speed of 560r/min under a load of 10N, and the glass ceramics were tested for wear resistance. And testing the average transmittance of the colored microcrystalline glass in the wave band of 300-800 nm. The antibacterial rate of the colored glass-ceramic was tested by a plate method using E.coli as a strain, and the obtained data are shown in the following table:
Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
Wear amount/mg | 2.1 | 2.2 | 2.1 | 3.1 | 2.8 | 2.4 | 4.5 |
Transmittance/% | 76.2 | 76.1 | 76.5 | / | / | / | / |
Antibacterial rate/% | 99.9 | 99.9 | 99.9 | 97.6 | 98.2 | 99.9 | 99.7 |
Conclusion: comparative example 1 does not use vanillin to modify chitosan, the antibacterial performance of chitosan is poor, at this time, aluminum loaded on the surface of the chitosan modified glass fiber is reduced, the deposition effect of nano aluminum on the surface of the chitosan modified glass fiber is poor, the wear resistance of the colored glass ceramics is poor, the abrasion loss is increased, and the antibacterial rate is reduced. Comparative example 2 does not use vanillin to modify chitosan, the concentration of the aluminum chloride aqueous solution is increased to 0.6mol/L, at the moment, the antibacterial property of the chitosan is deteriorated, the concentration of the aluminum chloride aqueous solution is increased, the dispersibility of nano aluminum is poor, the deposition distribution of nano aluminum on glass fibers is uneven, and the wear resistance of colored microcrystalline glass is affected. In comparative example 3, vanillin is used for modifying chitosan, the concentration of aluminum chloride aqueous solution is increased to 0.6mol/L, the modified chitosan is used for modifying glass fiber, a layer of modified chitosan is coated on the surface of the glass fiber, and at the moment, excessive nano aluminum is deposited on the surface of the chitosan modified glass fiber, so that the surface of the glass fiber loaded with aluminum becomes uneven, and the wear resistance of the colored glass-ceramic is affected. Comparative example 4, in which no aluminum was supported on glass fibers, the colored glass-ceramic had poor abrasion resistance and deteriorated abrasion resistance. According to the embodiment 1-3, vanillin is added to perform imine structure functionalization modification on chitosan, so that the antibacterial performance of the chitosan is improved, the modified chitosan is used to modify glass fiber, a layer of modified chitosan is coated on the surface of the glass fiber, then nano aluminum is loaded on the glass fiber, at the moment, the concentration of an aluminum chloride aqueous solution is 0.5mol/L, the concentration of the aluminum chloride aqueous solution is reduced, at the moment, nano aluminum is uniformly loaded on the surface of the chitosan modified glass fiber, the wear resistance of the glass fiber is enhanced, and the addition of the glass fiber loaded with aluminum enables the colored glass ceramics to still have excellent light transmittance, and the wear resistance and antibacterial performance of a glass ceramics are improved.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a colored glass ceramics is characterized in that: the method comprises the following steps:
step one: taking methyltriethoxysilane and ethyl orthosilicate, and uniformly stirring to obtain a mixture A; taking silica sol, glass fiber loaded with aluminum, water, acetic acid and hydrochloric acid, uniformly stirring, adding the mixture A, reacting for 2-3 hours, heating to 75-80 ℃, reacting for 2-3 hours, cooling to 25-35 ℃, adding KH-560 and isopropanol, and uniformly stirring to obtain the coating;
step two: grinding silicon dioxide, aluminum oxide, lithium oxide, zinc oxide, titanium dioxide, magnesium oxide, phosphorus pentoxide, zirconium dioxide and antimony trioxide for 30-40min, and preserving heat at 1600-1650 ℃ for 3-4h to obtain molten glass liquid;
Step three: pouring the glass liquid into a mould for cooling and molding, annealing and preserving heat for 4-5 hours at 600-650 ℃, cooling to 30-35 ℃, nucleating for 4-6 hours, crystallizing for 2-3 hours, and cooling to 30-35 ℃ to obtain a microcrystalline glass matrix;
Step four: and (3) coating the coating on a microcrystalline glass substrate, and curing to obtain the color microcrystalline glass ware.
2. The method for preparing the colored glass ceramics according to claim 1, which is characterized in that: the preparation method of the aluminum-loaded glass fiber comprises the following steps: taking chitosan modified glass fiber and aluminum chloride aqueous solution, uniformly stirring, heating to 160-165 ℃ for reaction for 3.5-4.5 hours, filtering, washing and drying to obtain the aluminum-loaded glass fiber.
3. The method for preparing the colored glass ceramics according to claim 2, which is characterized in that: the concentration of the aluminum chloride aqueous solution is 0.45-0.55mol/L.
4. The method for preparing the colored glass ceramics according to claim 2, which is characterized in that: the preparation method of the chitosan modified glass fiber comprises the following steps: and (3) dispersing the glass fiber and ethanol by ultrasonic, adding the modified chitosan, stirring uniformly, heating to 55-60 ℃ for reaction for 1-2h, filtering, washing and drying to obtain the chitosan modified glass fiber.
5. The method for preparing the colored glass ceramics according to claim 4, wherein the method comprises the following steps: the preparation method of the modified chitosan comprises the following steps: taking chitosan and absolute ethyl alcohol, reacting for 40-45min, adding vanillin, heating to 55-65 ℃, stirring for 10-20min, adding glacial acetic acid, reacting for 9-12h, performing rotary evaporation, filtering and drying to obtain the modified chitosan.
6. The method for preparing the colored glass ceramics according to claim 5, which is characterized in that: the mass ratio of the chitosan to the vanillin is (5.5-6.5): 9.
7. The method for preparing the colored glass ceramics according to claim 1, which is characterized in that: in the first step, the particle size of the silica sol is 10-20nm.
8. The method for preparing the colored glass ceramics according to claim 1, which is characterized in that: in the third step, the nucleation temperature is 710-740 ℃, and the crystallization temperature is 820-850 ℃.
9. The method for preparing the colored glass ceramics according to claim 1, which is characterized in that: the microcrystalline glass matrix comprises the following components in percentage by mole: 18-22mol% of aluminum oxide, 6-12mol% of lithium oxide, 3-5mol% of zinc oxide, 2-3mol% of titanium dioxide, 0.5-1.0mol% of magnesium oxide, 0.5-0.8mol% of phosphorus pentoxide, 0.4-0.7mol% of zirconium dioxide, 0.1-0.2mol% of antimony trioxide and the balance of silicon dioxide.
10. A colored glass-ceramic ware prepared by the method of any one of claims 1-9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311651319.6A CN117720277B (en) | 2023-12-05 | 2023-12-05 | Color glass ceramics and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311651319.6A CN117720277B (en) | 2023-12-05 | 2023-12-05 | Color glass ceramics and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN117720277A CN117720277A (en) | 2024-03-19 |
CN117720277B true CN117720277B (en) | 2024-06-14 |
Family
ID=90206314
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311651319.6A Active CN117720277B (en) | 2023-12-05 | 2023-12-05 | Color glass ceramics and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117720277B (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101205121A (en) * | 2007-12-18 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | Transparent titania super-hydrophilic coating using organosilicon as underlayment and preparation thereof |
CN102786229A (en) * | 2005-04-19 | 2012-11-21 | 肖特股份公司 | Glass or glass-ceramic articles with decorative coating |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5418194A (en) * | 1990-04-23 | 1995-05-23 | Corning Incorporated | Coated inorganic fiber reinforcement materials and ceramic composites comprising the same |
CN102992646A (en) * | 2012-11-28 | 2013-03-27 | 江苏宜达光电科技有限公司 | Film coating method for self-cleanness glass ceramics |
CN104445952B (en) * | 2014-11-14 | 2017-03-08 | 武汉理工大学 | A kind of high-hard, transparent devitrified glass and preparation method thereof |
CN107325651A (en) * | 2017-07-15 | 2017-11-07 | 合肥皖水信息科技有限公司 | A kind of fire-proof glass curtain wall |
CN108033688B (en) * | 2017-12-26 | 2020-08-28 | 中建材蚌埠玻璃工业设计研究院有限公司 | Silicon oxide-based super-hydrophobic coating and preparation method thereof |
CN117142772B (en) * | 2023-10-30 | 2024-01-02 | 鼎钰玻璃(扬州)有限公司 | Self-cleaning coated glass and preparation method thereof |
-
2023
- 2023-12-05 CN CN202311651319.6A patent/CN117720277B/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102786229A (en) * | 2005-04-19 | 2012-11-21 | 肖特股份公司 | Glass or glass-ceramic articles with decorative coating |
CN101205121A (en) * | 2007-12-18 | 2008-06-25 | 中国科学院上海硅酸盐研究所 | Transparent titania super-hydrophilic coating using organosilicon as underlayment and preparation thereof |
Also Published As
Publication number | Publication date |
---|---|
CN117720277A (en) | 2024-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109266057B (en) | Normal-temperature-cured super-weather-resistant high-hardness wear-resistant water-based inorganic nano ceramic coating and preparation method thereof | |
CN110172180B (en) | Inorganic fiber/silicon dioxide nano material and preparation method and application thereof | |
WO2022252930A1 (en) | Combined process antibacterial ceramic tile and production method therefor | |
CN113998901B (en) | Double-glass assembly reflective coating and preparation method thereof | |
CN117142772B (en) | Self-cleaning coated glass and preparation method thereof | |
CN111498859A (en) | Preparation method of high-transparency high-dispersibility white carbon black | |
CN117720277B (en) | Color glass ceramics and preparation method thereof | |
CN112340993A (en) | Glaze capable of increasing brightness and preparation process thereof | |
CN116590964A (en) | Low-formaldehyde wear-resistant antibacterial composite impregnated paper and preparation method thereof | |
KR20200005924A (en) | manufacturing method of ceramic binder with inorganic non-combustible material | |
CN111153607B (en) | Organic-inorganic mixed phosphate-based high-temperature-resistant basalt fiber impregnating compound and preparation method thereof | |
CN105862014B (en) | Magnesiumalloy surface modifying organic glass corrosion-inhibiting coating method | |
JPH06116507A (en) | Iridescent luster pigment | |
KR101445437B1 (en) | Anti-Reflection Film and Method of Producing The Same | |
CN107760133A (en) | A kind of preparation method of the organo-mineral complexing coating of nanometer of lanthanum hexaboride collaboration enhancing effect of heat insulation | |
CN112898811A (en) | Antibacterial self-repairing microcapsule, preparation method thereof and application thereof in coating | |
JP3097349B2 (en) | Method for producing pearlescent pigment | |
CN110386761A (en) | A kind of super-hydrophobic anti-reflection with high transparency penetrates the preparation method of coating | |
JP3955971B2 (en) | Base material with antireflection film | |
CN110436501B (en) | Preparation method for controlling size and thickness of flaky alumina | |
KR100732085B1 (en) | Organic-inorganic hybrid hard coating compositions and their preparation method with improved stability for storage and workability | |
JP2013043791A (en) | Modified hollow silica microparticle | |
JPS63223701A (en) | Coating film having high refractive index and its production | |
CN115636596B (en) | Low reflection glass and method for producing the same | |
CN1597618A (en) | Ceramic fiber mould plate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |