CN113831017B - Application to improving anatase TiO 2 Super-hydrophilic self-cleaning ceramic glaze coating and application method thereof - Google Patents
Application to improving anatase TiO 2 Super-hydrophilic self-cleaning ceramic glaze coating and application method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000000576 coating method Methods 0.000 title claims abstract description 67
- 229910010413 TiO 2 Inorganic materials 0.000 title claims abstract description 38
- 239000000919 ceramic Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000004140 cleaning Methods 0.000 title claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 36
- 239000010936 titanium Substances 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 31
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000411 inducer Substances 0.000 claims abstract description 26
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 40
- 238000001035 drying Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000009736 wetting Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical group [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010494 opalescence Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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Abstract
The invention relates to a method for improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze and the application method thereof, the coating comprises the following components by mass percent: 13-17 wt% of deionized water, 12-17 wt% of strong acid, 55-60 wt% of titanium source, 5-10 wt% of inducer and 6-12 wt% of absolute ethyl alcohol. The invention calcines the catalyst containing an inducer CaTi in an oxidizing atmosphere 2 O 5 Of TiO2 2 Precursor coating to promote the formation of anatase TiO at low temperature 2 The contact angle of the glaze is effectively reduced, the glaze is suitable for various glazes, the super-hydrophilic effect of the glaze is realized, the self-cleaning performance of different ceramic glazes is improved, and the glaze has wide application range and application prospect.
Description
Technical Field
The invention relates to the field of ceramic glaze surface cleaning, in particular to a coating for improving anatase TiO2 super-hydrophilic self-cleaning ceramic glaze and an application method thereof.
Background
With national economic development and social progress, the living standard of people is continuously improved, and the traditional building ceramics and sanitary ceramics have poor pollution resistance and pollution resistance, so that the expectation of people on high-quality products is difficult to meet. In order to increase the value of conventional ceramics, it becomes increasingly important to impart good self-cleaning properties thereto. The ceramic glaze is a vitreous thin layer on the surface of ceramic formed by using silicate raw materials such as quartz, calcite and the like as main raw materials and roasting and melting the raw materials at a certain temperature. In application CN202010117271.0 surfactant CaTi is added 2 O 5 The super-hydrophilic glaze is prepared by adding the phase-splitting glaze, but the super-hydrophilic glaze has strong opalescence, thereby greatly limiting the application of the super-hydrophilic glaze. The application overcomes the defects of only being suitable for split-phase glaze and the like, and utilizes an inducer CaTi 2 O 5 Is added to TiO 2 Immersing ceramic glaze in sol system, coating film and calcining to obtain anatase TiO 2 Overcomes the defects of the prior TiO 2 The coating is not firmly combined with the ceramic glaze surface and is calcined at high temperatureAnatase is easily transformed into rutile during firing, so that the hydrophilicity of the glaze surface is reduced and the like. Therefore, the application patent discloses the method for preparing the ceramic glaze by adding the inducer CaTi on the surface of the ceramic glaze 2 O 5 Of TiO2 2 The coating not only greatly reduces the wetting angle of the glaze surface and improves the self-cleaning performance of the ceramic glaze, but also is suitable for various glaze types, greatly widens the practical application field of the ceramic glaze, and has a promoting effect on the development of the ceramic industry.
Disclosure of Invention
The invention aims to prepare a catalyst for improving anatase TiO 2 A super-hydrophilic self-cleaning ceramic glaze coating provides a preparation and application method of a coating with super-hydrophilic performance, which has low cost and simple process, and can be produced in large scale.
In order to solve the technical problems, the technical scheme of the invention is as follows: application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 13-17 wt% of deionized water, 12-17 wt% of strong acid, 55-60 wt% of titanium source, 5-10 wt% of inducer and 6-12 wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated sulfuric acid or concentrated hydrochloric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, sequentially dropwise adding anhydrous ethanol and a titanium source into a beaker, and stirring by magnetic force until the anhydrous ethanol and the titanium source are uniformly mixed, and marking as a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Evenly stirring for 10-15 min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet in the glaze bath 2 O 5 Of TiO2 2 3-5 min in the sol, and then according to the speed of 1-3 mm/sSlowly lifting and pulling out; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO2 2 Slowly pulling out the sol for 1-2 min at the speed of 0.5-1 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The application method is characterized in that: the calcining temperature in the third step is 700-800 ℃, and the heat preservation time is 30-60 min.
The application method is characterized in that: the drying temperature in the third step is 45-60 ℃.
The application method is characterized in that: the wetting angle of the product obtained in the third step is 3.555-3.581 degrees, the alkali resistance is 1.25-1.50, and the residual amount of oil stain is 3.402-3.452.
The invention has the beneficial effects that:
(1) The invention introduces CaTi into the glaze surface 2 O 5 Inducer, making it decompose anatase TiO in situ at higher temp 2 The hydrophilicity of the glaze is improved, so that the glaze has self-cleaning performance. While CaTi 2 O 5 The inducer can decompose CaO and other alkaline components similar to the alkali components in the glaze in situ, and can be used for preparing SiO in the glaze 2 Chemical reaction occurs, so that the glaze and the coating are promoted to form an intermediate layer, and the bonding property of the coating and the glaze is enhanced.
(2) The CaTi 2 O 5 In-situ decomposition of anatase TiO by inducer 2 The preparation method of the coating is simple and is suitable for various ceramic glaze surfaces.
Drawings
FIG. 1 is a chart of the wetting angle of the article of example 1;
FIG. 2 is an inspection of the XRD of the article of example 1;
FIG. 3 is an SEM examination of an article of example 1.
Detailed Description
To further illustrate the technical means and effects of the present invention for achieving the predetermined objects, the following detailed description of the embodiments, methods, steps, features and effects of the coating for improving anatase TiO2 super-hydrophilic self-cleaning ceramic glaze and the application method thereof according to the present invention is provided with the following preferred embodiments:
example 1:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 14wt% of deionized water, 14wt% of strong acid, 56wt% of titanium source, 10wt% of inducer and 6wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated hydrochloric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, coating preparation: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, sequentially dropwise adding anhydrous ethanol and a titanium source into a beaker, and stirring by magnetic force until the anhydrous ethanol and the titanium source are uniformly mixed, and marking as a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Uniformly stirring for 10min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet in the glaze bath 2 O 5 Of TiO2 2 Dissolving in sol for 3min, and slowly pulling out at a speed of 1 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO2 2 Slowly pulling out the sol for 1min at the speed of 0.5 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 700 ℃, and the heat preservation time is 30min.
The drying temperature in the third step is 45 ℃.
And the wetting angle of the product obtained in the third step is 3.555 degrees, the alkali resistance is 1.25 degrees, and the residual amount of oil stain is 3.402 degrees.
From FIG. 2, it can be seen that the super-hydrophilic self-cleaning ceramic glaze coating layer surface is mainly composed of anatase TiO 2 (PDF card 21-1272) phase composition, and endows the glaze surface with excellent super-hydrophilic performance. It can be seen from fig. 3 that the glaze is composed of particles with uniform size, and the glaze is endowed with the characteristics of flatness, smoothness and the like.
Example 2:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 13wt% of deionized water, 15wt% of strong acid, 60wt% of titanium source, 5wt% of inducer and 7wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated sulfuric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, dropwise adding anhydrous ethanol and a titanium source into a beaker in sequence, and stirring the mixture uniformly by magnetic force to obtain a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Stirring for 11min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet in the glaze bath 2 O 5 Of TiO2 2 Dissolving in sol for 4min, and slowly pulling out at a speed of 2 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO2 2 Slowly pulling out the sol for 1.5min at the speed of 0.6 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 720 ℃, and the heat preservation time is 35min.
The drying temperature in the third step is 55 ℃.
And the wetting angle of the product obtained in the third step is 3.571 degrees, the alkali resistance is 1.28, and the oil stain residual amount is 3.404.
Example 3:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 15wt% of deionized water, 12wt% of strong acid, 55wt% of titanium source, 6wt% of inducer and 12wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated hydrochloric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, dropwise adding anhydrous ethanol and a titanium source into a beaker in sequence, and stirring the mixture uniformly by magnetic force to obtain a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Uniformly stirring for 12min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet in the glaze bath 2 O 5 Of TiO (2) 2 Dissolving in sol for 5min, and slowly pulling out at a speed of 3 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO (2) 2 Dissolving in sol for 2min, and slowly pulling out at a speed of 0.7 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 730 ℃, and the heat preservation time is 40min.
The drying temperature in the third step is 60 ℃.
The wetting angle of the product obtained in the third step is 3.556 degrees, the alkali resistance is 1.30, and the oil stain residual amount is 3.412.
Example 4:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 13wt% of deionized water, 13wt% of strong acid, 57wt% of titanium source, 7wt% of inducer and 10wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated sulfuric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, dropwise adding anhydrous ethanol and a titanium source into a beaker in sequence, and stirring the mixture uniformly by magnetic force to obtain a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Stirring for 13min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet completely in a solution containing CaTi 2 O 5 Of TiO2 2 Dissolving in sol for 4min, and slowly pulling out at a speed of 2 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO2 2 Slowly pulling out the sol for 1.8min at the speed of 0.8 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 740 ℃, and the heat preservation time is 45min.
The drying temperature in the third step is 53 ℃.
And the wetting angle of the product obtained in the third step is 3.559 degrees, the alkali resistance is 1.35, and the residual amount of oil stain is 3.418.
Example 5:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 13wt% of deionized water, 16wt% of strong acid, 55wt% of titanium source, 7wt% of inducer and 9wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated hydrochloric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, sequentially dropwise adding anhydrous ethanol and a titanium source into a beaker, and stirring by magnetic force until the anhydrous ethanol and the titanium source are uniformly mixed, and marking as a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Stirring for 14min to obtain the product containing CaTi 2 O 5 Of TiO (2) 2 Sol;
step two, glaze coating: immersing the glaze sheet completely in a solution containing CaTi 2 O 5 Of TiO2 2 Dissolving in sol for 5min, and slowly pulling out at a speed of 3 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO (2) 2 Slowly pulling out the sol for 1.6min at the speed of 0.9 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 750 ℃, and the heat preservation time is 50min.
The drying temperature in the third step is 60 ℃.
And step three, the wetting angle of the product obtained in the step three is 3.575 degrees, the alkali resistance is 1.40, and the residual amount of oil stain is 3.420.
Example 6:
application toEnhancement of anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 17wt% of deionized water, 17wt% of strong acid, 56wt% of titanium source, 8wt% of inducer and 11wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated sulfuric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, dropwise adding anhydrous ethanol and a titanium source into a beaker in sequence, and stirring the mixture uniformly by magnetic force to obtain a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Stirring uniformly for 15min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet completely in a solution containing CaTi 2 O 5 Of TiO2 2 Dissolving in sol for 3min, and slowly pulling out at a speed of 1 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO (2) 2 Dissolving in sol for 1.7min, and slowly pulling out at a speed of 1 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 800 ℃, and the heat preservation time is 55min.
The drying temperature in the third step is 45 ℃.
And the wetting angle of the product obtained in the third step is 3.581 degrees, the alkali resistance is 1.45, and the oil stain residual amount is 3.440.
Example 7:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized in that the coating consists of the following components in percentage by massComprises the following steps: 17wt% of deionized water, 12wt% of strong acid, 55wt% of titanium source, 9wt% of inducer and 7wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated hydrochloric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, dropwise adding anhydrous ethanol and a titanium source into a beaker in sequence, and stirring the mixture uniformly by magnetic force to obtain a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Stirring for 13min to obtain the product containing CaTi 2 O 5 Of TiO (2) 2 Sol;
step two, glaze coating: immersing the glaze sheet in the glaze bath 2 O 5 Of TiO2 2 Dissolving in sol for 5min, and slowly pulling out at a speed of 3 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO2 2 Dissolving in sol for 2min, and slowly pulling out at a speed of 0.5 mm/s;
step three, firing: and drying the coated glaze sheets, then placing the dried glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 750 ℃, and the heat preservation time is 30min.
The drying temperature in the third step is 60 ℃.
The wetting angle of the product obtained in the third step is 3.564 degrees, the alkali resistance is 1.48, and the oil stain residual amount is 3.446.
Example 8:
application to improving anatase TiO 2 The coating of the super-hydrophilic self-cleaning ceramic glaze is characterized by comprising the following components in percentage by mass: 15wt% of deionized water, 12wt% of strong acid, 58wt% of titanium source, 8wt% of inducer and 7wt% of absolute ethyl alcohol.
The titanium source is tetrabutyl titanate, the strong acid is concentrated sulfuric acid, and the inducer is CaTi 2 O 5 。
The application method of the coating is characterized by comprising the following steps:
step one, preparing a coating: according to the mass percentage of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, sequentially dropwise adding anhydrous ethanol and a titanium source into a beaker, and stirring by magnetic force until the anhydrous ethanol and the titanium source are uniformly mixed, and marking as a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Uniformly stirring for 14min to obtain the product containing CaTi 2 O 5 Of TiO2 2 Sol;
step two, glaze coating: immersing the glaze sheet completely in a solution containing CaTi 2 O 5 Of TiO2 2 Dissolving in sol for 4min, and slowly pulling out at a speed of 2 mm/s; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO (2) 2 Slowly pulling out the sol for 1min at the speed of 0.6 mm/s;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
The calcining temperature in the third step is 700 ℃, and the heat preservation time is 60min.
The drying temperature in the third step is 55 ℃.
The wetting angle of the product obtained in the third step is 3.556 degrees, the alkali resistance is 1.50, and the residual amount of greasy dirt is 3.452.
The present invention is not intended to be limited to the particular embodiments shown and described, and various modifications, equivalents and improvements made within the spirit and scope of the present invention are intended to be included therein.
Claims (6)
1. Application to improving anatase TiO 2 Coating of a superhydrophilic self-cleaning ceramic glaze, characterized in that of said coatingThe components by mass percentage are as follows: 13-17 wt% of deionized water, 12-17 wt% of strong acid, 55-60 wt% of titanium source and inducer CaTi 2 O 5 5 to 10 percent of anhydrous alcohol and 6 to 12 percent of absolute ethyl alcohol.
2. The coating of claim 1, wherein: the titanium source is tetrabutyl titanate, and the strong acid is concentrated sulfuric acid or concentrated hydrochloric acid.
3. Method for applying a coating according to claim 1 or 2, characterized in that it comprises the following steps:
step one, preparing a coating: according to the mass percentage composition of the coating, firstly, sequentially dropwise adding deionized water and strong acid into a beaker, and stirring by magnetic force until the deionized water and the strong acid are uniformly mixed, and marking as a solution A; then, sequentially dropwise adding anhydrous ethanol and a titanium source into a beaker, and stirring by magnetic force until the anhydrous ethanol and the titanium source are uniformly mixed, and marking as a solution B; then slowly dripping the solution A into the solution B, and magnetically stirring for 20min to form TiO 2 Sol, finally in TiO 2 Adding CaTi into the sol 2 O 5 Evenly stirring for 10-15 min to obtain the product containing CaTi 2 O 5 Of TiO (2) 2 Sol;
step two, glaze coating: immersing the glaze sheet in the glaze bath 2 O 5 Of TiO (2) 2 Slowly pulling out the sol at the speed of 1-3 mm/s for 3-5 min; then the glaze sheet is completely immersed in the solution containing CaTi 2 O 5 Of TiO2 2 Slowly pulling out the sol at the speed of 0.5-1 mm/s for 1-2 min;
step three, firing: and drying the coated glaze sheets, then putting the glaze sheets into a kiln to calcine in an oxidizing atmosphere, and naturally cooling the glaze sheets after being taken out of the kiln to obtain the product.
4. The application method according to claim 3, characterized in that: the calcining temperature in the third step is 700-800 ℃, and the heat preservation time is 30-60 min.
5. The method of application according to claim 3, characterized in that: the drying temperature in the third step is 45-60 ℃.
6. The method of application according to claim 3, characterized in that: the wetting angle of the product obtained in the third step is 3.555-3.581 degrees, the alkali resistance is 1.25-1.50 degrees, and the residual amount of oil stain is 3.402-3.452.
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| DE2829985A1 (en) * | 1978-07-07 | 1980-01-17 | Reimbold & Strick | Frit or glaze contg. calcium titanium silicate as opacifier - to obtain dense opaque white glaze which does not discolour |
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| US7365118B2 (en) * | 2003-07-08 | 2008-04-29 | Los Alamos National Security, Llc | Polymer-assisted deposition of films |
| US11519086B2 (en) * | 2019-05-02 | 2022-12-06 | King Fahd University Of Petroleum And Minerals | Fabrication of photoactive CaTiO3—TiO2 composite thin film electrodes via single step AACVD |
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|---|---|---|---|---|
| DE2829985A1 (en) * | 1978-07-07 | 1980-01-17 | Reimbold & Strick | Frit or glaze contg. calcium titanium silicate as opacifier - to obtain dense opaque white glaze which does not discolour |
| JP2001286755A (en) * | 2000-04-06 | 2001-10-16 | Showa Highpolymer Co Ltd | Photocatalytic composition which can be excited by visible light and photocatalytic thin film, and their manufacturing methods |
| JP2004097868A (en) * | 2002-09-05 | 2004-04-02 | Jfe Steel Kk | Photocatalyst and manufacturing method of composite material having photocatalyst film formed thereon |
| WO2010053459A1 (en) * | 2008-11-07 | 2010-05-14 | Univerza V Novi Gorici | Preparation of tio2/sio2 sols and use thereof for deposition of self-cleaning anti- fogging coatings |
| KR20100132898A (en) * | 2009-06-10 | 2010-12-20 | 주식회사 프레코 | Anti-sticking paints composition, anti-sticking sheet using thereof |
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