CN111499202B - Opaque glaze with high solar light reflectivity and preparation method thereof - Google Patents
Opaque glaze with high solar light reflectivity and preparation method thereof Download PDFInfo
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- CN111499202B CN111499202B CN202010608150.6A CN202010608150A CN111499202B CN 111499202 B CN111499202 B CN 111499202B CN 202010608150 A CN202010608150 A CN 202010608150A CN 111499202 B CN111499202 B CN 111499202B
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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
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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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
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
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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
- C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
- C03C2205/02—Compositions applicable for the manufacture of vitreous enamels or glazes for opaque enamels or glazes
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Abstract
The invention discloses opaque glaze with high solar light reflectivity and a preparation method thereof. The opacified glaze comprises the following raw materials: in percentage by mass8-12% of titanium frit, 8-10% of titanium dioxide and 18-24% of calcite; the molar ratio of calcium to titanium of the opacified glaze is 1.6-2.2; wherein the titanium frit comprises the following chemical composition: by mass percent, SiO2：52～55%、Al2O3：7～11%、CaO：15～19%、TiO2: 8 to 11 percent. The opaque glaze can be used for porcelain tiles, the use temperature can exceed 1150 ℃, and the defect that the glaze of the traditional opaque glaze is yellow due to the ultraviolet absorption effect of rutile titanium dioxide when the use temperature exceeds 1000 ℃ is avoided.
Description
Technical Field
The invention belongs to the field of building ceramics, and particularly relates to opaque glaze with high solar light reflectivity and a preparation method thereof.
Background
In the architectural ceramic industry, an opaque glaze is a common glaze for ceramics, and the opaque glaze refers to a phenomenon that after light passes through a glaze layer, the transmitted light is weakened and the glaze presents opacity to different degrees under the influences of the reflection action of an interface, the absorption action of glass, the scattering action of phase separation particles (generally referred to as gas phase, liquid phase or solid phase separation particles) in the glaze and the like. The opaque glaze generally has a strong covering effect, and most of the opaque glaze takes substances with higher refractive indexes as dispersed particles, so sunlight cannot penetrate through the opaque glaze, and the opaque glaze with good covering rate often has a strong reflection effect on the sunlight.
Common opacifiers for ceramic glazes include titanium dioxide, cerium oxide, tin oxide, zinc oxide, and the like. Titanium dioxide is an oxide with a high refractive index, and has a very strong reflection effect on light. Titanium dioxide is also commonly used as a main component of the impermeable ground coat to be applied to the ceramic chip, because the water absorption rate of the ceramic chip is high, when the ceramic chip absorbs water, water permeates the ceramic chip blank and appears on the surface of the ceramic chip, so that the generation of watermark affects the attractiveness of the ceramic chip, and the impermeable ground coat has high covering rate, so that the watermark cannot permeate the impermeable ground coat and appear on the surface of the ceramic chip. However, titanium dioxide is a polycrystalline oxide, and when the temperature exceeds 1000 ℃, the titanium dioxide exists in a rutile crystal form, and rutile has a strong absorption effect on purple light at high temperature, so that the glaze surface is yellow, and therefore, when the waterproof ground coat containing the titanium dioxide is used for ceramic tiles, the use temperature is required to be lower than 1050 ℃, and the waterproof ground coat cannot be used for ceramic products with high requirements on whiteness.
Disclosure of Invention
Aiming at the problems, the invention provides an opaque glaze with high solar light reflectivity and a preparation method thereof. The opaque glaze can be used for porcelain tiles, the use temperature can exceed 1150 ℃, and the defect that the glaze of the traditional opaque glaze is yellow due to the ultraviolet absorption effect of rutile titanium dioxide when the use temperature exceeds 1000 ℃ is avoided. In addition, the opaque glaze has high reflectivity to sunlight.
In a first aspect, the invention provides an opacified glaze with high solar light reflectivity, which comprises the following raw materials: by mass, 8-12% of titanium frit, 8-10% of titanium dioxide and 18-24% of calcite; wherein the molar ratio of calcium to titanium of the opacified glaze is 1.6-2.2. By controlling the molar ratio of calcium to titanium in the opacified glaze within the range, titanium dioxide and calcite in the opacified glaze can be promoted to react to generate titanium sphene in the sintering process, and the condition that the titanium dioxide exists in a rutile crystal phase at high temperature to cause the glaze to turn yellow is avoided. When the molar ratio of calcium to titanium in the opaque glaze exceeds 2.2, the minimum eutectic point of the glaze composition of the opaque glaze is low and the melting temperature range is narrowed due to the high calcium content in the opaque glaze, so that defects such as glaze pinholes, miliaria and the like are easily generated.
Preferably, the chemical composition of the opacified glaze comprises: by mass percent, SiO2：44～48%、Al2O3：19～21%、Fe2O3：0.05～0.19%、CaO：10～14%、TiO2：8～12%、MgO：0.1～0.5%、K2O：2.4～2.6%、Na2O: 0.5-1.2% and loss on ignition of 1.0-1.5%。
Preferably, the opaque glaze further comprises the following raw materials: the weight percentage of the potassium feldspar is 19-30%, the quartz is 15-20%, the calcined soil is 5-10%, and the kaolin is 12-16%.
Preferably, the mass ratio of the titanium frit to the titanium dioxide is 0.8-1.5. The mass ratio of the titanium frit to the titanium dioxide is within the above range, so that the opacifying performance (high whiteness and low yellow tone) of the opacifying glaze can be ensured, and the high-temperature fluidity of the glaze can be improved, thereby improving the flatness of the glaze surface.
Preferably, the chemical composition of the titanium frit comprises: by mass percent, SiO2：52～55%、Al2O3：7～11%、CaO：15～19%、TiO2：8～11%、Fe2O3：0.08～0.17%、MgO：2.05～3.5%、K2O：3.2～4.7%、Na2O：0.8～2.5%、P2O5 0.22～0.55%。
Preferably, the melting temperature of the opacified glaze is 1150-1220 ℃.
The titanium frit in the opaque glaze with high solar light reflectivity is precipitated with nano titanic sphene crystal grains at high temperature (about 920-950 ℃), and the nano titanic sphene crystal grains are used as crystal seeds to induce the titanium dioxide and calcite to react to generate titanic sphene crystal phases.
The grain size of the titanium sphene crystal phase can be 450-600 nm. The grain diameter of the crystal phase of the titanic sphene is within a visible light range, and according to a scattering theory, the grain diameter has the strongest scattering effect within the visible light wavelength range.
The content of a titanium sphene crystal phase in a phase composition of the opacified glaze after sintering is 18-22 wt%. The content of the titanium sphene crystal phase is related to the usage amount of titanium dioxide and titanium frit which are used as the raw materials of the opacified glaze. By using the opacified glaze composed of the raw materials, the glaze can be TiO2The content of the active ingredients is controlled to be about 8-12%. When TiO is in glaze2When the content of titanium sphene is less than 8%, the generated titanium sphene has low crystalline phase content, insufficient opacification degree and low whiteness; when TiO is in glaze2When the content of (2) is more than 12%, the content of titanium dioxide in the glaze is too high, so that a certain content of TiO is remained on the glaze surface after firing2Resulting in yellowing of the glaze.
The phase composition after the opacified glaze is sintered comprises 0.45-0.57% of quartz by mass, 1.0-1.2% of perovskite by mass and the balance of amorphous phase besides the titanium sphene crystalline phase.
Preferably, the b value (representing yellow tone) of the opacified glaze is 0.9-1.8.
Preferably, the opaque glaze further comprises 0.01-0.03 wt% of cobalt aluminate, so that the yellow color tone of the opaque glaze can be further inhibited.
In a second aspect, the invention provides a method for preparing the opaque glaze with high solar reflectance. The preparation method comprises the following steps: ball-milling and mixing the raw materials of the opaque glaze, controlling the screen residue of 325 meshes to be 0.5-0.8wt% and the iron content to be 0.15-0.3 wt%, and discharging the slurry to obtain the opaque glaze with high solar reflectance.
In a third aspect, the invention provides the application of the opaque glaze with high solar reflectance in ceramic products.
Drawings
FIG. 1 is a reflectance graph of a high solar reflectance opacified glaze according to example 1 of the present invention;
FIG. 2 is an SEM image of the high solar reflectance opacified glaze of example 1 after firing;
FIG. 3 is an XRD pattern of the high solar reflectance opacified glaze of example 1 of the present invention after firing;
FIG. 4 is a graph showing scattering intensity as a function of the particle size of the dispersed phase when zircon, rutile, and titanium titanite are used as opacifying agents, respectively; as can be seen from fig. 4, when the particle diameter of the dispersed phase particles is within the visible light wavelength range (0.35 μm or more), the scattering intensity is better;
FIG. 5 is a TG and DSC curve of the titanium frit used in example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.
The high solar reflectance opacified glaze and the preparation method thereof are exemplified as follows.
The factors influencing the solar reflectance of the opacified glaze include the following: the dispersed phase particle size, the number of dispersed phase particles, and the matrix refractive index. The higher the refractive index of the matrix is, the more the number of the dispersed phase particles is, and when the particle size of the dispersed phase is in the visible light wave band range, the higher the reflectivity of the matrix to sunlight is. The refractive index (2.4-2.7) of titanium dioxide is high, but the titanium dioxide exists in a rutile form at the temperature of over 950 ℃, and the rutile titanium dioxide can strongly absorb purple light at high temperature to cause the glaze to yellow. According to the method, titanium dioxide and titanium frit are jointly used, titanium sphene crystal grains with nano-scale grain sizes are precipitated from the titanium frit at high temperature, and the titanium sphene crystal grains are taken as crystal seeds to induce the titanium dioxide and calcite in the opacified glaze to react to generate a large amount of titanium sphene crystal phases. Because titanium dioxide and calcite reaction generate titanium sphene (the refractive index of titanium sphene can reach 2.0), this can realize controlling the lower titanium dioxide content in the glaze even not remaining titanium dioxide, when guaranteeing opalescence effect and reflection effect, effectively alleviate the yellow of glaze and transfer.
The raw material composition of the opacified glaze is determined through tests. By way of example, the opaque glaze comprises the following raw materials: by mass, 8-12% of titanium frit, 8-10% of titanium dioxide, 18-24% of calcite, 19-30% of potassium feldspar, 15-20% of quartz, 5-10% of calcined soil and 12-16% of kaolin. Preferably, the sum of the mass ratios of the raw materials of the opaque glaze is 100%.
The crystallization temperature of the titanium frit is 900-1000 ℃, and the titanium frit begins to precipitate titanium sphene crystals at the temperature higher than 900 ℃, so that the opacification is enhanced (as shown in fig. 5). In addition, the melting temperature of the titanium frit is lower and is 950-1100 ℃, so that the high-temperature fluidity of the glaze can be improved, more titanium dioxide and calcite are promoted to react to generate titanium sphene, and the whiteness of the glaze is improved.
In the raw material composition of the opacified glaze, if the mass percentage of the titanium frit is less than 8%, the content of the precipitated titanium sphene seed crystal is low, a good opacification effect cannot be achieved, and the poor fluxing effect is not beneficial to improving the high-temperature fluidity of the opacified glaze. If the mass percentage of the titanium frit is higher than 12%, the melting temperature of the opacified glaze is too low due to the excessively high content of the titanium frit, so that the generated titanium sphene is easily melted during the firing process. Through tests, the melting temperature of the opacified glaze is optimally controlled to 1150-1220 ℃.
In the composition of the opacified glaze, titanium dioxide exists in the form of titanium dioxide powder. For example, the titanium dioxide powder may have a particle size of 1 to 2 μm. The mass percent of the titanium dioxide is preferably controlled to be 8-10%. If the mass percent of the titanium dioxide is less than 8%, the content of the titanium dioxide is low, and the titanium dioxide cannot react with calcite to generate enough titanium sphene crystal phase; if the mass percentage of the titanium dioxide is higher than 10%, the titanium dioxide in the glaze is excessive, so that residual titanium dioxide still exists in a fired glaze layer, and the glaze surface is easy to yellow.
The molar ratio of calcium to titanium of the opacified glaze is 1.6-2.2. In experiments, it is found that when the molar ratio of calcium to titanium of the opacified glaze exceeds 2.2 due to the excessive addition of calcite, the lowest eutectic point of the glaze composition is low due to a small amount of sodium potassium in the glaze, which is not beneficial to exhausting of the glaze, and easily causes defects such as glaze pinholes and miliaria.
When titanium frit is not included in the raw materials of the opacified glaze and titanium titanite serving as an opacifier is generated only by reacting titanium dioxide, calcite and the like, the molar ratio of calcium to titanium is controlled to be 1.8-2.5, and the whiteness of the glaze surface is good. However, in this case, the glaze surface will have a yellowish hue, and the b value (representing the yellowish hue) in the Lab value of the opaque glaze is 3.5 to 6.5. At the moment, the content of titanium titanite crystal grains generated by the reaction of titanium dioxide and calcite is 8-11 wt%. This is because, when the titanium opacified glaze is prepared by simply using the raw glaze (titanium dioxide powder), titanium dioxide and calcite do not react sufficiently, the content of the generated titanium sphene is small, and the residual titanium dioxide on the glaze surface has a small amount of yellow hue due to the strong coloring ability of titanium dioxide.
When titanium dioxide is not included in the raw materials of the opacified glaze and only titanium sphene precipitated from the titanium frit is used as the opacifier, the content of the generated titanium sphene is 10-12 wt%. And because the melting temperature of the titanium frit is lower, the generated titanium sphene crystal grains are gradually dissolved along with the temperature rise, so that the reflection effect of the glaze surface is influenced, and the b value in the Lab value of the opaque glaze is between 2.5 and 4, and the yellow tone is obvious. In addition, in the absence of titanium dioxide (green glaze), since the melting temperature range of the titanium frit is low, when a proper amount of the titanium frit is added, the titanium frit reacts with other raw materials, resulting in a change in the composition of titanium sphene. For example, calcium oxide in the titanium frit preferentially reacts with quartz or alumina to form anorthite as the temperature increases, and the content of anorthite increases as the temperature increases.
The opacified glaze combines the raw glaze (titanium dioxide) and the titanium frit, the titanium frit is lower in temperature, the improvement of the high-temperature fluidity of the glaze is facilitated, in addition, the titanium frit can precipitate titanium sphene in the process of temperature rise, the titanium dioxide and calcite in the raw glaze are induced to fully react to generate the titanium sphene, and the content of the titanium dioxide in the opacified glaze after sintering is reduced as much as possible (as shown in figure 3, no crystalline phase of the titanium dioxide is detected in an XRD (X-ray diffraction) diagram). That is, the titanium frit of the present invention may act as a solvent and a seed crystal to promote the formation of titanite from titania and calcite.
The invention combines the raw glaze and the fritted glaze by using titanium dioxide and titanium fritted glaze to prepare the ceramic opaque glaze with a plurality of particle sizes in the visible light wavelength range. The opaque glaze has high reflectivity to sunlight, and meanwhile, the glaze surface is smooth and the whiteness is high. In some embodiments, the opaque glaze has a solar reflectance of 0.87 to 0.91. This is because when light is transmitted from one medium into another, transmission, absorption, scattering and reflection occur, and for the purpose of enhancing reflectivity, the transmission is reduced and the reflection is enhanced, while opacification minimizes transmission, which is advantageous for enhancing reflectivity.
In addition, tests show that the b value of the opacified glaze is between 0.9 and 1.8, the yellow tone is greatly reduced, and the reflectivity of the generated titanium sphene to sunlight is enhanced. This is because the yellow color of the glaze can be effectively suppressed by titanium sphene produced by the reaction of titanium dioxide and calcium oxide. The titanite has a high refractive index (2.0) and a good opacifying effect. Moreover, the glaze surface flatness and whiteness of the opaque glaze also achieve the best effect. In some embodiments, the opacified glaze may have a whiteness of 75-80 °.
When a proper amount (0.01-0.03 wt%) of cobalt aluminate is added into the opaque glaze, the yellow tone of the glaze surface can be further inhibited, the whiteness is enhanced, and the solar reflectance is enhanced.
The invention also provides a preparation method of the opaque glaze with high solar light reflectivity, which comprises the following steps: weighing the raw materials of the opaque glaze according to the proportion, ball-milling, discharging slurry, and sieving to remove iron to obtain the ceramic opaque glaze with high solar reflectance. In some embodiments, the chemical composition of the opacified glaze comprises: by mass percent, SiO2：44～48%、Al2O3：19～21%、Fe2O3：0.05～0.19%、CaO：10～14%、TiO2：8～12%、MgO：0.1～0.5%、K2O：2.4～2.6%、Na2O: 0.5-1.2% and loss on ignition of 1.0-1.5%. In the preparation method, the 325-mesh screen residue of the slurry is controlled to be 0.5-0.8wt%, and the iron content is controlled to be 0.15-0.3 wt%. The flow speed of the opacified glaze can be 50-70 seconds.
In the prior art, titanium dioxide is simply used for preparing the opaque glaze containing titaniferous sphene crystalline phase, and the problems that the titanium dioxide is not reacted sufficiently and the b value of the glaze surface is high exist. In order to solve the problems, the titanium dioxide is used, and simultaneously, a proper amount of titanium frit is added to achieve the effect to be achieved: 1. the content of generated titanium sphene is obviously increased; 2 the crystal phase grain diameter of the generated titanium sphene is about 500nm, and 3 the refractive index of the generated titanium sphene is 2.0. The three components are combined to prepare the opaque glaze with higher reflectivity. In some embodiments, the present opacifying glaze has a reflectance in the visible band of greater than 0.9 and a reflectance in the near infrared band of greater than 0.85.
The opacified glaze is applied to a ceramic product, and the chromatic value of the glaze surface is 88-92 in terms of L value, 0.08-0.18 in terms of a value and 0.9-1.8 in terms of b value.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
The reflectivity of the opacified glaze is tested according to GB/T31389-2015, the whiteness of the opacified glaze is tested according to a whiteness meter PN-48b, and the b value of the opacified glaze is tested according to an X-rite color premier 8200 colorimeter.
Example 1
Step 1, preparing the opaque glaze according to the formula: the opacified glaze comprises the following raw materials: 30% of potassium feldspar, 12% of titanium frit, 8% of titanium dioxide, 18% of calcite, 15% of quartz, 5% of calcined soil and 12% of kaolin. The chemical composition of the titanium frit comprises: by mass percent, SiO2：52～55%、Al2O3：7～11%、CaO：15～19%、TiO2：8～11%、Fe2O3：0.08～0.17%、MgO：2.05～3.5%、K2O：3.2～4.7%、Na2O：0.8～2.5%、P2O50.22 to 0.55 percent. Cobalt aluminate accounting for 0.02wt% is added into the opacified glaze. After ball milling and mixing the raw materials, controlling the residual content of 325-mesh sieve to be 0.5wt% and the iron content to be 0.3wt%, and discharging the slurry to obtain the opaque glaze with high solar reflectance;
step 4, printing red patterns on the surface of the blank sprayed with the opacified glaze in an inkjet mode, and controlling the gray level to be below 40%;
step 5, spraying high-temperature matte protective glaze on the surface of the biscuit after the red pattern is printed by ink jet, wherein the specific gravity of the high-temperature matte protective glaze is 1.3 g/cm3The glazing amount is 300g/m2(ii) a The high-temperature matte protective glaze comprises the following components: SiO 22 52.74%、Al2O3 21%、Fe2O3 0.26%、CaO 0.5%、MgO 0.17%、K2O 7.15%、Na23.39 percent of O and 1.2 percent of loss on ignition;
and 6, firing the biscuit sprayed with the high-temperature matte protective glaze in a kiln at the maximum firing temperature of 1150 ℃ for 65min to obtain the ceramic plate with high heat reflectivity.
As can be seen from FIG. 1, the solar reflectance of the ceramic plate with high thermal reflectance using the opaque glaze of the present invention is 0.87 to 0.91. As can be seen from FIG. 2, after the opaque glaze with high solar reflectance is fired, nano titanium sphene crystal grains with the grain size of 450-600 nm exist in the glaze layer. Referring to fig. 3, no titanium dioxide crystalline phase was detected in the XRD pattern. The titanic sphene crystal phase content in the phase composition of the opacified glaze after sintering is 18-22 wt%.
Comparative example 1
Essentially the same as example 1, except that: the opacified glaze comprises the following raw materials: the composite material comprises, by mass, 80% of titanium frit, 5% of calcined clay and 15% of kaolin. The chemical composition of the titanium frit comprises: by mass percent, SiO2：52～55%、Al2O3：7～11%、CaO：15～19%、TiO2：8～11%、Fe2O3：0.08～0.17%、MgO：2.05～3.5%、K2O：3.2～4.7%、Na2O：0.8～2.5%、P2O50.22 to 0.55 percent. Cobalt aluminate accounting for 0.02wt% is added into the opacified glaze. In the comparative example, the content of titanium sphene (generated by the reaction of titanium frit) after firing the opacified glaze was 10 to 12wt%, and the particle size of the titanium sphene was 450 to 550 nm. Through tests, the whiteness of the ceramic plate is 55, the b value is 2.5-4, and the solar reflectance is 0.68-0.73.
Comparative example 2
Essentially the same as example 1, except that: the opacified glaze comprises the following raw materials: by mass percentage, 40% of potash feldspar, 10% of titanium dioxide, 18% of calcite, 15% of quartz, 5% of calcined soil and 12% of kaolin. Cobalt aluminate accounting for 0.02wt% is added into the opacified glaze. In the comparative example, the content of titanium sphene (generated by the reaction of titanium dioxide and calcite) in the glaze surface after the opacified glaze is fired is 8-11 wt%, and the particle size of the titanium sphene is about 1 μm. Through tests, the whiteness of the ceramic plate is 58, the b value is 3.5-6.5, and the sunlight reflectivity is 0.7-0.75.
Comparative example 3
Essentially the same as example 1, except that: the opacified glaze comprises the following raw materials: by mass percentage, 33% of potash feldspar, 8% of titanium dioxide, 12% of titanium frit, 15% of calcite, 15% of quartz, 5% of calcined soil and 12% of kaolin. The chemical composition of the titanium frit comprises: by mass percent, SiO2：52～55%、Al2O3：7～11%、CaO：15～19%、TiO2：8～11%、Fe2O3：0.08～0.17%、MgO：2.05～3.5%、K2O：3.2～4.7%、Na2O：0.8～2.5%、P2O50.22 to 0.55 percent. Cobalt aluminate accounting for 0.02wt% is added into the opacified glaze. The comparative example opacified glaze had a perovskite molar ratio of 1.33. The content of titanium sphene generated by reaction after the opacified glaze is fired is 7-10 wt%, and the particle size of the titanium sphene is about 600nm-1 mu m. Through tests, the whiteness of the ceramic plate is 50, the b value is 5.5-9.5, and the sunlight reflectivity is 0.59-0.62.
Claims (6)
1. The opacified glaze with high solar light reflectivity is characterized by comprising the following raw materials: by mass, 8-12% of titanium frit, 8-10% of titanium dioxide and 18-24% of calcite; the molar ratio of calcium to titanium of the opacified glaze is 1.6-2.2; wherein the titanium frit comprises the following chemical composition: by mass percent, SiO2：52～55%、Al2O3：7～11%、CaO：15～19%、TiO2: 8-11%; the melting temperature of the titanium frit is 950-1100 ℃; the chemical composition of the opacified glaze comprises: by mass percent, SiO2：44～48%、Al2O3：19～21%、CaO：10～14%、TiO2：10～12%、Fe2O3：0.05～0.19%、MgO：0.1～0.5%、K2O：2.4～2.6%、Na2O: 0.5-1.2% and loss on ignition of 1.0-1.5%; precipitating titanium sphene crystal grains from the titanium frit at the temperature of 920-950 ℃, and inducing the titanium dioxide and calcite to react by taking the titanium sphene crystal grains as seed crystals to generate a titanium sphene crystal phase with the particle size of 450-600 nm; the content of a titanium sphene crystal phase in a phase composition after the opacified glaze is fired is 18-22 wt%; the b value of the opal glaze, which represents yellow tone in Lab value, is 0.9-1.8.
2. The opaque glaze with high solar light reflectivity according to claim 1, wherein the opaque glaze further comprises the following raw materials: the weight percentage of the potassium feldspar is 19-30%, the quartz is 15-20%, the calcined soil is 5-10%, and the kaolin is 12-16%.
3. The opaque glaze with high solar light reflectivity according to claim 1, wherein the mass ratio of the titanium frit to the titanium dioxide is 0.8-1.5.
4. The high solar reflectance opacified glaze according to claim 1 wherein the titanium frit has a chemical composition further comprising: in mass percent, Fe2O3：0.08～0.17%、MgO：2.05～3.5%、K2O：3.2～4.7%、Na2O：0.8～2.5%、P2O5 0.22～0.55%。
5. The opaque glaze with high solar light reflectivity according to claim 1, wherein the opaque glaze further comprises 0.01-0.03 wt% of cobalt aluminate.
6. The opaque glaze with high solar light reflectance according to claim 1, wherein the opaque glaze has a reflectance of more than 0.9 in the visible light band and a reflectance of more than 0.85 in the near infrared band.
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| CN115304277A (en) * | 2022-08-03 | 2022-11-08 | 重庆唯美陶瓷有限公司 | Titanium white opacified ground glaze and ceramic plate |
| CN115304276B (en) * | 2022-08-03 | 2023-12-26 | 东莞市唯美陶瓷工业园有限公司 | Composite glaze layer, ceramic plate and preparation method thereof |
| CN115650587B (en) * | 2022-12-26 | 2023-03-21 | 新明珠集团股份有限公司 | Reflective heat-insulation glaze, reflective heat-insulation ceramic tile and preparation method and application thereof |
| CN116947536B (en) * | 2023-09-18 | 2024-02-23 | 新明珠集团股份有限公司 | Zirconium-free ground glaze, titanium raw material opacified glazed tile and preparation method thereof |
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| GB1061818A (en) * | 1962-11-19 | 1967-03-15 | Hubertus Wessel | |
| JPS5864242A (en) * | 1981-10-13 | 1983-04-16 | Matsushita Electric Ind Co Ltd | Low-melting semitranslucent enamel frit |
| CN86105759B (en) * | 1986-07-29 | 1988-10-26 | 北京市建筑材料工业学校 | Singe-step glazing method with opal ti-zn system at medium or high tmep. |
| CN1031518A (en) * | 1987-08-22 | 1989-03-08 | 国家建筑材料工业局山东工业陶瓷研究设计院 | Titania milky glaze for making glazed brick |
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| CN106977104A (en) * | 2017-03-10 | 2017-07-25 | 华南理工大学 | A kind of preparation method of reflective insulation ceramics using titanium sphene as principal crystalline phase |
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