CN108409146B - Zirconium-free sapphirine microcrystal opaque glaze and manufacturing method thereof - Google Patents
Zirconium-free sapphirine microcrystal opaque glaze and manufacturing method thereof Download PDFInfo
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- CN108409146B CN108409146B CN201810544981.4A CN201810544981A CN108409146B CN 108409146 B CN108409146 B CN 108409146B CN 201810544981 A CN201810544981 A CN 201810544981A CN 108409146 B CN108409146 B CN 108409146B
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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
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
- C03C10/0045—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents containing SiO2, Al2O3 and MgO as main constituents
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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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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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
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
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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
Abstract
The invention discloses a zirconium-free sapphirine microcrystal opaque glaze and a manufacturing method thereof. The zirconium-free sapphirine microcrystal opaque glaze comprises the following components in percentage by mass: na (Na)2O：1～3%；K2O：2～3%；Al2O3：25～28%；MgO：8～10%；B2O3：5～7%；Li2O：0～1%；CaO：0～1%；P2O5: 0 to 1 percent; the balance being SiO2. The invention uses sapphirine to replace ZrSiO4The emulsion glaze is prepared by using the emulsion agent. The zirconium-free sapphirine microcrystal opaque glaze has the advantages of high glaze glossiness, high hardness, good wear resistance, good acid and alkali resistance and scratch resistance. In addition, compared with ZrSiO4The opaque glaze does not contain zircon sand and any radioactive element, has low cost, environmental protection and good opalescence effect, has the same production process as the zirconium system opaque fritted glaze, and reduces the production cost.
Description
Technical Field
The invention relates to the field of ceramic glaze, in particular to a zirconium-free sapphirine microcrystalline opaque glaze and a manufacturing method thereof.
Background
In order to cover the color and defects of the blank and expand the source of raw materials, the opaque glaze with good decoration effect and strong covering capability is widely used on the surface and the ground coat of the ceramic. The present commonly used opacified glaze for building sanitary ceramics is a stannic oxide system opacified glaze, a titanium oxide system opacified glaze and a zirconite system opacified glaze. The opacified glaze of the tin oxide system has good opacification effect, but is expensive and high in cost; titanium oxide is easy to be separated out from a melt in the form of anatase during high-temperature firing, so that the glaze surface is discolored; zircon system opacificationIn glaze, ZrSiO4The opacifier is the most widely used opacifier at present, has the advantages of high refractive index, high hardness, no influence of atmosphere and the like, enables the glaze layer to have good opacification effect, and can improve the mechanical property of the glaze layer. However, the zirconium resource in China is relatively poor, the price of the zirconium silicate raw material is rapidly increased in recent years, zirconite is associated with thorium and uranium which are radioactive elements, and the thorium and the uranium are difficult to remove in the later processing and are harmful to the health of people. In addition, in ZrSiO4In the opaque glaze, only ZrSiO with higher content is added4(10-15 wt%) and ZrSiO4Has a very fine particle size of (<1 μm), a good opacifying effect is obtained. But ZrSiO4The hardness of (Mohs hardness 7.5) is high, the preparation process of the ultrafine powder is complex and expensive, and the ball milling cost is increased along with the reduction of particles. Therefore, the development of the zirconium-free opaque glaze with low cost, environmental protection and good opacifying effect has important significance. Sapphire microcrystalline opaque glaze, the crystal precipitated from glaze layer is Mg2Al4SiO10The sapphirine has proper grain size and strong scattering effect on visible light, not only achieves the whiteness of the common zirconium white fritted glaze, but also can improve the glossiness, hardness, wear resistance, acid and alkali resistance and scratch resistance of the glaze surface and reduce the production cost.
Disclosure of Invention
The invention aims to provide a zirconium-free sapphirine microcrystal opaque glaze, which is characterized in that Mg is precipitated from a glaze layer2Al4SiO10The sapphirine crystal has strong scattering effect and good opacifying effect, improves the glossiness, hardness, wear resistance, acid and alkali resistance and scratch resistance of the glaze surface, and reduces the production cost.
The purpose of the invention is realized by the following technical scheme.
The zirconium-free sapphirine microcrystal opaque glaze comprises the following components in parts by weight: na (Na)2O：1%~3%；K2O：2%~3%；Al2O3：25%~28%；MgO：7%~10%； B2O3：5%~8%；Li2O：0～1%；CaO：0～1%；
P2O5: 0 to 1 percent; the balance being SiO2。
Preferably, the zirconium-free sapphirine microcrystalline opacified glaze consists of the following components in parts by weight: na (Na)2O：1.84%；
K2O：2.76%；Al2O3：27.62%；MgO：8.21%；B2O3：6.14%；Li2O：0.25%；CaO：0.28%；
P2O5：0.47%；SiO2：52.43%。
The method for manufacturing the zirconium-free sapphirine microcrystal opaque glaze comprises the following steps:
(1) mixing potash feldspar, albite, talc, quartz powder, boric acid, phosphorus pentoxide and bauxite, uniformly ball-milling, melting, water quenching, and ball-milling to obtain frit powder;
(2) adding water into the frit powder and performing ball milling to obtain glaze slip with proper consistency;
(3) sieving the glaze slip;
(4) adding water to adjust the density of the glaze slip;
(5) spraying glaze and firing.
Preferably, after the raw materials in the step (1) are uniformly mixed, the raw materials are melted at 1450-1500 ℃ for 40-60 min, and then water is added
Quenching and ball milling to obtain frit powder.
Preferably, 3 to 6 weight percent of kaolin based on the weight of the frit powder is added during the ball milling in the step (2), and the weight of the kaolin based on the weight of the frit powder
0.2% -0.5% of carboxymethyl cellulose.
Preferably, the ratio of the materials in the ball milling in the step (2) to the ball-water =1:2: 1.1.
Preferably, the mesh screen in the step (3) is 200-250 mesh screen.
Preferably, the screen residue in the screening in the step (3) is less than 0.15 wt%.
Preferably, the density of the glaze slip in the step (4) is adjusted to be 1.5-1.6 g/cm3。
Preferably, the firing system in the step (5) is 1200-1210 ℃ for 8-10 min, and the temperature rise speed is 10-20 ℃/min.
The process flow of the zirconium-free sapphirine microcrystal opaque glaze is as follows:
raw material detection → batching → uniform mixing → heat preservation at 1450 ℃ -1500 ℃ (water quenching → ball milling → sieving → glaze making → glazing → firing → finished product.
The invention uses sapphirine to replace ZrSiO4The emulsion glaze is prepared by using the emulsion agent. The width (250 nm) of the sapphirine is equivalent to the wavelength range of visible light, the length is 1-2 mu m, and strong scattering is generated, so that the sapphirine microcrystalline glaze has ZrSiO4The opalescent glaze has the opalescent effect, and simultaneously improves the hardness, the wear resistance, the acid and alkali resistance and the scratch resistance of the glaze. Because the sapphirine is compared with ZrSiO4Has smaller size and thus has higher glossiness.
Compared with the prior art, the invention has the following beneficial effects:
the zirconium-free sapphirine microcrystal opaque glaze has the advantages of high glaze glossiness, high hardness, good wear resistance, good acid and alkali resistance, scratch resistance, no zircon sand, no radioactive elements, low cost, good opalescence effect, completely the same production process as zirconium series opaque fritted glaze and capability of reducing the production cost.
Drawings
FIG. 1 is a scanning electron microscope image of the glaze surface of zirconium-free sapphirine micro-opacified glaze of example 1 after being corroded for 30s by 5wt% HF solution.
Detailed Description
Specific embodiments of the present invention will be further described with reference to the following examples, but the embodiments of the present invention are not limited thereto.
Example 1
The zirconium-free sapphirine microcrystalline opacified glaze of the embodiment comprises the following components in parts by weight: na (Na)2O：1.84%；K2O：2.76%；Al2O3：27.62%；MgO：8.21%；B2O3：6.14%；Li2O：0.25%；CaO：0.28%；P2O5：0.47%；SiO2：52.43%。
The raw material formula is calculated according to the formula proportionIn this example, 25.88 parts by weight of potash feldspar, 6.96 parts by weight of albite, 24.17 parts by weight of talc, 9.19 parts by weight of boric acid, 0.47 parts by weight of phosphorus pentoxide and 33.32 parts by weight of bauxite were selected as raw materials, and after uniform mixing, ball milling was performed, and heat preservation was performed at 1480 ℃ for 60min, and after quenching, frit was obtained, and then frit powder was obtained by ball milling. Ball milling 100g frit powder, 5g kaolin, 0.25g carboxymethyl cellulose and 110ml water, sieving with 200 mesh sieve to obtain 0.1g residue, and adding water to adjust glaze slurry density to 1.55g/cm during glazing3And spraying glaze, heating to 1200 ℃ at the speed of 10 ℃/min, and keeping the temperature for 10min to obtain the zirconium-free sapphirine microcrystal opaque glaze.
The zirconium-free sapphirine microcrystalline opaque glaze obtained in this example had a vickers hardness of 7.5GPa, L of 95.62, a of-0.61, b of 0.36 and a gloss of 85 GU.
The scanning electron micrograph of the glaze of the zirconium-free sapphirine micro-opacified glaze of the embodiment after being corroded for 30s by 5 parts by weight of HF solution is shown in figure 1.
Example 2
The zirconium-free sapphirine microcrystalline opacified glaze of the embodiment comprises the following components in parts by weight: na (Na)2O：1.87%；K2O：2.79%；Al2O3：27.90%；MgO：8.27%；B2O3：6.20%；Li2O：0.18%；CaO：0.32%；P2O5：0.50%；SiO2：51.97%。
According to the raw material formula calculated according to the formula proportion, in the embodiment, 26.81 parts by weight of potash feldspar, 6.91 parts by weight of albite, 21.84 parts by weight of talc, 0.92 parts by weight of quartz powder, 10.17 parts by weight of boric acid, 0.50 part by weight of phosphorus pentoxide and 32.85 parts by weight of bauxite are selected as raw materials, the raw materials are uniformly mixed and subjected to ball milling, the temperature is kept at 1480 ℃ for 60min, the clinker is obtained after quenching, and then the clinker powder is obtained through ball milling. Ball milling 100g frit powder, 5g kaolin, 0.25g carboxymethyl cellulose and 110ml water, sieving with 200 mesh sieve to obtain 0.1g residue, and adding water to adjust glaze slurry density to 1.55g/cm during glazing3And spraying glaze, heating to 1200 ℃ at the speed of 15 ℃/min, and keeping the temperature for 10min to obtain the zirconium-free sapphirine microcrystal opaque glaze.
The zirconium-free sapphirine microcrystalline opaque glaze obtained in this example had a vickers hardness of 8.7GPa, L of 95.57, a of-0.47, b of 0.20 and a gloss of 86 GU.
The scanning electron microscope picture of the glaze surface of the zirconium-free sapphirine micro-crystal opacified glaze of the embodiment after being corroded for 30s by 5 weight parts of HF solution is shown in figure 1.
Example 3
The zirconium-free sapphirine microcrystalline opacified glaze of the embodiment comprises the following components in parts by weight: na (Na)2O：1.00%；K2O：3.00%；Al2O3：28.00%；MgO：8.00%；B2O3：5.00%；CaO：1.00%；SiO2：54.00%。
According to the raw material formula calculated according to the formula proportion, in the embodiment, 22.27 parts by weight of potash feldspar, 0.29 part by weight of albite, 20.96 parts by weight of talc, 11.20 parts by weight of quartz powder, 8.16 parts by weight of boric acid and 20.96 parts by weight of bauxite are selected as raw materials, are uniformly mixed and then are subjected to ball milling, the temperature is kept for 60min at 1480 ℃, the clinker is obtained after quenching, and then the clinker powder is obtained through ball milling. Ball milling 100g frit powder, 5g kaolin, 0.25g carboxymethyl cellulose and 110ml water, sieving with 200 mesh sieve to obtain 0.1g residue, and adding water to adjust glaze slurry density to 1.55g/cm during glazing3And spraying glaze, heating to 1200 ℃ at the speed of 10 ℃/min, and keeping the temperature for 10min to obtain the zirconium-free sapphirine microcrystal opaque glaze.
The Vickers hardness of the zirconium-free sapphirine micro-crystal opacified glaze obtained in the embodiment is 8.5GPa, L is 95.58, a is-0.46, b is 0.31, and the glossiness is 84 GU.
The scanning electron microscope picture of the glaze surface of the zirconium-free sapphirine micro-crystal opacified glaze of the embodiment after being corroded for 30s by 5 weight parts of HF solution is shown in figure 1.
Example 4
The zirconium-free sapphirine microcrystalline opacified glaze of the embodiment comprises the following components in parts by weight: na (Na)2O：3.00%；K2O：2.00%；Al2O3：25.00%；MgO：10.00%；B2O3：7.00%；Li2O：1%；SiO2：52.00%。
The raw material formulation used was calculated according to the formulation ratio as above, and in this example, it was selectedThe method comprises the steps of uniformly mixing 18.21 parts by weight of potash feldspar, 17.82 parts by weight of albite, 25.89 parts by weight of talc, 11.16 parts by weight of boric acid and 26.92 parts by weight of bauxite, carrying out ball milling, keeping the temperature at 1480 ℃ for 60min, quenching to obtain a frit, and carrying out ball milling to obtain frit powder. Ball milling 100g frit powder, 5g kaolin, 0.25g carboxymethyl cellulose and 110ml water, sieving with 200 mesh sieve to obtain 0.1g residue, and adding water to adjust glaze slurry density to 1.55g/cm during glazing3And spraying glaze, heating to 1200 ℃ at the speed of 20 ℃/min, and keeping the temperature for 10min to obtain the zirconium-free sapphirine microcrystal opaque glaze.
The zirconium-free sapphirine microcrystalline opaque glaze obtained in this example had a vickers hardness of 8.5GPa, L of 95.59, a of-0.41, b of 0.34, and a gloss of 88 GU.
The scanning electron microscope picture of the glaze surface of the zirconium-free sapphirine micro-crystal opacified glaze of the embodiment after being corroded for 30s by 5 weight parts of HF solution is shown in figure 1. It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The zirconium-free sapphirine microcrystal opaque glaze is characterized by comprising the following components in percentage by mass:
Na2O：1～3%；
K2O：2～3%；
Al2O3：25～28%；
MgO：8～10%；
B2O3：5～7%；
Li2O：0～1%；
CaO：0～1%；
P2O5：0～1%；
the balance being SiO2。
2. The zirconium-free sapphirine microcrystalline opaque glaze of claim 1, wherein the zirconium-free sapphirine microcrystalline opaque glaze comprises the following components in percentage by mass:
Na2O：1.84%；
K2O：2.76%；
Al2O3：27.62%；
MgO：8.21%；
B2O3：6.14%；
Li2O：0.25%；
CaO：0.28%；
P2O5：0.47%；
SiO2：52.43%。
3. the method for preparing the zirconium-free sapphirine microcrystalline opacified glaze as set forth in any one of claims 1-2, which comprises the steps of:
(1) mixing potash feldspar, albite, talc, quartz powder, boric acid, phosphorus pentoxide and bauxite, uniformly ball-milling, melting, water quenching, and ball-milling to obtain frit powder;
(2) adding water into the frit powder obtained in the step (1) for ball milling to obtain glaze slurry;
(3) sieving the glaze slip obtained in the step (2);
(4) adding water to adjust the density of the glaze slip;
(5) spraying glaze and sintering to obtain the zirconium-free sapphirine microcrystal opaque glaze.
4. The method for preparing zirconium-free sapphirine microcrystalline opaque glaze according to claim 3, wherein the melting temperature in the step (1) is 1450-1500 ℃.
5. The method for preparing zirconium-free sapphirine microcrystalline opaque glaze according to claim 3, wherein the melting time in the step (1) is 40-60 min.
6. The method for preparing zirconium-free sapphirine microcrystalline opaque glaze according to claim 3, wherein kaolin is added in an amount of 4-6% by weight of the frit powder and carboxymethyl cellulose is added in an amount of 0.2-0.5% by weight of the frit powder during the ball milling in the step (2).
7. The method for preparing zirconium-free sapphirine microcrystalline opaque glaze according to claim 3, wherein the weight ratio of the materials, the balls and the water in the ball milling in the step (2) is 1:2: 1.1.
8. The method for preparing zirconium-free sapphirine microcrystalline opacified glaze according to claim 3, wherein the mesh used in the step (3) is 200-250 mesh; the residue on sieving is less than 0.15 wt%.
9. The method for preparing zirconium-free sapphirine microcrystalline opacified glaze according to claim 3, wherein the density of the glaze slip in the step (4) is adjusted to 1.5-1.6 g/cm3。
10. The method for preparing the zirconium-free sapphirine microcrystalline opaque glaze according to claim 3, wherein the firing in the step (5) is carried out at 1200-1210 ℃ for 8-10 min at a temperature rise rate of 10-20 ℃/min.
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| CN107082566A (en) * | 2017-03-31 | 2017-08-22 | 华南理工大学 | Single-phase cordierite transparent wear glaze and preparation method thereof |
| CN107129150A (en) * | 2017-06-27 | 2017-09-05 | 佛山市大千色釉料有限公司 | A kind of high abrasion glaze for glazed tile and preparation method thereof |
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| CN107082566A (en) * | 2017-03-31 | 2017-08-22 | 华南理工大学 | Single-phase cordierite transparent wear glaze and preparation method thereof |
| CN107129150A (en) * | 2017-06-27 | 2017-09-05 | 佛山市大千色釉料有限公司 | A kind of high abrasion glaze for glazed tile and preparation method thereof |
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| Title |
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| Effect of ZnO/MgO ratio on the crystallization and optical properties of spinel opaque glazes;Jingpei Cai;《Journal of the American Ceramic Society》;20171102;第101卷(第4期);第1754-1764页 * |
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