CN116082062B - Antistatic metal glaze, antistatic metal glaze ceramic tile and preparation method thereof - Google Patents
Antistatic metal glaze, antistatic metal glaze ceramic tile and preparation method thereof Download PDFInfo
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- CN116082062B CN116082062B CN202310368423.8A CN202310368423A CN116082062B CN 116082062 B CN116082062 B CN 116082062B CN 202310368423 A CN202310368423 A CN 202310368423A CN 116082062 B CN116082062 B CN 116082062B
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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
- 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
-
- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
Abstract
The invention relates to the technical field of building ceramics, in particular to an antistatic metal glaze, an antistatic metal glaze ceramic tile and a preparation method thereof, wherein the antistatic metal glaze comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 8-15% of active fluxing agent I, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate according to mass percentage. The antistatic metal glaze provided by the scheme has excellent metal texture effect and antistatic performance at the same time, so that the defects of the prior art are overcome.
Description
Technical Field
The invention relates to the technical field of building ceramics, in particular to an antistatic metal glaze, an antistatic metal glaze ceramic tile and a preparation method thereof.
Background
The glaze is a vitreous thin layer attached to the surface of the ceramic green body, and is prepared by mixing common mineral raw materials and chemical raw materials according to a certain proportion, finely grinding into slurry liquid, distributing the slurry liquid on the surface of the green body, and calcining at a high temperature. It has physical and chemical properties similar to that of glass state, and can raise the mechanical strength, heat stability and chemical stability of product, and the glaze may be also decorated with various patterns to strengthen the artistic effect and infection of product.
The metal glaze is used as a special artistic glaze and applied to the surface of the ceramic tile, has an elegant and luxurious metal-imitating effect, and is widely applied to the building decoration industry, in particular to an archaized ceramic tile. The existing metal glaze is usually prepared by adding heavy metal elements such as ferric oxide, aluminum phosphate and the like into a formula of the light glaze, so that the fired glaze can simultaneously present the reflection luster and the imitation metal color of the light glaze, but the glaze effect of the existing metal glaze is simple superposition of two glaze effects, so that the existing metal glaze cannot present metal texture, and the decoration requirement of a user is difficult to meet.
In daily life, chemical fiber clothes, common plastic tools, paint furniture and various household appliances can generate electrostatic phenomena, the electrostatic can absorb a large amount of dust in the air, the dust contains toxic substances and germs, the toxic substances and germs are light and irritate the skin, the luster and the tenderness of the skin are affected, and the skin is on spots and sores, and even bronchial asthma and arrhythmia are caused seriously; similarly, in the industrial fields of information industry, electronic industry, textile industry, petrochemical industry and the like, electrostatic phenomena are common, when static electricity is gathered to a certain extent, electronic elements are destroyed, interference signals are generated, and fire disaster is caused, so that indoor decoration in daily household indoor decoration and in the fields of information industry, electronic industry, textile industry, petrochemical industry and the like must meet antistatic requirements, wherein the antistatic performance of decorative material tiles of wall surfaces and floors is the most important link, and the existing tile with the metal texture imitation effect has no antistatic function, so that the requirements of daily household and the fields of information industry, electronic industry, textile industry, petrochemical industry and the like on the antistatic performance of metal glaze tiles cannot be met.
Disclosure of Invention
The invention aims to provide an antistatic metal glaze which has excellent metal texture effect and antistatic performance at the same time so as to overcome the defects of the prior art.
The second aim of the invention is to provide a preparation method of the antistatic metal glaze ceramic tile, which is simple and has strong operability, and the obtained antistatic metal glaze ceramic tile has excellent metal luster and antistatic performance.
The third object of the present invention is to provide an antistatic metal glazed tile prepared by the above method, which has a metal gloss of 80 ° or more and a surface resistance of 5×10 5 ～5×10 7 Omega, has metallic texture effect and antistatic property.
To achieve the purpose, the invention adopts the following technical scheme:
the antistatic metal glaze comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 8-15% of active fluxing agent I, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate by mass percent.
Further, the iron frit comprises 26-42% of kaolin, 34-46% of ferric phosphate, 13-23% of active fluxing agent II, 6-9% of calcined talcum, 2-4% of crystal nucleus agent and 0.9-3% of metal color mixing oxide according to mass percentage.
Further, the iron oxide content of the iron frit is 19-22% according to the mass percentage;
the nucleating agent is titanium dioxide.
Further, the active fluxing agent I comprises albite and zinc oxide;
the active fluxing agent II comprises zinc oxide, wollastonite and albite;
the metal hueing oxide includes at least one of copper oxide and chromium oxide.
Further, according to mass percentage, the antistatic metal glaze comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 7-12% of albite, 1-3% of zinc oxide, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate;
the iron frit comprises, by mass, 26-42% of kaolin, 34-46% of ferric phosphate, 2-4% of wollastonite, 8-12% of albite, 3-7% of zinc oxide, 6-9% of calcined talcum, 2-4% of titanium dioxide, 0.4-1% of copper oxide and 0.5-2% of chromium oxide.
The preparation method of the antistatic metal glaze ceramic tile is used for preparing the antistatic metal glaze ceramic tile using the antistatic metal glaze material and comprises the following steps of:
A. mixing kaolin, ferric phosphate, an active fluxing agent II, calcined talcum, a crystal nucleus agent and metal color mixing oxide uniformly according to the proportion, calcining and water quenching to obtain an iron frit;
B. Uniformly mixing kaolin, ferric phosphate, an active fluxing agent I, apatite, lithium carbonate, calcined talcum, sodium tripolyphosphate and the iron frit in the step A according to the proportion to obtain an antistatic metal glaze;
C. and B, diluting the antistatic metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit firing ceramic tile blank, drying and firing to obtain the antistatic metal glaze ceramic tile.
In the step C, the antistatic metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground antistatic metal glaze is applied to the biscuit fired ceramic tile blank through screen printing, and the mesh number of the screen is 120-160 meshes.
Further, in the step C, the mass mixing ratio of the antistatic metal glaze, the stamp-pad ink and the water is 1:1:1, a step of;
according to the mass percentage, the grinding fineness is 325 meshes of sieve, the screen residue is 0.3-0.5%, and the grinding time is 11.5-12.5 h;
the firing temperature of the antistatic metal glaze ceramic tile is 1200-1220 ℃.
Further, in step a, the firing profile of the iron frit is:
(1) Raising the temperature from normal temperature to 500 ℃ for 1-3 hours;
(2) Raising the temperature from 500 ℃ to 1100 ℃ for 0.5 to 1.5 hours;
(3) Raising the temperature from 1100 ℃ to 1500 ℃ for 0.5-1.5 hours;
(4) Preserving heat for 0.5-1 h at 1500 ℃.
Antistatic metal glazed tile using the antistatic goldThe antistatic metal glazed tile is prepared by a preparation method of glazed tiles, wherein the metal glossiness of the antistatic metal glazed tile is more than or equal to 80 degrees, and the surface resistance is 5 multiplied by 10 5 ～5×10 7 Ω。
The technical scheme provided by the embodiment of the application can comprise the following beneficial effects:
1. the cooperation of kaolin, ferric phosphate, iron frit and calcined talcum can generate iron-containing spinel crystals which can enable the glaze to present a metal texture effect, the iron-containing spinel crystals are of an equiaxed crystal system, the symmetry degree of the crystals is high, the main form is octahedron, the bottoms and the surfaces of the crystals are parallel to the glaze, light is most easily reflected, and the bottoms and the surfaces of the crystals are parallel to the glaze and are the necessary condition that the glaze presents the metal texture effect, so that the metal texture effect which can be achieved by the antistatic metal glaze in the technical scheme is difficult to achieve by the conventional metal glaze, the defect that the metal glaze cannot present metal texture in the prior art is overcome, and the decoration requirement of a user is difficult to meet.
2. Through the cooperation of the olivine-type lithium iron phosphate crystal and the iron-containing spinel crystal, lithium ion electrons migrate under the action of electrostatic voltage to generate electrostatic current, and the electrostatic current is led out through a conductive network formed by the glazed iron-containing spinel crystal, so that the antistatic performance of the antistatic metal glazed tile is remarkably improved, and the requirements of daily families, information industry, electronic industry, textile industry, petrochemical industry and other industrial fields on the antistatic performance of the metal glazed tile are met.
3. The preparation method is simple, the operability is strong, the metal glossiness of the obtained antistatic metal glaze ceramic tile is more than or equal to 80 degrees, and the surface resistance can reach 5 multiplied by 10 5 ～5×10 7 Omega, has excellent metal feel effect and antistatic property.
Detailed Description
The technical scheme provides an antistatic metal glaze, which comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 8-15% of active fluxing agent I, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate according to mass percentage.
In order to make the glaze have excellent metal texture and good antistatic performance, the technical scheme provides an antistatic metal glaze, which comprises raw materials including kaolin, ferric phosphate, iron frit, an active fluxing agent I, apatite, lithium carbonate and calcined talcum.
The existing metal glaze is usually prepared by adding heavy metal elements such as ferric oxide, aluminum phosphate and the like into a formula of the light glaze, so that the fired glaze can simultaneously present the reflection luster and the imitation metal color of the light glaze, but the glaze effect of the existing metal glaze is simple superposition of two glaze effects, so that the existing metal glaze cannot present metal texture, and the decoration requirement of a user is difficult to meet.
Firstly, in order to enable the ceramic tile glaze to show metal texture effect, the technical scheme adds kaolin, ferric phosphate, ferric frit and calcined talcum into an antistatic metal glaze formula, the cooperation of the kaolin, ferric phosphate, ferric frit and calcined talcum can generate iron-containing spinel crystals which can enable the glaze to show metal texture effect, the iron-containing spinel crystals are of an equiaxial crystal system, the symmetry degree of the crystals is high, the main form is octahedron, the bottoms and the faces of the crystals are parallel to the glaze, light is most easily reflected, and the bottoms and the faces of the crystals are parallel to the glaze and are the necessary condition that the glaze shows the metal texture effect, so that the metal texture effect achieved by the antistatic metal glaze in the technical scheme is difficult to achieve by the conventional metal glaze, the defect that the metal glaze cannot show metal texture in the prior art is overcome, and the decoration requirement of a user is difficult to meet.
Secondly, indoor decoration in daily families and in the fields of information industry, electronic industry, textile industry, petrochemical industry and the like must meet antistatic requirements, wherein antistatic performance of decorative material tiles of wall surfaces and floors is the most important link, and the existing tile with the metal texture imitating effect has no antistatic function and cannot meet the requirements of daily families and in the fields of information industry, electronic industry, textile industry, petrochemical industry and the like on antistatic performance of metal glaze tiles.
The raw materials of the formula of the antistatic metal glaze also comprise lithium carbonate, the lithium carbonate is decomposed into lithium oxide at high temperature, the lithium oxide has high activity and strong fluxing effect, the viscosity of the glaze can be obviously reduced, olivine type lithium iron phosphate crystals can be generated by reacting with ferric phosphate, and the lithium iron phosphate crystals have a conductive effect and can lead out static electricity in ceramic tiles, so that the antistatic effect is achieved; meanwhile, the iron-containing spinel crystal generated in the technical scheme can form a conductive network on the glaze surface to conduct static out, and also has antistatic performance. The two are matched for use, lithium ion electrons migrate under the action of electrostatic voltage to generate electrostatic current, and the electrostatic current leads out static electricity through a conductive network formed by the glazed iron-containing spinel crystals, so that the antistatic performance of the antistatic metal glazed tile is remarkably improved, and the requirements of daily families and industrial fields such as information industry, electronic industry, textile industry, petrochemical industry and the like on the antistatic performance of the metal glazed tile are met.
In addition, the formula of the antistatic metal glaze also comprises apatite, wherein the apatite has fluxing function and can generate phosphorus pentoxide during calcination; meanwhile, phosphorus pentoxide can be generated during calcination of ferric phosphate in the antistatic metal glaze formula, and is strong in cation field due to high coordination number, and phase separation is easily caused by separation from a glazed glass phase network structure in the heat treatment process, so that metal ions in the glaze are enriched by the phase separation, and iron-containing spinel crystals are easier to separate out.
In addition, the raw material of the anti-static metal glaze formula in the technical scheme, namely the calcined talcum is not only one of the raw materials for forming the ferrite spinel crystal, but also has a fluxing effect, and the calcined talcum and the active fluxing agent I are added into the formula together, so that the effects of reducing the firing temperature and promoting sintering are achieved; besides, the kaolin also contains free active silica, provides a network skeleton for the glazed glass phase, and reacts with apatite, active fluxing agent I and calcined talcum to generate a silicate glass network structure when calcined, so that the glazed glass phase is formed, gaps among crystal particles in the glaze can be filled, crystal particles can be bonded, the glaze is compact and smooth, and the strength, mechanical strength, thermal stability, chemical stability and antifouling performance of the glaze after being calcined can be ensured.
Finally, the antistatic metal glaze material in the technical scheme also comprises sodium tripolyphosphate which is a glaze regulator, the viscosity of the glaze slurry can be adjusted, the glazing quality is improved, the phenomena of glaze elimination, stripes or uneven surfaces and the like are prevented from occurring on the glaze surface, and the antistatic performance and the metal texture effect are further influenced.
Further, according to mass percentage, the antistatic metal glaze in the technical scheme comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 8-15% of active fluxing agent I, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate.
The kaolin is an important component of a glass phase of the glaze and is one of raw materials containing ferrite spinel crystals, so that the addition of the kaolin in the formula of the antistatic metal glaze is limited to 15-23%, and if the addition of the kaolin is more than 23%, the glaze is burnt, so that the glaze is yellow and the metal texture effect is poor; if the amount of kaolin added is less than 15%, the content of aluminum ions in the crystallization raw material becomes small, the precipitation amount of iron-containing spinel crystals becomes small, and the metallic texture effect and antistatic performance are reduced.
The ferric phosphate is one of the raw materials of the iron-containing spinel crystal and the olivine-type lithium iron phosphate crystal, and can promote the precipitation of the two crystals, and the antistatic performance of the antistatic metal glaze in the technical scheme mainly depends on the olivine-type lithium iron phosphate crystal, so that the addition of ferric phosphate is limited to 12-18%, and if the addition of ferric phosphate is more than 18%, the metal ions such as magnesium ions, aluminum ions and the like of the rest of crystallization raw materials correspondingly decrease, thereby being unfavorable for the precipitation of the iron-containing spinel crystal and causing the reduction of the metal texture effect and the antistatic performance; if the addition amount of the ferric phosphate is less than 12%, precipitation of olivine-type lithium iron phosphate crystals is not facilitated, and the antistatic performance is reduced.
The lithium carbonate has fluxing effect and is one of the raw materials of the olivine type lithium iron phosphate crystal, so that the addition amount is limited to 6-10%, and if the addition amount of the lithium carbonate is more than 10%, the fluxing effect is too strong, the precipitation of the iron-containing spinel crystal and the olivine type lithium iron phosphate crystal is affected, and the metal texture effect and the antistatic performance are deteriorated; if the amount of lithium carbonate added is less than 6%, the amount of precipitated olivine-type lithium iron phosphate crystals becomes small, resulting in a decrease in antistatic properties.
The apatite has fluxing effect and can promote precipitation of iron-containing spinel crystals and olivine-type lithium iron phosphate crystals, so that the addition amount is limited to 6-10%, if the addition amount of the apatite is more than 10%, the fluxing effect is too strong, so that overmany glazed glass phases are caused, the precipitation amount of the iron-containing spinel crystals and the olivine-type lithium iron phosphate crystals is reduced, and the metal texture effect and the antistatic performance are deteriorated; if the addition amount of apatite is less than 6%, the enrichment of metal ions becomes small, the precipitation of iron-containing spinel crystals becomes small, and the metallic texture effect and antistatic performance become poor.
The iron frit mainly provides iron ions, and the iron ions of the iron-containing spinel crystal in the technical scheme are mainly derived from the iron frit, so that the addition amount of the iron frit is large, if the addition amount of the iron frit is more than 40%, the content of lithium iron phosphate and lithium carbonate in the antistatic metal glaze is correspondingly reduced, the precipitation amount of olivine-type lithium iron phosphate crystal is reduced, and the antistatic performance is deteriorated; if the addition amount of the iron frit is less than 30%, the content of iron ions in the crystallization raw material is correspondingly reduced, the precipitation amount of iron-containing spinel crystals is reduced, and the metallic texture effect and the antistatic performance are reduced.
The calcined talcum has fluxing effect and is one of the raw materials of the iron-containing spinel crystal, so that the addition amount of the calcined talcum is 3-6%, if the addition amount of the calcined talcum is more than 6%, the fluxing effect is dominant, so that the glazed glass phase is excessive, the precipitation of the corresponding iron-containing spinel crystal is reduced, and the metal texture effect and the antistatic performance are affected; if the addition amount of the calcined talc is less than 3%, the content of metal ion magnesium in the crystallization raw material becomes small, which is not favorable for precipitation of iron-containing spinel crystals, and also affects the metal texture effect and antistatic performance.
The active fluxing agent I mainly plays a fluxing role and is also an important component of a glazed glass phase, so that the addition amount of the active fluxing agent I is 8-15%, and if the addition amount of the active fluxing agent is more than 15%, the fluxing effect is too strong, the precipitation amount of ferrite-containing spinel crystals and olivine-type lithium iron phosphate crystals is reduced, and the metallic luster effect and antistatic performance are affected; if the addition amount of the active flux is less than 8%, the high-temperature viscosity of the glaze is too high while the glaze is burned, the precipitation of iron-containing spinel crystals and olivine-type lithium iron phosphate crystals becomes difficult, and the metallic luster effect and the antistatic performance are also affected.
The sodium tripolyphosphate is used as a glaze regulator for regulating the viscosity of glaze slurry and improving glazing quality, so that the addition amount is limited to 0.2-0.5%.
Therefore, in the technical scheme, through the cooperation of the raw materials in the formula of the antistatic metal glaze and the limitation of the components of the raw materials in the addition amount range, the precipitation amount of the iron-containing spinel crystal and the olivine-type lithium iron phosphate crystal is larger, and the metal texture effect and the antistatic performance meet the actual requirements.
Further, the iron frit comprises 26-42% of kaolin, 34-46% of ferric phosphate, 13-23% of active fluxing agent II, 6-9% of calcined talcum, 2-4% of crystal nucleus agent and 0.9-3% of metal color mixing oxide according to mass percentage.
In one embodiment of the technical scheme, the iron frit comprises kaolin, ferric phosphate, an active fluxing agent II, calcined talcum, a crystal nucleus agent and metal color mixing oxide, and in the preparation process of the iron frit, part of iron-containing spinel crystals are generated by the reaction of the kaolin, the ferric phosphate and the calcined talcum in raw materials, so that the crystal content in a glaze formula system is further improved, the metal texture effect can be greatly improved, and the antistatic performance can also be improved.
Meanwhile, the iron frit raw material in the scheme also comprises a crystal nucleus agent, which can reduce crystallization activation energy and crystallization peak temperature, promote the precipitation of iron-containing spinel crystals and further improve the metal texture effect and antistatic performance. Besides, the raw materials of the iron frit in the technical scheme also comprise ferric phosphate, phosphorus pentoxide is generated during the calcination of the ferric phosphate, the coordination number of the phosphorus pentoxide is high, a cation field is strong, the iron frit is easily separated from a glass phase of the iron frit in the heat treatment process to cause phase separation, and a phase separation promoting crystal nucleus agent is enriched in one phase, and plays a role of crystal nucleus when the iron frit is enriched to a certain degree; meanwhile, the phase separation promotes the enrichment of metal ions in the iron frit, which is beneficial to the formation of iron-containing spinel crystals. In addition, when the iron frit is added into the antistatic metal glaze, the enrichment degree of metal ions in the antistatic metal glaze can be improved, precipitation of iron-containing spinel crystals in the antistatic metal glaze is facilitated, and the metal luster effect and the antistatic performance are further improved.
Therefore, the crystal nucleus agent and ferric phosphate cooperate to promote the precipitation of the iron-containing spinel crystals in the antistatic metal glaze, improve the enrichment degree of metal ions in the formula of the antistatic metal glaze, further increase the precipitation amount of the iron-containing spinel crystals and further improve the metal texture effect and antistatic performance.
In addition, the metal color mixing oxide can color the material formed by the glass phase unit and the crystallization unit, and the metal color mixing oxide is added in the formula of the iron frit and combined with iron ions in the crystallization unit, so that the iron-containing spinel crystal is further colored, and the metallic luster effect is improved.
Furthermore, the kaolin in the iron frit formula of the technical scheme also contains free active silicon dioxide, is a network skeleton of an iron frit glass phase, and reacts with the calcined talcum with fluxing action and the active fluxing agent II in the iron frit formula to form a silicate network structure during calcination, so that the iron frit glass phase is formed, and gaps among crystal particles in the iron frit are filled, and the crystal particles are bonded.
More specifically, according to the mass percentage, the iron frit in the technical scheme comprises 26-42% of kaolin, 34-46% of ferric phosphate, 13-23% of active fluxing agent II, 6-9% of calcined talcum, 2-4% of crystal nucleus agent and 0.9-3% of metal color mixing oxide.
The kaolin is an important component of the iron frit glass phase and is one of the raw materials of the iron-containing spinel, so that the addition amount of the kaolin is limited to 26-42%, and if the addition amount of the kaolin is more than 42%, the iron frit is not beneficial to precipitation of iron-containing spinel crystals while the iron frit is burned, and the metal texture effect and the antistatic performance are reduced; if the amount of kaolin added is less than 26%, the content of aluminum ions in the crystallization raw material becomes small, and precipitation of iron-containing spinel crystals becomes small, thereby affecting the metallic texture effect and antistatic performance.
Iron phosphate is one of the raw materials of the iron-containing spinel crystal, and can promote the precipitation of the crystal, so that the addition amount is limited to 34-46%, and if the addition amount of the iron phosphate is more than 46%, the metal ions such as magnesium, aluminum and the like of the rest of crystallization raw materials correspondingly decrease, thereby being unfavorable for the precipitation of the iron-containing spinel crystal and reducing the metal texture effect and antistatic performance; if the addition amount of the ferric phosphate is less than 34%, the iron content and phosphorus pentoxide which is conducive to enrichment of metal ions are correspondingly reduced, precipitation of iron-containing spinel crystals is also not facilitated, and the metal texture effect and antistatic performance are reduced.
The calcined talcum has fluxing effect and is one of the raw materials of the iron-containing spinel crystal, so that the addition amount of the calcined talcum is 6-9%, if the addition amount of the calcined talcum is more than 9%, the fluxing effect is dominant, and the formed iron frit glass phase is excessive, the corresponding iron-containing spinel crystal is less precipitated, and the metal texture effect and antistatic performance are affected; if the addition amount of the calcined talc is less than 6%, the content of magnesium ions in the crystallization raw material becomes small, and precipitation of iron-containing spinel crystals is not facilitated, and the metal texture effect and the antistatic performance are also affected.
The active fluxing agent II mainly plays a fluxing role and is also an important component of an iron frit glass phase, so that the addition amount of the active fluxing agent II is 13-23%, and if the addition amount of the active fluxing agent is more than 23% and the fluxing effect is too strong, the precipitation amount of iron-containing spinel crystals becomes small and the metal texture effect and antistatic performance are reduced; if the amount of the active flux is less than 13%, the iron frit is burned, and the high-temperature viscosity is too high, so that the crystal precipitation becomes difficult, and the metallic texture effect and the antistatic performance are reduced.
The crystal nucleus agent can promote the precipitation of iron-containing spinel crystals in the system, so that the addition amount of the crystal nucleus agent is 2-4%, and if the addition amount of the crystal nucleus agent is more than 4% because the crystal nucleus agent is introduced as a high-temperature refractory substance, the high-temperature viscosity of the iron frit is too large, the crystallization effect is affected, the precipitation amount of the iron-containing spinel crystals is reduced, and the metal texture effect and the antistatic property are reduced; if the addition amount of the crystal nucleus agent is less than 2%, the crystallization effect is also affected by too low content of the substance playing a role in crystallization, the precipitation amount of the ferrite-containing spinel crystal is also reduced, and the metallic texture effect and the antistatic performance are also reduced.
The metal color mixing oxide is combined with iron ions in the formula, so that the iron-containing spinel crystal is further colored, the metallic luster effect is improved, and if the addition amount is too high and too low, the metal color is deviated, so that the addition amount is limited to 0.9-3%.
According to the technical scheme, kaolin, ferric phosphate, an active fluxing agent, calcined talcum, a crystal nucleus agent and metal color mixing oxide are matched, and the components of the raw materials are limited in an addition amount range, so that iron clinker is calcined to form iron-containing spinel crystals; because the mass percentage of the iron frit in the anti-static metal glaze is higher, after the iron frit is added into the anti-static metal glaze and calcined again, the metal texture effect can be greatly improved, and the anti-static performance can be improved; besides, the method is also beneficial to improving the enrichment degree of metal ions in the antistatic metal glaze, so that the precipitation amount of the iron-containing spinel crystals is further increased, and the metallic luster effect and the antistatic performance are further improved.
Further, the iron oxide content of the iron frit is 19-22% according to the mass percentage;
the nucleating agent is titanium dioxide.
In one embodiment of the present disclosure, the iron oxide content of the iron frit is 19-22%, if the iron oxide content of the iron frit is too low, the precipitation of iron-containing spinel crystals in the antistatic metal glaze becomes small, which affects the metal texture effect and antistatic performance, and if the iron oxide content of the iron frit is too high, the content of other metal ions is correspondingly reduced, the precipitation of iron-containing spinel crystals also becomes small, which also affects the metal texture effect and antistatic performance.
In a preferred embodiment of the present technical solution, the iron oxide content of the iron frit is 21.07%, and by further limiting the iron oxide content in the iron frit, the precipitation amount of the iron-containing spinel crystal is maximized, and the metal texture effect and the antistatic performance are optimized.
In another preferred embodiment of the present invention, the nucleating agent is titanium dioxide, the bond strength between titanium and oxygen in the titanium dioxide is high, under the high temperature condition, titanium tends to form four coordinated titano tetrahedron, and the four coordinated titano tetrahedron is mutually mixed and melted with silicon oxygen tetrahedron of silicate network structure in the glass phase, when the temperature is reduced, titanium tends to form six coordinated titano octahedron, and from the state of mutual mixed and melted with silicon oxygen tetrahedron, the liquid phase rich in titanium dioxide component is separated, thus the crystal nucleus is easy to be formed, the precipitation of ferrite-containing spinel crystal in the formula is promoted, and the metal texture effect and antistatic performance are further improved.
Further illustratively, the active fluxing agent I includes albite and zinc oxide;
the active fluxing agent II comprises zinc oxide, wollastonite and albite;
the metal hueing oxide includes at least one of copper oxide and chromium oxide.
In one embodiment of the technical scheme, the active fluxing agent I comprises albite and zinc oxide, the active fluxing agent II comprises zinc oxide, wollastonite and albite, and the zinc oxide, wollastonite and albite can reduce the sintering temperature of the antistatic metal glaze and reduce the high-temperature viscosity of the antistatic metal glaze, so that the precipitation of iron-containing spinel crystals and olivine-type lithium iron phosphate crystals in the antistatic metal glaze is promoted, and the metal texture effect and antistatic performance are further improved.
In another embodiment of the present disclosure, the metal hueing oxide includes at least one of copper oxide and chromium oxide, which are combined with iron ions in the formulation to further color the iron-containing spinel crystals and enhance the metallic luster effect.
Further, according to mass percentage, the antistatic metal glaze comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 7-12% of albite, 1-3% of zinc oxide, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate;
The iron frit comprises, by mass, 26-42% of kaolin, 34-46% of ferric phosphate, 2-4% of wollastonite, 8-12% of albite, 3-7% of zinc oxide, 6-9% of calcined talcum, 2-4% of titanium dioxide, 0.4-1% of copper oxide and 0.5-2% of chromium oxide.
In a preferred embodiment of the technical scheme, the antistatic metal glaze comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 7-12% of albite, 1-3% of zinc oxide, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate according to mass percentage; according to mass percentage, the iron frit comprises 26-42% of kaolin, 34-46% of ferric phosphate, 2-4% of wollastonite, 8-12% of albite, 3-7% of zinc oxide, 6-9% of calcined talcum, 2-4% of titanium dioxide, 0.4-1% of copper oxide and 0.5-2% of chromium oxide, and the anti-static performance and the metal texture effect are improved by limiting the specific content and types of the active fluxing agent.
Still further, in a more preferred embodiment of the present technical solution, the antistatic metallic glaze comprises, by mass, 20% of kaolin, 15% of iron phosphate, 35% of iron frit, 10% of albite, 2% of zinc oxide, 8% of apatite, 6% of lithium carbonate, 3.7% of calcined talc and 0.3% of sodium tripolyphosphate; according to the mass percentage, the iron frit comprises 30% of kaolin, 40% of ferric phosphate, 3% of wollastonite, 10% of albite, 5% of zinc oxide, 8% of calcined talcum, 2.5% of titanium dioxide, 0.5% of copper oxide and 1% of chromium oxide, and the antistatic performance and the metal texture effect are optimized while the cost is saved by further optimizing each component in the formula.
The preparation method of the antistatic metal glaze ceramic tile is used for preparing the antistatic metal glaze ceramic tile using the antistatic metal glaze material and comprises the following steps of:
A. mixing kaolin, ferric phosphate, an active fluxing agent II, calcined talcum, a crystal nucleus agent and metal color mixing oxide uniformly according to the proportion, calcining and water quenching to obtain an iron frit;
B. uniformly mixing kaolin, ferric phosphate, an active fluxing agent I, apatite, lithium carbonate, calcined talcum, sodium tripolyphosphate and the iron frit in the step A according to the proportion to obtain an antistatic metal glaze;
C. and B, diluting the antistatic metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit firing ceramic tile blank, drying and firing to obtain the antistatic metal glaze ceramic tile.
The technical scheme also provides a preparation method of the antistatic metal glaze ceramic tile, which comprises the following steps:
A. the kaolin, the ferric phosphate, the active fluxing agent II, the calcined talcum, the crystal nucleus agent and the metal color mixing oxide are uniformly mixed according to the proportion, and the iron clinker is obtained through calcination and water quenching.
B. And (3) uniformly mixing kaolin, ferric phosphate, an active fluxing agent I, apatite, lithium carbonate, calcined talcum, sodium tripolyphosphate and the iron frit obtained in the step A according to the proportion to obtain the antistatic metal glaze, wherein the preparation method is simple, the operability is strong, and the obtained antistatic metal glaze has excellent metal texture effect and antistatic performance.
C. The antistatic metal glaze material obtained in the step B is diluted by adding water and stamp-pad ink and then is ground, the diluted and ground antistatic metal glaze material is applied to a biscuit firing ceramic tile blank, and the biscuit firing ceramic tile blank is dried and fired to obtain the antistatic metal glaze ceramic tile, the preparation method is simple, the operability is strong, the metal glossiness of the prepared antistatic metal glaze ceramic tile is more than or equal to 80 degrees, and the surface resistance reaches 5 multiplied by 10 5 ～5×10 7 Omega, has excellent metal feel effect and antistatic property.
Further describing, in the step C, the antistatic metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground antistatic metal glaze is applied to the biscuit fired ceramic tile blank through screen printing, and the mesh number of the screen is 120-160 meshes.
In one embodiment of the technical scheme, in the step C, the antistatic metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground antistatic metal glaze is applied to the biscuit firing ceramic tile blank through screen printing, wherein compared with the common glaze spraying process, the screen printing process has the characteristics of uniform glazing and high glaze thickness stability, the glaze is applied to the biscuit firing ceramic tile blank by using the process, and after glaze firing, the crystal deviation of the bottom and the surface of ferrite crystal separated from the glaze is small, so that the metal texture effect of the glaze is stable; in addition, the process can ensure that the precipitated olivine-type lithium iron phosphate crystals are uniformly distributed on the glaze, and is helpful for ensuring consistent antistatic performance of the glaze of the ceramic tile.
In a preferred embodiment of the technical scheme, the mesh number of screen printing is 120-160 meshes, if the screen is too thin, the printing process is difficult to control, the screen is easy to adhere, the firing temperature range of the glaze is narrowed, and the quality of the glaze is affected; if the screen is too thick, the thickness of the glaze will be too thin, and the metallic effect of the glaze will be poor.
Since the thickness of the glaze affects the metallic effect of the glaze, in a more preferred embodiment of the present invention, the mesh number of the screen printing is 140 mesh, and the thickness of the glaze is controlled by controlling the mesh number of the screen, so that the metallic effect of the glaze is optimal.
Further described, in the step C, the mass mixing ratio of the antistatic metallic glaze, the stamp-pad ink and the water is 1:1:1, a step of;
according to the mass percentage, the grinding fineness is 325 meshes of sieve, the screen residue is 0.3-0.5%, and the grinding time is 11.5-12.5 h;
the firing temperature of the antistatic metal glaze ceramic tile is 1200-1220 ℃.
In one embodiment of the present technical solution, in step C, the mass mixing ratio of the antistatic metallic glaze, the stamp-pad ink and the water is 1:1:1, by further adjusting the proportion of the antistatic metal glaze, the stamp-pad ink and the water, the viscosity of the obtained antistatic metal glaze reaches the best, if the viscosity of the glaze is too low, the fluidity is too good after the glaze is applied, the stable and clear-boundary patterns are not formed, and if the viscosity of the glaze is higher, the fluidity is worse after the glaze is applied, and the surface of the glaze layer is rough easily.
In a preferred embodiment of the technical scheme, in the step C, according to mass percent, the grinding fineness is 325 meshes, the screen residue is 0.3-0.5%, the grinding time is 11.5-12.5 hours, the granularity of the obtained glaze is proper by controlling the grinding time and the ball milling fineness, the glaze is matched with a printing process, the metal texture effect and the antistatic performance are improved, if the granularity of the glaze is too small, brown eyes and pinholes are easy to appear on the glaze formed after calcination of the glaze, and the antifouling performance of the glaze is reduced; if the grain size of the glaze is too large, the sintering degree is insufficient, and the metal texture effect and the antistatic performance are reduced.
In a preferred embodiment of the technical scheme, in the step C, according to the mass percentage, the grinding fineness is 325 meshes, the screen residue is 0.5%, and the grinding time is 12 hours, so that the granularity of the glaze is best matched with the printing process, and the glaze has good antifouling performance, metal texture effect and antistatic performance.
In another preferred embodiment of the technical scheme, in the step C, the glaze firing temperature is 1200-1220 ℃, the firing temperature is consistent with that of the existing ceramic tile products, the purpose of industrial production is easily achieved while the product performance is ensured, and larger deviation between an experiment stage and an industrialization stage is reduced.
In the step C, water and stamp-pad ink are added for dilution, so that the viscosity of the glaze can be adjusted, the thixotropic property of the glaze can be obtained to meet the actual requirement, and the glazing quality is improved. The water can be tap water or distilled water, the viscosity of the stamp-pad ink is 6000-8000 CP, the type is not limited, and the stamp-pad ink can meet the actual requirement.
Further illustratively, in step a, the firing profile of the iron frit is:
(1) Raising the temperature from normal temperature to 500 ℃ for 1-3 hours;
(2) Raising the temperature from 500 ℃ to 1100 ℃ for 0.5 to 1.5 hours;
(3) Raising the temperature from 1100 ℃ to 1500 ℃ for 0.5-1.5 hours;
(4) Preserving heat for 0.5-1 h at 1500 ℃.
In one embodiment of the present disclosure, a firing profile of the iron frit includes three heating steps and one heat preservation step, and in the heating step from normal temperature to 500 ℃, moisture, gas oxides and volatile substances in the iron frit raw material are volatilized under high temperature conditions; then, the temperature is increased to 1100 ℃ from 500 ℃, and in the temperature increasing process, at the same time of the oxidative decomposition of ferric phosphate in the raw material of the iron frit, kaolin in the raw material reacts with the calcined talcum with fluxing action and the active fluxing agent II to form a silicate network structure, so that an iron frit glass phase is formed; then, in the heating process of 1100 ℃ to 1500 ℃, the iron-containing spinel crystals are separated out, so that the crystal content in a glaze formula system is further improved, the metal texture effect can be greatly improved, the antistatic performance can be improved, and in the heating process, the glass phase and the iron-containing spinel crystals are eutectic, and the glass phase fills gaps among the iron-containing spinel crystal grains and bonds the iron-containing spinel crystal particles; finally, heat preservation is carried out at 1500 ℃ to enable the ferrite spinel crystal to grow uniformly, thereby improving the metal texture effect and the antistatic performance.
Further, in a preferred embodiment of the present disclosure, the firing profile of the iron frit is: (1) raising the temperature from normal temperature to 500 ℃ for 2 hours; (2) raise from 500 ℃ to 1100 ℃ for 1 hour; (3) increasing from 1100 ℃ to 1500 ℃ for 1 hour; (4) at 1500℃for 0.5h. By further optimizing the time of each heating or heat preservation process, the energy consumption is effectively reduced, the precipitation amount and the growth uniformity of the iron-containing spinel crystal are ensured, and the metal texture effect and the antistatic performance are improved.
The antistatic metal glaze ceramic tile is prepared by the preparation method of the antistatic metal glaze ceramic tile, the metal glossiness of the antistatic metal glaze ceramic tile is not less than 80 degrees, and the surface resistance is 5 multiplied by 10 5 ～5×10 7 Ω。
The technical proposal also provides an antistatic metal glazed tile, the metal glossiness of which is more than or equal to 80 degrees, and the surface resistance of which is 5 multiplied by 10 5 ～5×10 7 Omega, has excellent metal feel effect and antistatic property.
The technical scheme of the invention is further described by the following specific embodiments.
Example 1-preparation method of antistatic Metal glazed ceramic tile
A. Uniformly mixing 26% of kaolin, 37% of ferric phosphate, 4% of wollastonite, 12% of albite, 7% of zinc oxide, 9% of calcined talcum, 2% of titanium dioxide, 1% of copper oxide and 2% of chromium oxide according to mass percentage, calcining and water quenching to obtain iron frit;
B. Uniformly mixing 23% of kaolin, 18% of ferric phosphate, 7.8% of albite, 1% of zinc oxide, 6% of apatite, 8% of lithium carbonate, 6% of calcined talcum, 0.2% of sodium tripolyphosphate and 30% of iron frit in the step A according to mass percentage to obtain an antistatic metal glaze;
C. and B, diluting the antistatic metal glaze in the step B with water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit fired ceramic tile blank through screen printing cloth, drying and firing to obtain the antistatic metal glaze ceramic tile.
Example 2-preparation method of antistatic Metal glazed ceramic tile
A. According to the mass percentage, uniformly mixing 35% of kaolin, 38% of ferric phosphate, 3.5% of wollastonite, 8% of albite, 3% of zinc oxide, 6% of calcined talcum, 4% of titanium dioxide, 1% of copper oxide and 1.5% of chromium oxide, calcining and water quenching to obtain iron frit;
B. uniformly mixing 18% of kaolin, 15% of ferric phosphate, 12% of albite, 1.5% of zinc oxide, 8.7% of apatite, 8% of lithium carbonate, 3% of calcined talcum, 0.3% of sodium tripolyphosphate and 33.5% of iron frit in the step A according to the mass percentage to obtain an antistatic metal glaze;
C. and B, diluting the antistatic metal glaze in the step B with water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit fired ceramic tile blank through screen printing cloth, drying and firing to obtain the antistatic metal glaze ceramic tile.
Example 3-preparation method of antistatic Metal glazed ceramic tile
A. Uniformly mixing 30% of kaolin, 40% of ferric phosphate, 3% of wollastonite, 10% of albite, 5% of zinc oxide, 8% of calcined talcum, 2.5% of titanium dioxide, 0.5% of copper oxide and 1% of chromium oxide according to mass percentage, calcining and water quenching to obtain iron frit;
B. uniformly mixing 20% of kaolin, 15% of ferric phosphate, 10% of albite, 2% of zinc oxide, 8% of apatite, 6% of lithium carbonate, 3.7% of calcined talcum, 0.3% of sodium tripolyphosphate and 35% of iron frit in the step A according to the mass percentage to obtain an antistatic metal glaze;
C. and B, diluting the antistatic metal glaze in the step B with water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit fired ceramic tile blank through screen printing cloth, drying and firing to obtain the antistatic metal glaze ceramic tile.
Example 4-preparation method of antistatic Metal glazed ceramic tile
A. According to the mass percentage, uniformly mixing 42% of kaolin, 34% of ferric phosphate, 2% of wollastonite, 9% of albite, 4% of zinc oxide, 6.1% of calcined talcum, 2% of titanium dioxide, 0.4% of copper oxide and 0.5% of chromium oxide, calcining and water quenching to obtain iron frit;
B. uniformly mixing 16% of kaolin, 12% of ferric phosphate, 7% of albite, 3% of zinc oxide, 10% of apatite, 10% of lithium carbonate, 5% of calcined talcum, 0.5% of sodium tripolyphosphate and 36.5% of iron frit in the step A according to the mass percentage to obtain an antistatic metal glaze;
C. And B, diluting the antistatic metal glaze in the step B with water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit fired ceramic tile blank through screen printing cloth, drying and firing to obtain the antistatic metal glaze ceramic tile.
Example 5-preparation method of antistatic Metal glazed ceramic tile
A. According to the mass percentage, 31 percent of kaolin, 46 percent of ferric phosphate, 2 percent of wollastonite, 8 percent of albite, 3 percent of zinc oxide, 6 percent of calcined talcum, 2 percent of titanium dioxide, 0.5 percent of copper oxide and 1.5 percent of chromium oxide are uniformly mixed, calcined and water quenched to obtain iron frit;
B. uniformly mixing 15% of kaolin, 15% of ferric phosphate, 10% of albite, 2.4% of zinc oxide, 8% of apatite, 6.2% of lithium carbonate, 3% of calcined talcum, 0.4% of sodium tripolyphosphate and 40% of iron frit in the step A according to the mass percentage to obtain an antistatic metal glaze;
C. and B, diluting the antistatic metal glaze in the step B with water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to the biscuit fired ceramic tile blank through screen printing cloth, drying and firing to obtain the antistatic metal glaze ceramic tile.
The antistatic metal glaze tile was prepared by using the preparation methods in the above examples, respectively, the surface effect of the prepared antistatic metal glaze tile was observed, the gloss of the glaze was tested by using a gloss meter, and the antistatic performance test was performed on the obtained antistatic metal glaze tile by using the test method of GB/T26539-2011 antistatic ceramic tile, the test results of which are shown in table 1 below.
Table 1 results of Performance test of different antistatic Metal glazed tiles in examples
As can be seen from the performance test results of the examples in the above table, the antistatic metal glaze tile prepared by the preparation method of the antistatic metal glaze tile has lifelike metal texture and excellent metal glossiness and antistatic performance, wherein the metal glossiness is more than or equal to 80 degrees, and the surface resistance can reach 5 multiplied by 10 5 ～5×10 7 Ω。
Comparative example 1: the preparation method and the raw materials in comparative example 1 and example 3 are the same, except that the addition amount of the raw materials in the formulation of the antistatic metallic glaze is different from that in example 3, specifically: the antistatic metal glaze comprises 24% of kaolin, 19% of ferric phosphate, 10.8% of albite, 3% of zinc oxide, 6% of apatite, 6% of lithium carbonate, 2% of calcined talcum, 0.2% of sodium tripolyphosphate and 29% of iron frit.
Comparative example 2: the preparation method and the raw materials in comparative example 1 and example 3 are the same, except that the addition amount of the raw materials in the formulation of the antistatic metallic glaze is different from that in example 3, specifically: the antistatic metal glaze comprises, by mass, 20% of kaolin, 11% of ferric phosphate, 11% of albite, 2% of zinc oxide, 8% of apatite, 13% of lithium carbonate, 3.5% of calcined talcum, 0.5% of sodium tripolyphosphate and 31% of iron frit.
The antistatic metal glaze tiles were prepared by using the preparation methods in the above comparative examples, respectively, the surface effects of the prepared antistatic metal glaze tiles were observed, the gloss of the glaze was tested by using a gloss meter, and the antistatic performance test was performed on the obtained antistatic metal glaze tiles using the test method of GB/T26539-2011 antistatic ceramic tile, the test results of which are shown in table 2 below.
Table 2 results of performance tests of different antistatic metallic glazed tiles in comparative example
As is clear from table 2, when the addition amount of the formulation raw materials is not within the limit of the present embodiment, the metal texture effect and antistatic performance of the obtained antistatic metal glaze tile are not satisfactory.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (7)
1. An antistatic metallic glaze, characterized in that: according to mass percentage, comprises 15 to 23 percent of kaolin, 12 to 18 percent of ferric phosphate, 30 to 40 percent of iron frit, 8 to 15 percent of active fluxing agent I, 6 to 10 percent of apatite, 6 to 10 percent of lithium carbonate, 3 to 6 percent of calcined talcum and 0.2 to 0.5 percent of sodium tripolyphosphate;
The iron frit comprises 26-42% of kaolin, 34-46% of ferric phosphate, 13-23% of active fluxing agent II, 6-9% of calcined talcum, 2-4% of crystal nucleus agent and 0.9-3% of metal color mixing oxide according to mass percentage;
the iron oxide content of the iron frit is 19-22% according to the mass percentage;
the crystal nucleus agent is titanium dioxide;
the metal hueing oxide includes at least one of copper oxide and chromium oxide;
wherein, the firing curve of the iron frit is:
(1) Raising the temperature from normal temperature to 500 ℃ for 1-3 hours;
(2) Raising the temperature from 500 ℃ to 1100 ℃ for 0.5 to 1.5 hours;
(3) Raising the temperature from 1100 ℃ to 1500 ℃ for 0.5-1.5 hours;
(4) Preserving heat for 0.5-1 h at 1500 ℃.
2. An antistatic metallic glaze according to claim 1, wherein:
the active fluxing agent I comprises albite and zinc oxide;
the active fluxing agent II comprises zinc oxide, wollastonite and albite.
3. An antistatic metallic glaze as in claim 2, wherein:
according to mass percentage, the antistatic metal glaze comprises 15-23% of kaolin, 12-18% of ferric phosphate, 30-40% of iron frit, 7-12% of albite, 1-3% of zinc oxide, 6-10% of apatite, 6-10% of lithium carbonate, 3-6% of calcined talcum and 0.2-0.5% of sodium tripolyphosphate;
The iron frit comprises, by mass, 26-42% of kaolin, 34-46% of ferric phosphate, 2-4% of wollastonite, 8-12% of albite, 3-7% of zinc oxide, 6-9% of calcined talcum, 2-4% of titanium dioxide, 0.4-1% of copper oxide and 0.5-2% of chromium oxide.
4. A method for preparing an antistatic metallic glazed tile, characterized in that it comprises the following steps:
A. mixing kaolin, ferric phosphate, an active fluxing agent II, calcined talcum, a crystal nucleus agent and metal color mixing oxide uniformly according to the proportion, calcining and water quenching to obtain an iron frit;
B. uniformly mixing kaolin, ferric phosphate, an active fluxing agent I, apatite, lithium carbonate, calcined talcum, sodium tripolyphosphate and the iron frit in the step A according to the proportion to obtain an antistatic metal glaze;
C. b, diluting the antistatic metal glaze in the step B with water and stamp-pad ink, grinding, applying the diluted and ground antistatic metal glaze to a biscuit firing ceramic tile blank, drying and firing to obtain an antistatic metal glaze ceramic tile;
in the step a, the firing curve of the iron frit is:
(1) Raising the temperature from normal temperature to 500 ℃ for 1-3 hours;
(2) Raising the temperature from 500 ℃ to 1100 ℃ for 0.5 to 1.5 hours;
(3) Raising the temperature from 1100 ℃ to 1500 ℃ for 0.5-1.5 hours;
(4) Preserving heat for 0.5-1 h at 1500 ℃.
5. The method for preparing the antistatic metallic glaze tile according to claim 4, wherein: in the step C, the antistatic metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground antistatic metal glaze is applied to the biscuit fired ceramic tile blank through screen printing, and the mesh number of the screen is 120-160 meshes.
6. The method for preparing the antistatic metallic glaze tile according to claim 4, wherein: in the step C, the mass mixing ratio of the antistatic metal glaze, the stamp-pad ink and the water is 1:1:1, a step of;
according to the mass percentage, the grinding fineness is 325 meshes, the screen residue is 0.3-0.5%, and the grinding time is 11.5-12.5 h;
the firing temperature of the antistatic metal glaze ceramic tile is 1200-1220 ℃.
7. An antistatic metal glazed tile, characterized in that: the antistatic metal glaze ceramic tile prepared by the preparation method of any one of claims 3 to 6, wherein the metal glossiness of the antistatic metal glaze ceramic tile is more than or equal to 80 degrees, and the surface resistance is 5 multiplied by 10 5 ～5×10 7 Ω。
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