CN116082063B - Acid-resistant alkali metal glaze, acid-resistant alkali metal glaze ceramic and preparation methods thereof - Google Patents

Acid-resistant alkali metal glaze, acid-resistant alkali metal glaze ceramic and preparation methods thereof Download PDF

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CN116082063B
CN116082063B CN202310368426.1A CN202310368426A CN116082063B CN 116082063 B CN116082063 B CN 116082063B CN 202310368426 A CN202310368426 A CN 202310368426A CN 116082063 B CN116082063 B CN 116082063B
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acid
glaze
resistant
alkali
metal
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CN116082063A (en
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罗强
王金凤
钟保民
徐瑜
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Foshan Donghua Shengchang New Material Co ltd
Foshan Dongpeng Ceramic Co Ltd
Foshan Dongpeng Ceramic Development Co Ltd
Guangdong Dongpeng Holdings Co Ltd
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Foshan Donghua Shengchang New Material Co ltd
Foshan Dongpeng Ceramic Co Ltd
Foshan Dongpeng Ceramic Development Co Ltd
Guangdong Dongpeng Holdings Co Ltd
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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
    • 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
    • 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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

The invention relates to the technical field of building ceramics, in particular to an acid-resistant alkali metal glaze, an acid-resistant alkali metal glaze ceramic and a preparation method thereof, wherein the acid-resistant alkali metal glaze comprises, by mass, 35-45% of kaolin, 27-33% of ferric phosphate, 7-10% of apatite, 7-13% of albite, 6-10% of calcined talcum, 1-4% of crystal nucleus agent, 3-5% of boron frit, 0.1-0.5% of color-doped metal oxide and 0.2-0.5% of sodium tripolyphosphate; the boron frit comprises, by mass, 35-45% of quartz, 28-43% of borax, 3-7% of sodium carbonate, 8-13% of calcined alumina, 4-6% of calcined talcum and 4-7% of albite. The acid-resistant alkali metal glaze provided by the scheme has excellent metal texture and acid-resistant alkali performance, so that the defects of the prior art are overcome.

Description

Acid-resistant alkali metal glaze, acid-resistant alkali metal glaze ceramic and preparation methods thereof
Technical Field
The invention relates to the technical field of building ceramics, in particular to an acid-alkali resistant metal glaze, an acid-alkali resistant metal glaze ceramic 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 luster imitation 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.
The ceramic product needs to be frequently contacted with various acid-base salt environments in daily life, such as an acid-base cleaning agent and the like, has higher acid-base resistance requirement on ceramic, and the metal glaze used on the surface of the existing ceramic product has poor acid-base resistance capability because of containing various metal elements, so that the corrosion and the falling of the glaze can be caused by long-term contact, the service life of the ceramic is reduced, and the glaze is easy to generate oxidation reaction to blacken, so that the ceramic product loses the original ornamental value and the normal use of the ceramic product is influenced.
Disclosure of Invention
The invention aims to provide an acid-resistant alkali metal glaze which has excellent metal texture and acid-resistant alkali performance so as to overcome the defects in the prior art.
The second aim of the invention is to provide a preparation method of the acid and alkali resistant metal glaze ceramic, which is simple and has strong operability, and the prepared acid and alkali resistant metal glaze ceramic has good metal texture effect and acid and alkali resistance.
The third purpose of the invention is to provide the acid-alkali resistant metal glaze ceramic prepared by the preparation method of the acid-alkali resistant metal glaze ceramic, wherein the metal glossiness is more than or equal to 90 degrees, and the low-concentration acid/alkali resistance at least reaches GLB (grade V).
To achieve the purpose, the invention adopts the following technical scheme:
the acid-resistant alkali metal glaze comprises, by mass, 35-45% of kaolin, 27-33% of ferric phosphate, 7-10% of apatite, 7-13% of albite, 6-10% of calcined talcum, 1-4% of nucleating agent, 3-5% of boron frit, 0.1-0.5% of color-doped metal oxide and 0.2-0.5% of sodium tripolyphosphate;
the boron frit comprises, by mass, 35-45% of quartz, 28-43% of borax, 3-7% of sodium carbonate, 8-13% of calcined alumina, 4-6% of calcined talcum and 4-7% of albite.
Further, the nucleating agent is titanium dioxide.
Further, the color-mixing metal oxide is any one or a combination of two of chromium oxide and copper oxide.
Further, the toned metal oxide is copper oxide;
the acid-resistant alkali metal glaze comprises, by mass, 38% of kaolin, 30% of ferric phosphate, 8% of apatite, 10% of albite, 8% of calcined talcum, 1.5% of titanium dioxide, 4% of boron frit, 0.2% of copper oxide and 0.3% of sodium tripolyphosphate;
the boron frit comprises, by mass, 40% of quartz, 35% of borax, 5% of sodium carbonate, 10% of calcined alumina, 5% of calcined talcum and 5% of albite.
A method for preparing acid and alkali resistant metal glaze ceramic, which is used for preparing the acid and alkali resistant metal glaze ceramic using the acid and alkali resistant metal glaze, and comprises the following steps:
A. uniformly mixing quartz, borax, sodium carbonate, calcined alumina, calcined talcum and albite according to a proportion, calcining and water quenching to obtain boron frit;
B. uniformly mixing kaolin, ferric phosphate, apatite, albite, calcined talcum, crystal nucleus agent, color-mixing metal oxide, sodium tripolyphosphate and boron frit in the step A according to the proportion to obtain acid and alkali resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze material in the step B by adding water and stamp-pad ink, grinding, applying diluted and ground acid-resistant alkali metal glaze material to the biscuit firing ceramic tile blank, and drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
In the step C, the acid-resistant alkali metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground acid-resistant alkali metal glaze is applied to the biscuit fired ceramic tile blank through screen printing, and the mesh number of the screen printing is 60-100 meshes.
Further, in the step C, the mass mixing ratio of the acid-resistant alkali 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 250 meshes, the screen residue is 0.3-0.5%, and the grinding time is 7.5-8.5 h.
Further, in the step C, the glaze firing temperature is 1200-1220 ℃.
Further, in the step a, the firing profile of the boron 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 1400 ℃ for 0.5-1 h;
(4) Preserving heat for 0.5-1 h at 1400 ℃.
The acid and alkali resistant metal glaze ceramic is prepared by the preparation method of the metal glaze ceramic, the metal glossiness of the metal glaze ceramic is more than or equal to 90 degrees, and the low-concentration acid/alkali resistance at least reaches GLB (grade V).
The technical scheme provided by the embodiment of the application can comprise the following beneficial effects:
1. the cooperation of kaolin, ferric phosphate 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 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 shows metal texture effect, so that the metal texture effect which can be achieved by the acid-resistant alkali metal glaze in the technical scheme is difficult to achieve by the conventional common 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.
2. Borax in the raw material of the boron frit reacts with calcined alumina, calcined talcum and albite to generate boron aluminate with stronger acid and alkali resistance, so that the acid and alkali resistance of the boron frit can be obviously improved by adding the boron frit into the formula of the acid and alkali resistance metal frit, and the defects that in the prior art, the metal frit is poor in acid and alkali resistance, corrosion and falling of a glaze surface can be caused by long-term contact, the service life of ceramic is shortened, and the glaze surface is easy to generate oxidation reaction to blacken, so that the ceramic product loses the original ornamental value and the normal use of the ceramic product is influenced are overcome.
3. Under the synergistic effect of crystal nucleus agent, apatite, ferric phosphate and boron frit, the precipitation amount of the iron-containing spinel crystal reaches the expected after the acid-resistant alkali metal glaze is calcined, so that the glaze of the prepared acid-resistant alkali metal glaze ceramic product has a good metal texture effect.
4. The preparation method is simple, the operability is strong, the metallic glossiness of the obtained acid and alkali resistant metallic glaze ceramic glaze is more than or equal to 90, the low concentration acid/alkali resistance at least reaches GLB (grade V), and the acid and alkali resistant ceramic glaze has excellent metallic texture effect and acid and alkali resistant performance.
Detailed Description
The technical scheme provides an acid-resistant alkali metal glaze, which comprises, by mass, 35-45% of kaolin, 27-33% of ferric phosphate, 7-10% of apatite, 7-13% of albite, 6-10% of calcined talcum, 1-4% of crystal nucleus agent, 3-5% of boron frit, 0.1-0.5% of color-doped metal oxide and 0.2-0.5% of sodium tripolyphosphate;
the boron frit comprises, by mass, 35-45% of quartz, 28-43% of borax, 3-7% of sodium carbonate, 8-13% of calcined alumina, 4-6% of calcined talcum and 4-7% of albite.
In order to ensure that the glaze has excellent metal texture and good acid and alkali resistance, the technical scheme provides an acid and alkali resistant metal glaze, wherein the raw materials comprise kaolin, ferric phosphate, apatite, albite, calcined talcum, crystal nucleus agent, boron frit, color-doped metal oxide and sodium tripolyphosphate.
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 make the glaze surface show metal texture effect, the kaolin, the ferric phosphate and the calcined talcum are added into the formula of the acid-resistant alkali metal glaze, the kaolin, the ferric phosphate and the calcined talcum are matched to generate the iron-containing spinel crystal which can make the glaze surface show metal texture effect, the iron-containing spinel crystal is an equiaxed crystal system, the symmetry degree of the crystal is high, the main form is an octahedron, the bottom and the surface of the crystal are parallel to the glaze surface, the light is most easily reflected, and the bottom and the surface of the crystal are parallel to the glaze surface and are the necessary conditions for the glaze surface to show metal texture effect, therefore, the metal texture effect which can be achieved by the acid-resistant alkali metal glaze in the technical scheme is difficult to achieve by the conventional common 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, the metal glaze used on the glaze of the existing ceramic product contains various metal elements, so that the acid and alkali resistance is poor, the corrosion and the falling of the glaze can be caused by long-term contact, the service life of the ceramic is reduced, the glaze is easy to generate oxidation reaction to turn black, the ceramic product loses the original ornamental value, and the normal use of the ceramic product is influenced.
The raw materials of the acid-resistant alkali metal glaze formula in the technical scheme also comprise boron frit, borax in the boron frit raw materials reacts with calcined alumina, calcined talcum and albite to generate boroaluminate with strong acid and alkali resistance, so that the acid and alkali resistance of the boron frit can be obviously improved by adding the boron frit into the acid and alkali-resistant metal glaze formula, the defects that in the prior art, the metal glaze is poor in acid and alkali resistance, corrosion and falling of a glaze surface can be caused by long-term contact, the service life of ceramic is reduced, the glaze surface is easy to generate oxidation reaction to turn black, the original ornamental value of a ceramic product is lost, and the normal use of the ceramic product is influenced are overcome.
Specifically, the boron frit in the technical scheme comprises quartz, borax, sodium carbonate, calcined alumina, calcined talcum and albite; wherein, borax mainly provides diboron trioxide which exists in the form of a boron-oxygen triangle [ BO3] and belongs to a layered structure; the calcined talcum and the albite can provide enough free oxygen to enable the boron-oxygen tetrahedron [ BO3] to be converted into boron-oxygen tetrahedron [ BO4], namely the diboron trioxide is converted into a three-dimensional space network structure similar to the silicon-oxygen tetrahedron [ SiO4] from a layered structure, the three-dimensional space network structure has stronger acid and alkali resistance, in the process, the diboron trioxide reacts with the calcined alumina, the calcined talcum and the albite to generate boroaluminate, the boron-oxygen tetrahedron [ BO4] exists in the form of boroaluminate, and the acid and alkali resistance of the boro frit is obviously improved by adding the boro frit into an acid and alkali resistance metal glaze formula.
In addition, the diboron trioxide has fluxing action, so that the raw materials borax, talcum, sodium carbonate and albite of the boron frit in the technical scheme are good fluxing agents, and the boron frit has the effects of reducing firing temperature and promoting sintering when being added into a boron frit formula.
Meanwhile, the raw material of the boron frit in the technical scheme also comprises quartz, wherein the main component of the quartz is silicon dioxide, the silicon dioxide belongs to network generating body oxide, and a network skeleton is provided for a glass phase of the boron frit; meanwhile, the silicon dioxide exists in the form of silicon oxygen tetrahedron [ SiO4], the silicon oxygen tetrahedrons are connected by angles to form a three-dimensional space network structure, and the improvement of the acid and alkali resistance of the boron frit is facilitated.
Furthermore, the raw materials of the boron frit in the scheme also comprise calcined alumina, and besides the calcined alumina can react with the decomposition product of borax, namely diboron trioxide, the calcined alumina has high mechanical strength, excellent wear resistance, acid and alkali resistance and high temperature resistance, and can be added into a boron frit formula to provide a support for a boron frit glass phase, so that the acid and alkali resistance of the boron frit can be improved while the collapse of the boron frit is avoided.
In addition, the boron frit is a glassy frit after being fired at high temperature, has low viscosity, forms obvious viscosity difference with the acid-resistant alkali metal frit after being added into the formula of the acid-resistant alkali metal frit, has high matching degree of the viscosity difference of the boron frit and the acid-resistant alkali metal frit, is favorable for precipitation of iron-containing spinel crystals in the acid-resistant alkali metal frit, and further improves metal texture effect.
More specifically, according to mass percent, the boron frit in the technical scheme comprises 35-45% of quartz, 28-43% of borax, 3-7% of sodium carbonate, 8-13% of calcined alumina, 4-6% of calcined talcum and 4-7% of albite.
In the boron frit, borax is mainly used, so that the addition amount is limited to 28-43%, the sufficient acid and alkali resistance of the boron frit is ensured, and if the addition amount of the borax is more than 43%, the viscosity of the boron frit is too low due to the fluxing effect of the diboron trioxide provided in the borax, the viscosity matching degree with the acid-resistant alkali metal glaze is poor, the precipitation of ferrite-containing spinel crystals in the acid-resistant alkali metal glaze formula is not facilitated, and the metal texture effect is poor; if the addition amount of borax is less than 28%, the content of the provided diboron trioxide is reduced, which is unfavorable for the formation of boroaluminate, and the acid and alkali resistance of the boron frit is reduced, so that the acid resistance of the acid-alkali-resistant metal glaze is affected.
The quartz and the calcined alumina are important components of the glass phase of the boron frit, and the acid-base resistance of the boron frit can be increased, so that the addition amount of the quartz and the calcined alumina is respectively limited to 35-45% and 8-13%, and if the addition amount of the quartz and the calcined alumina is higher than the above range, the high-temperature viscosity is too high while the boron frit is burned, the viscosity matching degree with the acid-base resistant metal glaze is poor, the precipitation of iron-containing spinel crystal is not facilitated, and the metal texture effect is affected; if the addition amount of quartz and calcined alumina is lower than the range, the acid and alkali resistance of the boron frit is affected, so that the acid and alkali resistance of the acid and alkali resistant metal glaze is deteriorated; meanwhile, the high-temperature viscosity of the boron frit is too low, the viscosity matching degree with the acid-resistant alkali metal glaze is poor, precipitation of iron-containing spinel crystals is not facilitated, and the metal texture effect of the acid-resistant alkali metal glaze is affected.
The calcined talc, the sodium carbonate and the albite mainly play a role of fluxing agents, and ideal effects can be achieved by adding a small amount of 4-6%, 3-7% and 4-7% of the calcined talc and the albite respectively, if the addition amount of the sodium carbonate, the calcined talc and the albite is out of the range, the viscosity of the boron frit is too high or too low, the viscosity matching degree with the acid-resistant alkali metal glaze is poor, the precipitation of iron-containing spinel crystals is not facilitated, and the metal texture effect of the acid-resistant alkali metal glaze is affected.
Therefore, according to the technical scheme, the quartz, the borax, the sodium carbonate, the calcined alumina, the calcined talcum and the albite are compounded, and the components of the raw materials are limited in the range of the addition amount, so that the boron frit has stronger acid and alkali resistance; meanwhile, the boron frit in the technical scheme forms obvious viscosity difference with the acid-resistant alkali metal glaze after high-temperature calcination, and the viscosity difference matching degree of the boron frit and the acid-resistant alkali metal glaze is high, so that the precipitation of iron-containing spinel crystals in the acid-resistant alkali metal glaze is facilitated; in addition, the boron frit does not contain heavy metal elements such as lead, cadmium and the like, is safe and environment-friendly, and does not influence the health.
In addition, the formula raw materials of the acid-resistant alkali metal glaze further comprise a crystal nucleus agent, which can reduce crystallization activation energy and crystallization peak temperature, promote crystallization and further improve the metal texture effect of the acid-resistant alkali metal glaze.
In addition, the raw materials of the acid-resistant alkali metal glaze formula in the technical scheme also comprise apatite, and besides fluxing action, the apatite can also produce phosphorus pentoxide during calcination; meanwhile, phosphorus pentoxide can be generated during iron phosphate calcination, and is high in coordination number, a cation field is strong, phase separation is easily caused by separation from a glass phase in a heat treatment process, a phase separation promoting crystal nucleus agent is enriched in one phase, and the phosphorus pentoxide plays a role of crystal nucleus when enriched to a certain degree; meanwhile, the phase separation promotes the enrichment of metal ions in the acid-resistant alkali metal glaze, so that the precipitation of iron-containing spinel crystals is easier.
Meanwhile, the boron frit in the technical scheme can promote precipitation of the iron-containing spinel crystals, so that the precipitation amount of the iron-containing spinel crystals reaches the expected value after the acid-resistant alkali metal glaze is calcined under the synergistic effect of the crystal nucleus agent, the apatite, the ferric phosphate and the boron frit, and the prepared acid-resistant alkali metal glaze ceramic product glaze has a good metal texture effect.
In addition, the color-mixing metal oxide can color the material formed by the glass phase unit and the crystallization unit, and the color-mixing metal oxide is added in the formula of the acid-resistant alkali metal glaze, and is 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.
Finally, the raw material of the acid-resistant alkali metal glaze formula in the technical scheme, namely the calcined talc is not only one of the raw materials formed by the iron-containing spinel crystal, but also has fluxing action, and the calcined talc and the active fluxing agent albite are added into the formula together, so that the calcined talc has the effects of reducing the firing temperature and promoting sintering; besides, the raw material kaolin in the acid-resistant alkali metal glaze formula in the technical scheme provides a network skeleton for the glazed glass phase, and during calcination, the kaolin and apatite, albite and calcined talcum with fluxing action and other components are subjected to physical or chemical reaction to generate a silicate glass network structure, 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 of the ceramic, the mechanical strength, the thermal stability, the chemical stability and the antifouling performance of the ceramic after calcination can be ensured.
Besides, the formula of the acid-resistant alkali metal glaze 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, and then the acid-resistant alkali performance and the metal texture effect are influenced.
Further, according to mass percentage, the formula of the acid-resistant alkali metal glaze in the technical scheme comprises 35-45% of kaolin, 27-33% of ferric phosphate, 7-10% of apatite, 7-13% of albite, 6-10% of calcined talcum, 1-4% of crystal nucleus agent, 3-5% of boron frit, 0.1-0.5% of color-doped metal oxide and 0.2-0.5% of sodium tripolyphosphate.
The boron frit not only can improve the acid and alkali resistance of the acid-resistant alkali metal glaze, but also is beneficial to the precipitation of iron-containing spinel crystals, so that the addition amount is limited to 3-5%, and if the addition amount of the boron frit is more than 5%, the boron frit has a certain fluxing effect, so that the addition amount is too much, the fluxing effect is enhanced, the glass phase of the glaze is increased after the acid-resistant alkali metal glaze is calcined, the precipitation of the iron-containing spinel is reduced, and the metal texture effect is affected; if the addition amount of the boron frit is less than 3%, the formed acid and alkali resistant boroaluminate is reduced, and the acid and alkali resistant performance is reduced.
The kaolin is an important component of a glazed glass phase and is one of raw materials formed by iron-containing spinel, so that the addition amount of the kaolin is limited to 35-45%, and if the addition amount of the kaolin is more than 45%, the glaze is burnt, so that the yellowing of the glaze is caused, and the metal texture effect is poor; if the amount of kaolin added is less than 35%, the content of aluminum ions as a crystallization raw material of the iron-containing spinel crystal becomes small, precipitation of the iron-containing spinel becomes small, and metallic texture effect is affected.
Iron phosphate is one of the raw material components for forming iron-containing spinel crystals, and contributes to precipitation of iron-containing spinel crystals, so that the addition amount is limited to 27-33%, and if the addition amount of iron phosphate is more than 33%, the rest of the crystallization raw materials correspondingly decrease, thereby being unfavorable for precipitation of iron-containing spinel crystals and deteriorating the metal texture effect; if the addition amount of ferric phosphate is less than 27%, the contents of ferric ions and phosphorus pentoxide which are used as crystallization raw materials and contribute to enrichment of metal ions in the formula are correspondingly reduced, and the precipitation of iron-containing spinel crystals is also not facilitated, so that the metal texture effect is reduced.
The apatite has fluxing effect and can promote precipitation of iron-containing spinel crystals, so that the addition amount is limited to 7-10%, and if the addition amount of the apatite is more than 10%, the fluxing effect is too strong, so that overmuch glazed glass phase is caused, the precipitation amount of the iron-containing spinel crystals is reduced, and the metal texture effect is influenced; if the addition amount of the apatite is less than 7%, phosphorus pentoxide which is beneficial to enrichment of metal ions in the formula is correspondingly reduced, precipitation of iron-containing spinel crystals is not facilitated, and the metal texture effect is affected.
The albite mainly plays a role in fluxing, and an ideal effect can be achieved only by adding 7-13%, and if the adding amount of the albite is more than 13%, the fluxing effect is too strong, so that the glazed glass phase is too much, the precipitation amount of the ferrite-containing spinel crystal is reduced, and the metal texture effect is affected; if the addition amount of the albite is less than 7%, the high-temperature viscosity is too high while the glaze is burned, the precipitation of the iron-containing spinel crystal becomes difficult, and the metal texture effect is also affected.
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 6-10%, and if the addition amount of the calcined talcum is more than 10%, the fluxing effect is dominant, so that the glazed glass phase is excessive, the precipitation amount of the iron-containing spinel crystal is reduced, and the metal texture effect is influenced; if the addition amount of the calcined talc is less than 6%, the content of magnesium ions in the crystal raw material of the iron-containing spinel crystal becomes small, and precipitation of the iron-containing spinel crystal is also not facilitated, and the metallic texture effect is also affected.
The crystal nucleus agent can promote the precipitation of the iron-containing spinel crystals in the system, so that the addition amount of the crystal nucleus agent is 1-4%, 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 glaze is too large, the crystallization effect of the iron-containing spinel crystals is affected, and the metal texture effect is reduced; if the addition amount of the nucleating agent is less than 1%, the crystallization effect of the iron-containing spinel crystal is also affected by too low a content of a substance playing a role in nucleating, and the metallic texture effect is also reduced.
The color-mixing metal oxide is combined with iron ions in the formula to further color the iron-containing spinel crystal, and if the addition amount is too high and too low, the metal color is deviated to influence the metal texture, so that the addition amount is limited to 0.1-0.5%.
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 acid-resistant alkali metal glaze formula 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 synthesis amount of the acid-resistant alkali boroaluminate are larger, and the metal texture effect and the acid-resistant alkali can meet the requirements.
Further, the nucleating agent is titanium dioxide.
In one embodiment of the technical scheme, the crystal nucleus agent is titanium dioxide, the bond strength of titanium and oxygen in the titanium dioxide is high, under the high-temperature condition, titanium tends to form four-time coordinated titano-tetrahedron, and the four-time coordinated titano-tetrahedron is mutually mixed and melted with silicon oxygen tetrahedron of a silicate network structure in a glass phase, when the temperature is reduced, titanium tends to form six-time coordinated titano-octahedron, and a liquid phase rich in titanium dioxide component is separated from the original state of being mutually mixed and melted with the silicon oxygen tetrahedron, so that crystal nuclei are easy to form, the precipitation of crystals in a formula is promoted, and the metal texture effect is further improved.
Further, the color-mixing metal oxide is any one or the combination of two of chromium oxide and copper oxide.
In one embodiment of the present disclosure, the color-adjusting metal oxide is any one or a combination of copper oxide and chromium oxide, which are combined with iron ions in the formulation to color the iron-containing spinel.
Further illustratively, the color matching metal oxide is copper oxide;
the acid-resistant alkali metal glaze comprises, by mass, 38% of kaolin, 30% of ferric phosphate, 8% of apatite, 10% of albite, 8% of calcined talcum, 1.5% of titanium dioxide, 4% of boron frit, 0.2% of copper oxide and 0.3% of sodium tripolyphosphate;
the boron frit comprises, by mass, 40% of quartz, 35% of borax, 5% of sodium carbonate, 10% of calcined alumina, 5% of calcined talcum and 5% of albite.
In a preferred embodiment of the technical scheme, the color-mixing metal oxide is copper oxide, and the acid-resistant alkali metal glaze comprises, by mass, 38% of kaolin, 30% of ferric phosphate, 8% of apatite, 10% of albite, 8% of calcined talcum, 1.5% of titanium dioxide, 4% of boron frit, 0.2% of copper oxide and 0.3% of sodium tripolyphosphate; the boron frit comprises 40% of quartz, 35% of borax, 5% of sodium carbonate, 10% of calcined alumina, 5% of calcined talcum and 5% of albite, and the acid and alkali resistance and metal texture effects of the glaze are optimized while the cost is saved by further optimizing the components in the formula.
A method for preparing acid and alkali resistant metal glaze ceramic, which is used for preparing the acid and alkali resistant metal glaze ceramic using the acid and alkali resistant metal glaze, and comprises the following steps:
A. uniformly mixing quartz, borax, sodium carbonate, calcined alumina, calcined talcum and albite according to a proportion, calcining and water quenching to obtain boron frit;
B. uniformly mixing kaolin, ferric phosphate, apatite, albite, calcined talcum, crystal nucleus agent, color-mixing metal oxide, sodium tripolyphosphate and boron frit in the step A according to the proportion to obtain acid and alkali resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze material in the step B by adding water and stamp-pad ink, grinding, applying diluted and ground acid-resistant alkali metal glaze material to the biscuit firing ceramic tile blank, and drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
The technical scheme also provides a preparation method of the acid and alkali resistant metal glaze ceramic, which comprises the following steps:
A. the quartz, borax, sodium carbonate, calcined alumina, calcined talcum and albite are uniformly mixed according to the proportion, calcined and water quenched to obtain the boron frit, the preparation method is simple, the prepared boron frit is suitable for large-scale popularization, the prepared boron frit has stronger chemical corrosion resistance, and the prepared boron frit forms obvious viscosity difference with acid-resistant and alkali-resistant metal glaze after being calcined, thereby being beneficial to precipitation of the medium crystal of the acid-resistant and alkali-resistant metal glaze and improving the metal texture effect.
B. And (3) uniformly mixing kaolin, ferric phosphate, apatite, albite, calcined talcum, crystal nucleus agent, color-mixing metal oxide, sodium tripolyphosphate and the boron frit obtained in the step A according to the proportion to obtain the acid-alkali resistant metal glaze, wherein the preparation method is simple, the operability is strong, and the prepared acid-alkali resistant metal glaze has good metal texture effect and acid and alkali resistance.
C. And B, diluting the acid-resistant alkali metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground acid-resistant alkali metal glaze to a biscuit-fired ceramic tile blank, drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic, wherein the preparation method is simple, the operability is strong, and the obtained acid-resistant alkali metal glaze ceramic glaze has excellent metal texture effect and acid-resistant alkali energy.
In addition, in the glaze firing process, the iron-containing spinel crystal is subjected to a growth and melting process, and part of the precipitated iron-containing spinel crystal begins to melt and is quenched at a high temperature, and due to abrupt change of a temperature field, a series of reactions are carried out on melted metal ions in the acid-resistant alkali metal glaze system to generate the iron-containing spinel crystal again, and the reactions are accompanied with volume expansion, so that the compactness of a glaze surface formed after the acid-resistant alkali metal glaze is calcined is improved, the permeation of acid-base chemical substances can be effectively prevented, and the acid-base resistance is improved.
Meanwhile, as the contact area between the iron-containing spinel crystals is larger, and the direct bonding degree between the iron-containing spinel crystals is higher, the low-temperature molten material in the silicate glass network structure is distributed in a triangular area formed between the iron-containing spinel crystals due to the lower melting point and better fluidity in the glaze firing process, so that the surface of the glassy low-temperature molten material is surrounded by the hard iron-containing spinel crystals, and the surface layer directly facing the acid-base substance chemical substances is the iron-containing spinel crystals, thereby effectively improving the acid-base resistance.
Further, in the step C, the acid-resistant alkali metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground acid-resistant alkali metal glaze is applied to the biscuit fired ceramic tile blank through screen printing, and the mesh number of the screen printing is 60-100 meshes.
In one embodiment of the technical scheme, in the step C, the acid-resistant alkali metal glaze material in the step B is diluted by water and stamp-pad ink and then is ground, and the diluted and ground acid-resistant alkali metal glaze material 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 material is applied to the biscuit firing ceramic tile blank through the process, and after glaze firing, the dispersion of the bottom and the surface crystals of the ferrite crystal precipitated on the ceramic glaze surface is small, so that the glaze metal texture effect is stable.
In a preferred embodiment of the technical scheme, the mesh number of screen printing is 60-100 mesh, 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 silk screen is too thick, the thickness of the glaze can be too thin, the metallic texture effect of the glaze is poor, and the antifouling performance is reduced.
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 80 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 acid-resistant alkali 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 250 meshes, the screen residue is 0.3-0.5%, and the grinding time is 7.5-8.5 h.
In one embodiment of the present technical solution, in step C, the mass mixing ratio of the acid-resistant alkali metal glaze, the stamp-pad ink and the water is 1:1:1, by further adjusting the proportion of the acid-resistant alkali metal glaze, the stamp-pad ink and the water, the viscosity of the acid-resistant alkali metal glaze is optimal, if the viscosity of the glaze slip is too low, the fluidity is too good after the glaze is applied, the stable and clear-boundary pattern is not formed, and if the viscosity of the glaze slip is higher, the fluidity is poor 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 the mass percent, the grinding fineness is 250 meshes, the screen residue is 0.3-0.5%, the grinding time is 7.5-8.5 h, 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 is improved, if the granularity of the glaze is too small, brown eyes and pinholes are easy to appear on the calcined glaze, and the antifouling performance of the glaze is reduced; if the granularity of the glaze is bigger, the sintering degree is insufficient, and the metal texture effect is affected.
In a preferred embodiment of the technical scheme, in the step C, according to the mass percentage, the grinding fineness is 250 meshes, the screen residue is 0.5%, and the grinding time is 8 hours, so that the granularity of the obtained glaze is matched with the printing process, and the glaze has good antifouling performance and good metal texture effect.
In the step C, water and stamp-pad ink are added for dilution to adjust the viscosity of the glaze slurry, so that the glaze slurry can obtain thixotropic property meeting actual requirements, and 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, in the step C, the glaze firing temperature is 1200-1220 ℃.
In an embodiment of the present technical solution, in the step C, the glaze firing temperature is 1200-1220 ℃, which is consistent with the firing temperature of the existing ceramic product, so that the purpose of industrial production is easily achieved while the product performance is ensured, and the large deviation between the experimental stage and the industrialization stage is reduced.
Further illustratively, in step a, the firing profile of the boron 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 1400 ℃ for 0.5-1 h;
(4) Preserving heat for 0.5-1 h at 1400 ℃.
In one embodiment of the technical scheme, the firing curve of the boron frit comprises a three-stage heating process and a one-stage heat preservation process, borax is melted and decomposed into diboron trioxide in the heating process from normal temperature to 500 ℃, and in the process, boron oxide is converted into boron oxide tetrahedron [ BO4] from boron oxide triangle [ BO3], namely, the boron trioxide is converted into a three-dimensional space network structure similar to silicon oxygen tetrahedron [ SiO4] from a layered structure, the boron oxide has stronger acid and alkali resistance, and in the process, the boron oxide reacts with calcined alumina, calcined talcum and albite to generate boron aluminate, and the boron oxide tetrahedron [ BO4] exists in the form of boron aluminate; then, the temperature is increased to 1100 ℃ from 500 ℃, and the sodium carbonate in the boron frit raw material is oxidatively decomposed, and quartz in the boron frit raw material, sodium carbonate, calcined alumina, calcined talcum, albite and the like form an aluminosilicate glass phase; then, in the heating process of 1100 ℃ to 1400 ℃, the boroaluminate is fused into an aluminosilicate glass phase network structure to become a part of the glass phase network structure, and the high-temperature viscosity of the glass phase can be effectively reduced; finally, the temperature is kept at 1400 ℃, so that the boron aluminate is more thoroughly blended, the sintered glassy boron frit is higher in acid and alkali resistance, and when the boron aluminate is added into an acid and alkali resistant metal glaze formula, obvious viscosity difference is formed between the boron aluminate and the acid and alkali resistant metal glaze, the viscosity difference matching degree of the boron aluminate and the acid and alkali resistant metal glaze is higher, precipitation of iron-containing spinel crystals in the acid and alkali resistant metal glaze is facilitated, and the metal texture effect is further improved.
Still further, in a preferred embodiment of the present disclosure, the firing profile of the boron 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 1400 ℃ for 0.5h; (4) incubating at 1400 for 0.5h. The time of each heating or heat preservation process is further optimized, so that the acid and alkali resistance is further improved while the energy consumption is effectively reduced, and the precipitation of iron-containing spinel crystals in the acid and alkali resistance metal glaze is further facilitated after the acid and alkali resistance metal glaze is added into the formula of the acid and alkali resistance metal glaze, so that the metal texture effect is further improved.
The acid and alkali resistant metal glaze ceramic is prepared by the preparation method of the metal glaze ceramic, the metal glossiness of the metal glaze ceramic is more than or equal to 90 degrees, and the low-concentration acid/alkali resistance at least reaches GLB (grade V).
The technical scheme also provides the acid and alkali resistant metal glaze ceramic, wherein the metal glossiness is more than or equal to 90, and the low-concentration acid/alkali resistance at least reaches GLB (grade V), so that the acid and alkali resistant metal glaze ceramic has excellent metal texture effect and acid and alkali resistance.
The technical scheme of the invention is further described by the following specific embodiments.
Example 1-preparation method of acid and alkali-resistant Metal glazed ceramic
A. According to the mass percentage, evenly mixing 35% quartz, 43% borax, 3% sodium carbonate, 8% calcined alumina, 5% calcined talcum and 6% albite, calcining and water quenching to obtain boron frit;
B. uniformly mixing 35% of kaolin, 33% of ferric phosphate, 7% of apatite, 13% of albite, 6% of calcined talcum, 2.7% of crystal nucleus agent, 0.1% of color-mixing metal oxide, 0.2% of sodium tripolyphosphate and 3% of boron frit in the step A according to mass percentage to obtain acid-alkali resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground acid-resistant alkali metal glaze to the biscuit fired ceramic tile blank through screen printing, drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
Example 2-preparation method of acid and alkali-resistant Metal glazed ceramic
A. Uniformly mixing 38% of quartz, 39% of borax, 7% of sodium carbonate, 8% of calcined alumina, 4% of calcined talcum and 4% of albite according to mass percentage, calcining and water quenching to obtain boron frit;
B. uniformly mixing 40% of kaolin, 30% of ferric phosphate, 7% of apatite, 8% of albite, 10% of calcined talcum, 1% of crystal nucleus agent, 0.2% of color-mixing metal oxide, 0.3% of sodium tripolyphosphate and 3.5% of boron frit in the step A according to mass percentage to obtain acid-alkali resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground acid-resistant alkali metal glaze to the biscuit fired ceramic tile blank through screen printing, drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
Example 3-preparation method of acid and alkali-resistant Metal glazed ceramic
A. Uniformly mixing 40% of quartz, 35% of borax, 5% of sodium carbonate, 10% of calcined alumina, 5% of calcined talcum and 5% of albite according to mass percentage, calcining and water quenching to obtain boron frit;
B. uniformly mixing 38% of kaolin, 30% of ferric phosphate, 8% of apatite, 10% of albite, 8% of calcined talcum, 1.5% of nucleating agent, 0.2% of color-mixing metal oxide, 0.3% of sodium tripolyphosphate and 4% of boron frit in the step A according to the mass percentage to obtain an acid-alkali resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground acid-resistant alkali metal glaze to the biscuit fired ceramic tile blank through screen printing, drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
Example 4-preparation method of acid and alkali-resistant Metal glazed ceramic
A. Uniformly mixing 42% of quartz, 30% of borax, 3% of sodium carbonate, 13% of calcined alumina, 5% of calcined talcum and 7% of albite according to mass percentage, calcining and water quenching to obtain boron frit;
B. uniformly mixing 41% of kaolin, 28% of ferric phosphate, 10% of apatite, 7% of albite, 6% of calcined talcum, 4% of crystal nucleus agent, 0.5% of color-mixing metal oxide, 0.5% of sodium tripolyphosphate and 3% of boron frit in the step A according to the mass percentage to obtain an acid-alkali resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground acid-resistant alkali metal glaze to the biscuit fired ceramic tile blank through screen printing, drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
Example 5-preparation method of acid and alkali-resistant Metal glazed ceramic
A. According to the mass percentage, evenly mixing 45% quartz, 28% borax, 5% sodium carbonate, 10% calcined alumina, 6% calcined talcum and 6% albite, calcining and water quenching to obtain boron frit;
B. uniformly mixing 45% of kaolin, 27% of ferric phosphate, 7% of apatite, 7% of albite, 6% of calcined talcum, 2.3% of nucleating agent, 0.4% of color-mixing metal oxide, 0.3% of sodium tripolyphosphate and 5% of boron frit in the step A according to the mass percentage to obtain an acid-base resistant metal glaze;
C. and B, diluting the acid-resistant alkali metal glaze in the step B by adding water and stamp-pad ink, grinding, applying the diluted and ground acid-resistant alkali metal glaze to the biscuit fired ceramic tile blank through screen printing, drying and glaze firing to obtain the acid-resistant alkali metal glaze ceramic.
The acid-alkali-resistant metal glaze ceramic is prepared by adopting the different preparation methods in the embodiment, the surface effect of the prepared acid-alkali-resistant metal glaze ceramic tile is observed, the gloss of the glaze is tested by using a gloss meter, and the obtained acid-alkali-resistant metal glaze ceramic tile is tested by using GB/T3810.13-2016 ceramic tile test method part 13: the acid and alkali resistance test was carried out by the test method of the chemical resistance test, and the test results are shown in Table 1 below.
Table 1 results of Performance test of different acid and alkali resistant Metal glazed ceramics in examples
Figure SMS_1
From the performance test results of the examples in the table, the acid-alkali resistant metal glaze ceramic prepared by the preparation method of the acid-alkali resistant metal glaze ceramic has lifelike glaze metal texture, excellent metallic luster and acid-alkali resistance, wherein the metallic luster is more than or equal to 90 degrees, and the low-concentration acid/alkali resistance at least reaches GLB (grade V).
Comparative example 1: the preparation method and the raw materials described in comparative example 1 and example 3 are the same, but the addition amount of the raw materials in the boron frit is different from example 3, specifically: the boron frit comprises, by mass, 32% of quartz, 44% of borax, 6% of sodium carbonate, 5% of calcined alumina, 6% of calcined talcum and 7% of albite.
Comparative example 2: comparative example 1 was identical to the preparation method and raw materials described in example 3, except that the addition amount of the raw materials in the formulation of the acid-resistant alkali metal glaze was different from example 3, specifically, 34% of kaolin, 26% of iron phosphate, 10% of apatite, 11% of albite, 11% of calcined talc, 3% of a crystal nucleus agent, 4% of boron frit, 0.5% of a color-doped metal oxide and 0.5% of sodium tripolyphosphate, in terms of mass%.
The acid-alkali-resistant metal glaze ceramic is prepared by adopting different preparation methods in the comparative examples, the surface effect of the prepared acid-alkali-resistant metal glaze ceramic tile is observed, the gloss of the glaze is tested by using a gloss meter, and the obtained acid-alkali-resistant metal glaze ceramic tile is subjected to GB/T3810.13-2016 part 13 of the ceramic tile test method: the acid and alkali resistance test was carried out by the test method of the chemical resistance test, and the test results are shown in Table 2 below.
Table 2 results of Performance test of different acid and alkali resistant Metal glazed ceramics in comparative examples
Figure SMS_2
As is clear from table 2, when the addition amount of the formulation raw materials is not within the range defined in the present embodiment, the metal feel effect and acid and alkali resistance of the obtained acid and alkali resistant glazed tile are hardly 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 acid-resistant alkali metal glaze, characterized in that: according to mass percentage, the material comprises 35-45% of kaolin, 27-33% of ferric phosphate, 7-10% of apatite, 7-13% of albite, 6-10% of calcined talcum, 1-4% of nucleating agent, 3-5% of boron frit, 0.1-0.5% of color mixing metal oxide and 0.2-0.5% of sodium tripolyphosphate, wherein the nucleating agent is titanium dioxide, and the color mixing metal oxide is any one or combination of two of chromium oxide and copper oxide;
the boron frit comprises, by mass, 35-45% of quartz, 28-43% of borax, 3-7% of sodium carbonate, 8-13% of calcined alumina, 4-6% of calcined talcum and 4-7% of albite;
wherein, the firing curve of the boron 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 1400 ℃ for 0.5-1 h;
(4) Preserving heat for 0.5-1 h at 1400 ℃.
2. An acid-resistant alkali metal glaze according to claim 1, wherein:
the color-mixing metal oxide is copper oxide;
the acid-resistant alkali metal glaze comprises, by mass, 38% of kaolin, 30% of ferric phosphate, 8% of apatite, 10% of albite, 8% of calcined talcum, 1.5% of titanium dioxide, 4% of boron frit, 0.2% of copper oxide and 0.3% of sodium tripolyphosphate;
the boron frit comprises, by mass, 40% of quartz, 35% of borax, 5% of sodium carbonate, 10% of calcined alumina, 5% of calcined talcum and 5% of albite.
3. A preparation method of acid and alkali resistant metal glaze ceramic is characterized in that: an acid-alkali-resistant metal glaze ceramic for producing an acid-alkali-resistant metal glaze using the acid-alkali-resistant metal glaze according to any one of claims 1 to 2, comprising the steps of:
A. uniformly mixing quartz, borax, sodium carbonate, calcined alumina, calcined talcum and albite according to a proportion, calcining and water quenching to obtain boron frit;
B. uniformly mixing kaolin, ferric phosphate, apatite, albite, calcined talcum, crystal nucleus agent, color-mixing metal oxide, sodium tripolyphosphate and boron frit in the step A according to the proportion to obtain acid and alkali resistant metal glaze;
C. adding water and stamp-pad ink into the acid-resistant alkali metal glaze material in the step B for dilution, grinding, applying diluted and ground acid-resistant alkali metal glaze material cloth to a biscuit fired ceramic tile blank, drying and glaze firing to obtain acid-resistant alkali metal glaze ceramic;
in the step a, the firing curve of the boron frit is as follows:
(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 1400 ℃ for 0.5-1 h;
(4) Preserving heat for 0.5-1 h at 1400 ℃.
4. A method for preparing an acid and alkali resistant metal glazed ceramic according to claim 3, wherein: in the step C, the acid-resistant alkali metal glaze in the step B is diluted by water and stamp-pad ink and then is ground, the diluted and ground acid-resistant alkali metal glaze is applied to the biscuit fired ceramic tile blank through screen printing, and the mesh number of the screen printing is 60-100 meshes.
5. A method for preparing an acid and alkali resistant metal glazed ceramic according to claim 3, wherein: in the step C, the mass mixing ratio of the acid-resistant alkali 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 250 meshes, the screen residue is 0.3-0.5%, and the grinding time is 7.5-8.5 h.
6. A method for preparing an acid and alkali resistant metal glazed ceramic according to claim 3, wherein: in the step C, the glaze firing temperature is 1200-1220 ℃.
7. An acid and alkali resistant metal glaze ceramic, which is characterized in that: the metal glaze ceramic is prepared by the preparation method of the metal glaze ceramic according to any one of claims 3 to 6, wherein the metal glossiness of the metal glaze ceramic is more than or equal to 90 degrees, and the low-concentration acid/alkali resistance reaches at least GLB (grade V).
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