CN113264783B - Prestressed ceramic and preparation method thereof - Google Patents
Prestressed ceramic and preparation method thereof Download PDFInfo
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- 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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- 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
- C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
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- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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- 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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Abstract
The invention discloses a prestressed ceramic and a preparation method thereof, wherein the prestressed ceramic comprises a blank body and a first prestressed layer positioned on the surface of the blank body, and the thermal expansion coefficient of the first prestressed layer is smaller than that of the blank body; the raw materials of the first pre-stress layer comprise calcite, kaolin, quartz, spodumene, zinc oxide, barium carbonate and frit; wherein, the frit comprises kaolin, quartz, talc, dolomite, alumina, zinc oxide, wollastonite and spodumene. According to the prestressed ceramic, the first prestressed layers are respectively arranged on the surface and the bottom surface of the blank body, and when the ceramic is subjected to a certain external tensile stress, the prestress of the first prestressed layers can be offset, so that the strength and toughness of the ceramic are greatly improved, the ceramic structure is prevented from being damaged, and the problems of low impact resistance and low strength of the conventional ceramic are solved.
Description
Technical Field
The invention relates to the technical field of building ceramics, in particular to prestressed ceramics and a preparation method thereof.
Background
With the ever-increasing economy of China, the requirements of people on the quality of life are continuously improved, so that the demand on materials is higher and higher, and particularly, the requirements on building ceramics are not only on exquisite and attractive appearance, but also on excellent performance. As is well known, ceramics have the defects of high brittleness, low impact resistance, low strength, thickness and difficulty in transportation, and are easy to break due to failure to bear stress concentration. Therefore, how to increase the hardness of the ceramic is a target to be overcome by ceramic enterprises.
At present, the methods for enhancing the strength of ceramics include: densification enhancement, in-situ authigenic crystal phase enhancement, introduction of enhanced phase enhancement, prestress enhancement and the like. The densification enhancement is to improve the crystallization effect of the ceramic at high temperature by controlling the sintering condition, so as to improve the strength of the ceramic, but the method adopting the densification enhancement has limited enhancement range and also has limitation to the material; the in-situ authigenic crystal phase is enhanced, and the size of the crystal is improved mainly through sintering, so that the strength of the ceramic is improved; the method of introducing the reinforcing phase to strengthen generally adopts a physical strengthening method, and the method of adopting the in-situ authigenic crystal phase to strengthen and introducing the reinforcing phase to strengthen has limited amplitude of increasing the strength of the ceramic, and can not meet the requirement of people on the strength of the ceramic.
The prestress enhancement method is to form a prestress layer on the surface of a material by a certain chemical method, and the prestress layer can offset the material when the material is subjected to a certain external tensile stress, so that the breaking strength of the material is improved, and the ceramic structure is prevented from being damaged. The technology is currently applied in many fields, such as concrete materials, dental ceramics, tempered glass, and the like. However, the technology of the prestress enhancement method is mainly applied to daily ceramics at present, and is rarely applied to the field of building ceramics, and in the preparation of the existing prestress daily ceramics, in order to enable the ceramics to have prestress, six surfaces of the ceramics are coated, so that the technology is not suitable for large-scale industrial production and is not suitable for production of building ceramics. Therefore, how to apply the prestress reinforcement method to the architectural ceramics becomes a problem which is currently focused on by extensive researchers.
Disclosure of Invention
Aiming at the problems brought forward by the background technology, the invention aims to provide a prestressed ceramic, wherein a first prestressed layer and a second prestressed layer are respectively arranged on the surface and the bottom surface of a blank body, and when the ceramic is subjected to a certain external tensile stress, the ceramic is counteracted by the first prestressed layer and the second prestressed layer, so that the strength and the toughness of the ceramic are greatly improved, the ceramic structure is prevented from being damaged, the problems of low impact resistance and low strength of the existing ceramic are solved, and a prestressed reinforcement method is applied to the field of building ceramics.
The invention also aims to provide a preparation method of the prestressed ceramic, which can be used for respectively arranging a first prestressed layer and a second prestressed layer on the surface and the bottom surface of a blank in a cloth pressing forming mode or a glaze spraying mode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the prestressed ceramic comprises a blank body and a first prestressed layer positioned on the surface of the blank body, wherein the thermal expansion coefficient of the first prestressed layer is smaller than that of the blank body;
the raw materials of the first pre-stress layer comprise calcite, kaolin, quartz, spodumene, zinc oxide, barium carbonate and frit;
the frit comprises the raw materials of kaolin, quartz, talc, dolomite, alumina, zinc oxide, wollastonite and spodumene.
Further, the first pre-stress layer comprises, by weight, 30-40 parts of calcite, 5-15 parts of kaolin, 15-20 parts of quartz, 10-20 parts of spodumene, 2-5 parts of zinc oxide, 5-10 parts of barium carbonate and 10-20 parts of frit.
Furthermore, the frit comprises, by weight, 10-20 parts of kaolin, 10-20 parts of quartz, 5-20 parts of talc, 10-25 parts of dolomite, 5-10 parts of alumina, 1-4 parts of zinc oxide, 10-15 parts of wollastonite and 5-10 parts of spodumene.
Further, a second pre-stress layer is arranged on the bottom surface of the pre-stress ceramic, and the raw materials of the second pre-stress layer comprise, by weight, 30-40 parts of calcite, 5-15 parts of kaolin, 15-20 parts of quartz, 10-20 parts of spodumene, 2-5 parts of zinc oxide, 5-10 parts of barium carbonate and 10-20 parts of frit;
the frit comprises the following raw materials of 10-20 parts of kaolin, 10-20 parts of quartz, 5-20 parts of talc, 10-25 parts of dolomite, 5-10 parts of alumina, 1-4 parts of zinc oxide, 10-15 parts of wollastonite and 5-10 parts of spodumene.
Further, the thickness of the first pre-stress layer and the second pre-stress layer is 200-300 μm.
A preparation method of prestressed ceramics is used for preparing the prestressed ceramics, and comprises the following steps:
(1) sintering the frit;
(2) mixing the fired frit with other raw materials of the pre-stress layer, adding water, ball milling to obtain pre-stress glaze slurry,
(3) applying the pre-stress glaze slurry on the surface of the blank to obtain a first pre-stress layer, or drying the pre-stress glaze slurry to prepare pre-stress powder, applying the pre-stress powder on the surface of the blank, and performing compression molding to form the first pre-stress layer on the surface of the blank;
(4) and (4) firing the semi-finished ceramic obtained in the step (3) to obtain the prestressed ceramic.
Further, in the step (3), the pre-stress glaze slip is dried and passes through a 250-mesh screen to obtain pre-stress powder.
Further, in the step (1), the temperature of the sintering treatment of the frit is 1520 ℃ and the holding time is 30 min.
Further, in the step (3), applying the pre-stress glaze slurry to the bottom surface of the blank to obtain a second pre-stress layer; or applying the pre-stress powder material to the bottom surface of the blank respectively, and performing press forming in a material distribution mode to form a second pre-stress layer on the bottom surface of the blank.
Further, in the step (4), the firing process of the semi-finished ceramic product comprises heat preservation for 20min at 570-575 ℃ and heat preservation for 1h at 1175-1185 ℃.
The technical scheme has the following beneficial effects:
1. according to the technical scheme, the first pre-stress layer is arranged on the surface of the ceramic, chemical reaction occurs between components in the high-temperature firing process, so that the thermal expansion coefficients of the blank and the first pre-stress layer are different, the thermal expansion coefficient of the first pre-stress layer is smaller than that of the blank, and therefore pre-stress is formed on the surface of the blank.
2. The frit is added into the raw materials of the pre-stress layer, the formula of the frit contains a large amount of calcium and magnesium solvents, under the high-temperature condition, anorthite and cordierite crystals are generated in the frit, and both the anorthite and the cordierite crystals have the characteristic of small expansion coefficients, so that the pre-stress of the pre-stress ceramic can be further improved, and the toughness of the first pre-stress layer can be further improved through the cordierite crystals.
3. The second pre-stress layer is arranged on the bottom surface of the pre-stress ceramic, so that the strength of the pre-stress ceramic is improved more obviously, and the surface and the bottom surface of the blank are subjected to uniform thermal stress in the blank sintering process.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
The prestressed ceramic comprises a blank body and a first prestressed layer positioned on the surface of the blank body, wherein the thermal expansion coefficient of the first prestressed layer is smaller than that of the blank body;
the raw materials of the first pre-stress layer comprise calcite, kaolin, quartz, spodumene, zinc oxide, barium carbonate and frit;
the frit comprises kaolin, quartz, talc, dolomite, alumina, zinc oxide, wollastonite and spodumene.
It is worth explaining that the prestressed ceramic of the technical scheme is provided with a first prestressed layer on the surface of the ceramic, chemical reactions occur among components in the high-temperature firing process, so that the thermal expansion coefficients of the green body and the first prestressed layer are different, and the thermal expansion coefficient of the first prestressed layer is smaller than that of the green body, so that prestress is formed on the surface of the green body, and when the ceramic is subjected to a certain tensile stress from the outside, the prestress can offset the applied tensile stress, so that the breaking strength of the ceramic is improved, and the ceramic structure is prevented from being damaged.
Preferably, the thermal expansion coefficient of the green body is: the coefficient of thermal expansion of the first pre-stress layer is =1.2~ 1.5.
Specifically, the green material and the frit of the first pre-stress layer both contain spodumene, the spodumene contains lithium with strong activation capability, the spodumene can be used as a strong fluxing agent in the first pre-stress layer, the viscosity of the formula of the first pre-stress layer is adjusted, the sintering and solid solution temperature is reduced, free silicon in the formula can be promoted to be solid-dissolved, and when the content of the spodumene added is large, crystals with low thermal expansion coefficient can be generated, so that the crystal lattice contraction is caused, the thermal expansion coefficient is reduced, the surface elastic modulus of the first pre-stress layer can be improved, the thermal expansion coefficient of the first pre-stress layer is smaller than that of a green body, and the pre-stress is improved. Moreover, spodumene is alpha-spodumene, belonging to a monoclinic system, can generate crystal form transformation at 850 ℃ in the heating process, and is transformed into beta-spodumene from the alpha-spodumene, the transformation tends to be complete at 1000 ℃, high-temperature metastable state variant gamma-spodumene appears at the time, belonging to a hexagonal system, the gamma-spodumene can be transformed into the beta-spodumene at 1100 ℃, the lattice structure can absorb SiO dissociated from the phase transformation in kaolin along with the change of lattices in the transformation process of different crystal forms2And additionally SiO2Solid solution is formed, and the beta-spodumene solid solution and mullite can be generated, thereby improving the strength of the green body.
Further, frit is introduced into the raw materials of the first pre-stress layer in the technical scheme, so that a cosolvent in a formula of the first pre-stress layer can form a liquid phase at 1000-1100 ℃, and mullite crystals are promoted to be formed, and the mullite crystals have the characteristics of uniform expansion, excellent thermal shock stability, high loading softening point, high hardness, good chemical corrosion resistance and the like, the bending strength of the mullite crystals reaches 570MPa, and the fracture toughness KIC of the mullite crystals reaches 5.7MPa, so that the strength of the pre-stress ceramic can be increased, the toughness and the impact resistance of the pre-stress ceramic can be increased, and cracks or fractures caused by external force on the pre-stress ceramic are avoided. And the frit formula contains a large amount of calcium and magnesium solvents, under the high-temperature condition, anorthite and cordierite crystals are generated in the frit, and both the anorthite and the cordierite crystals have the characteristic of small expansion coefficients, so that the prestress of the prestressed ceramic can be further improved, and the toughness of the first prestress layer can be further increased by the cordierite crystals.
Meanwhile, a large amount of calcite is added into the formula of the raw materials of the first pre-stress layer, the calcite accounts for 30-40% of the total mass of the raw materials of the first pre-stress layer, the large amount of calcite can react with kaolin and quartz at 1000-1100 ℃ to generate anorthite crystals, and the anorthite plays a role in fluxing in the glaze, so that the sintering temperature can be reduced, the sintering time is shortened, mutual diffusion of the components of the raw materials of the blank and the first pre-stress layer is promoted in the sintering process of the calcite, a good blank glaze intermediate layer is formed, the stress caused by the difference of expansion coefficients between the blank and the first pre-stress layer is relieved, the blank and the first pre-stress layer are combined more firmly, and the strength of the pre-stress ceramic is further enhanced. Meanwhile, the liquid phase obtained by melting at 1000-1100 ℃ can enhance the transparency of the prestressed ceramic after being cooled into a glass phase.
Therefore, the first pre-stress layer is arranged on the surface of the pre-stress ceramic, so that the strength and toughness of the ceramic can be enhanced, the strength improvement effect is obvious, the strength of the existing ceramic is generally 43-47 Mpa, the strength of the ceramic prepared by the technical scheme is 69.24-83.72 Mpa, and the strength is improved by 73% compared with the strength of the existing ceramic.
Preferably, the prestressed ceramic of the present invention is a building ceramic, and more preferably, the prestressed ceramic is a tile or a rock plate. Through this technical scheme, can make the ceramic tile realize "frivolousization", when the thickness of ceramic tile is thinner, still have great hardness, easy to assemble and transportation.
Further, the raw materials of the first pre-stress layer comprise, by weight, 30-40 parts of calcite, 5-15 parts of kaolin, 15-20 parts of quartz, 10-20 parts of spodumene, 2-5 parts of zinc oxide, 5-10 parts of barium carbonate and 10-20 parts of frit.
It is worth mentioning that when the content of the frit is more than 20 parts, the content of the quartz is too high, the quartz has a very high melting temperature and is difficult to melt, so that the sintered prestressed ceramic contains a large amount of glass phases, and the strength of the prestressed ceramic is reduced due to too much glass phases; when the amount of the frit is less than 10 parts, the amount of alumina contained therein is too small, which also decreases the strength of the ceramic tile.
Spodumene and calcite in raw materials of the first pre-stress layer are used for adjusting the thermal expansion coefficient of the first pre-stress layer, when the content of spodumene and calcite is too high, the expansion coefficient of the first pre-stress layer is far smaller than that of a blank, the shrinkage of the blank is larger than that of the first pre-stress layer in the cooling process, the first pre-stress layer is compressed by the blank, compressive stress is generated in the first pre-stress layer, and if the compressive stress is larger than the compressive strength of the first pre-stress layer, annular cracks are easily generated in the first pre-stress layer, even the first pre-stress layer is peeled off, so that the flexural strength of the pre-stress ceramic is influenced. Similarly, if the content of spodumene and calcite is too low, network cracks may occur, which may cause the first pre-stress layer to be fractured, and may also affect the rupture strength of the pre-stress ceramic. If the content of quartz in the raw material of the first pre-stress layer is too high, the quartz is difficult to melt due to high melting temperature, so that the pre-stress ceramic contains a large amount of glass phase inside after sintering, and the strength of the pre-stress ceramic is reduced due to too much glass phase.
Furthermore, the frit comprises, by weight, 10-20 parts of kaolin, 10-20 parts of quartz, 5-20 parts of talc, 10-25 parts of dolomite, 5-10 parts of alumina, 1-4 parts of zinc oxide, 10-15 parts of wollastonite and 5-10 parts of spodumene.
It is worth to say that the frit formula contains a certain amount of spodumene, so that the prestress of the prestressed ceramic can be further improved; meanwhile, the frit formula contains a large amount of calcium solvent-wollastonite and magnesium solvent-dolomite, which has the functions of fluxing and reducing the sintering temperature, and the dolomite can promote the dissolution of quartz and the formation of mullite, thereby improving the strength of the prestressed ceramic. In addition, the firing temperature of the prestressed ceramic is 1175-1185 ℃, and alumina cannot be completely melted in the firing process, so that alumina is selected to be added into the clinker, and when the prestressed ceramic is prepared, the clinker is fired at 1520 ℃ to completely melt the alumina.
Further, a second pre-stress layer is arranged on the bottom surface of the pre-stress ceramic, and the raw materials of the second pre-stress layer comprise, by weight, 30-40 parts of calcite, 5-15 parts of kaolin, 15-20 parts of quartz, 10-20 parts of spodumene, 2-5 parts of zinc oxide, 5-10 parts of barium carbonate and 10-20 parts of frit;
the frit comprises the following raw materials of 10-20 parts of kaolin, 10-20 parts of quartz, 5-20 parts of talc, 10-25 parts of dolomite, 5-10 parts of alumina, 1-4 parts of zinc oxide, 10-15 parts of wollastonite and 5-10 parts of spodumene.
It is worth saying that the second pre-stress layer is arranged on the bottom surface of the pre-stress ceramic, so that the strength of the pre-stress ceramic is improved more obviously, and the surface and the bottom surface of the blank are subjected to uniform thermal stress in the blank sintering process. Specifically, in one embodiment of the present invention, the materials and the formulation ratio of each material of the second pre-stress layer and the first pre-stress layer are the same.
Furthermore, the thickness of the first pre-stress layer and the second pre-stress layer is 200-300 mu m.
When the thicknesses of the first pre-stress layer and the second pre-stress layer are too thick, the compressive stress generated on the surface of the blank is too large, and cannot form integral stress balance and energy balance with the internal tensile stress, so that the ceramic material is easily damaged from an internal tensile stress region, and the effect of the pre-stress layer is reduced.
A method for preparing a pre-stressed ceramic, which is used for the pre-stressed ceramic, and comprises the following steps:
(1) sintering the frit;
(2) mixing the fired frit with other raw materials of the pre-stress layer, adding water, ball milling to obtain pre-stress glaze slurry,
(3) applying the pre-stress glaze slurry on the surface of the blank to obtain a first pre-stress layer, or preparing the pre-stress glaze slurry into pre-stress powder by adopting a spray drying tower, applying the pre-stress powder on the surface of the blank, and performing compression molding to obtain the blank and form the first pre-stress layer on the surface of the blank;
(4) and (4) firing the semi-finished ceramic obtained in the step (3) to obtain the prestressed ceramic.
Specifically, in the step (2), the ball-milled pre-stress glaze slurry is screened by a 100-mesh sieve, the prepared pre-stress glaze slurry has a water content of 70% (mass percent) and a specific gravity of 1.5-1.6, and if the fineness of the pre-stress glaze slurry is too large, the suspension property of the pre-stress glaze slurry is increased, the consistency is increased, the fluidity is reduced, the thickness of the pre-stress glaze slurry is easily increased, and the pre-stress glaze slurry is difficult to melt at high temperature, so that the formation of a first pre-stress layer and a second pre-stress layer is influenced, and the strength improvement effect of the pre-stress ceramic is not obvious; if the water content of the pre-stress glaze slurry is too high, the fluidity of the pre-stress glaze slurry is increased, the specific gravity is reduced, and the adhesion is reduced, so that when the pre-stress glaze slurry is applied to the surface of a blank, the pre-stress glaze slurry flows down from the surface of the blank, the first pre-stress layer is too thin, and the strength of the prepared pre-stress ceramic is reduced. If the specific gravity of the prestressed glaze slurry is too high, the first prestressed layer is uneven in thickness and easy to crack and dissolve glaze when glaze spraying is carried out; if the specific gravity of the prestressed glaze slurry is too low, glazing needs to be carried out for a longer time, the operation is troublesome, and the dry glaze phenomenon is easily caused.
Preferably, the water content of the prestressed powder is 6-7%.
It is worth mentioning that in the technical scheme, a glaze spraying mode can be adopted, the prestress glaze slurry is applied to the surface of the blank to form the first prestress layer, or a material distribution mode can be adopted to press and form the prestress powder, and the first prestress layer is formed on the surface of the blank. Specifically, the cloth mode is as follows: firstly, spraying the obtained pre-stressed glaze slurry into pre-stressed powder through a spray drying tower, paving a layer of blank before pressing, then paving a layer of pre-stressed powder, simultaneously pressing and forming the two layers of powder to obtain a blank body, and forming a first pre-stressed layer on the surface of the blank body, wherein the pressure value of a press is 15-25 MPa. By adopting the method of twice material distribution, the green body and the first pre-stress layer are simultaneously pressed and formed, so that the green body and the first pre-stress layer can be prevented from being layered, and the bonding property and the density of the green body and the first pre-stress layer can be improved by simultaneously pressing and forming, thereby laying a certain foundation for improving the strength of the sintered ceramic tile.
Specifically, in the step (2), 40-60 parts of water, 0.1 part of sodium carboxymethylcellulose and 0.3 part of sodium tripolyphosphate are added into a ball mill according to parts by weight for ball milling. The sodium carboxymethyl cellulose and the sodium tripolyphosphate are added in the ball milling process for ball milling, so that the raw materials are mixed more uniformly and have certain cohesive force, and can be better attached to the surface and the bottom surface of the blank.
Preferably, in the step (3), the pre-stress glaze slip is granulated by a spray drying tower and passes through a 250-mesh screen to obtain pre-stress powder.
It is worth to say that after the prestressed powder is applied to the surface and the bottom surface of the blank body, the blank body is pressed and formed in a cloth mode, the operation is simple, processes such as glaze spraying and glaze spraying are not needed, and various ceramics with different colors and patterns can be produced according to different cloth systems.
Specifically, in the step (3), the prestressed powder passes through a 250-mesh screen, the granularity of the prestressed powder is finer through sieving, and the prestressed powder can be pressed more compactly under the action of a press; during sintering, the reaction of the components forms a crystalline phase, so that the strength of the green body is enhanced, namely the strength of the ceramic is enhanced by adopting a physical method and a chemical method simultaneously.
Preferably, in the step (1), the temperature of the frit for the firing treatment is 1520 ℃ and the holding time is 30 min.
In the step (1), the purpose of firing treatment of the frit is that anorthite and cordierite crystals are generated from the frit under a high-temperature condition; the spodumene contains lithium with strong activation capability, the viscosity of the formula is adjusted, the solid solution temperature point is reduced, free silicon in the formula can be promoted to be solid-dissolved, and lattice contraction is caused, so that the surface elastic modulus of the spodumene is improved, and the prestress is improved; because the alumina can not be completely melted at 1175-1185 ℃, the alumina can be completely melted when the frit is subjected to high-temperature firing treatment at 1520 ℃.
Further, in the step (3), applying a pre-stress glaze slurry to the bottom surface of the blank to obtain a second pre-stress layer; or applying the prestressed powder material on the bottom surface of the blank respectively, and performing press forming in a material distribution mode to form a second prestressed layer on the bottom surface of the blank.
The second pre-stress layer is arranged on the bottom surface of the blank body, so that the pre-stress of the pre-stress ceramic can be further improved, and the strength of the pre-stress ceramic is improved.
Preferably, in the step (4), the firing process of the semi-finished ceramic includes heat preservation at 570-575 ℃ for 20min and heat preservation at 1175-1185 ℃ for 1 h.
Specifically, the quartz crystal form is heated to 570-575 ℃ from room temperature, the crystal form transformation of quartz, namely the transformation from beta-quartz to alpha-quartz, can be promoted, at this stage, the quartz crystal form transformation can generate great stress, the volume changes, in order to prevent the product from cracking, the temperature needs to be kept at 570-575 ℃ for 20min to ensure that the quartz can fully realize the crystal form transformation, and preferably, when the temperature is set to 573 ℃, the quartz can fully realize the crystal form transformation. According to the technical scheme, the firing temperature of the prestressed ceramic is 1175-1185 ℃, the prestressed ceramic has high breaking strength at 1175-1185 ℃, the heat is preserved for 1 hour at 1175-1185 ℃, the growth of mullite and anorthite crystals can be promoted, the breaking strength of the prestressed ceramic is further improved, and preferably, the firing temperature is 1180 ℃, and at the moment, the prepared prestressed ceramic has the highest breaking strength. If the firing temperature is higher or lower than 1175-1185 ℃, the flexural strength of the obtained prestressed ceramic is reduced.
The technical scheme of the invention is further illustrated by combining specific examples and comparative examples
Examples 1 to 8
The prestressed ceramic comprises a green body and a first prestressed layer positioned on the surface of the green brick, wherein the raw materials of the first prestressed layer comprise calcite, kaolin, quartz, spodumene, zinc oxide, barium carbonate and frit, and the thickness of the first prestressed layer is 270 mu m. The material formulation of the first pre-stress layer is shown in table 1 below.
According to the weight portion, the frit comprises 15 portions of kaolin, 15 portions of quartz, 12 portions of talc, 17 portions of dolomite, 8 portions of alumina, 3 portions of zinc oxide, 13 portions of wollastonite and 8 portions of spodumene.
The preparation method of the prestressed ceramic comprises the following steps:
(1) sintering the frit at 1520 ℃, and preserving heat for 30 min;
(2) mixing the fired frit with other raw materials of the pre-stress layer, adding water, carrying out ball milling to obtain pre-stress glaze slurry, wherein the pre-stress glaze slurry has the water content of 70% and the specific gravity of 1.5 in percentage by mass;
(3) applying the pre-stress glaze slurry to the surface of the blank to obtain a first pre-stress layer;
(4) and (4) firing the semi-finished ceramic obtained in the step (3), and respectively preserving heat for 20min at 573 ℃ and 1h at 1175-1185 ℃ to obtain the prestressed ceramic. The firing temperature is shown in table 1 below.
Specifically, the raw material formula and the preparation method are adopted to prepare the prestressed ceramic, and the flexural strength of the obtained prestressed ceramic is detected as shown in the following table 1.
TABLE 1 raw material formulation ratio of the first pre-stressed layer, process parameters of the pre-stressed ceramic, and flexural strength of the pre-stressed ceramic in examples 1-8
As can be seen from table 1, when the prestressed ceramic is prepared by using the raw material formulation ratio and the preparation method of the first prestressed layer in examples 1 to 8, the flexural strength of the obtained prestressed ceramic can reach 69.24 to 80.92MPa, while the strength of the existing ceramic is generally 43 to 47MPa, so that the strength of the prestressed ceramic of the technical scheme is greatly improved by 73% compared with the strength of the existing ceramic.
Examples 9 to 10
The formulation of the first pre-stress layer in examples 9-10 is the same as in examples 1-2, except that the method of preparation of examples 9-10 is different from that of examples 1-2, and the method of preparation of examples 9-10 comprises the steps of:
(1) sintering the frit at 1520 ℃, and preserving heat for 30 min;
(2) mixing the fired frit with other raw materials of the pre-stress layer, adding water, ball-milling, and ball-milling to obtain pre-stress glaze slurry;
(3) preparing the prestressed glaze slurry into prestressed powder by adopting a spray drying tower, wherein the fineness of the prestressed powder is 250;
(4) applying the prestressed powder material on the surface of the blank, and performing compression molding in a material distribution mode to obtain a blank body and form a first prestressed layer on the surface of the blank body;
(5) and (4) firing the semi-finished ceramic obtained in the step (4), and respectively preserving heat for 20min at 573 ℃ and 1h at 1180 ℃ to obtain prestressed ceramic and obtain the prestressed ceramic.
Specifically, the flexural strength of the prestressed ceramic prepared by the above raw material formulation and preparation method is 81.34, and the flexural strength of the prestressed ceramic of example 10 is 78.01, as detected, the prestressed powder is applied to the surface of the blank, press-formed in a cloth manner, and a first prestressed layer is formed on the surface of the blank, and the prestressed ceramic prepared by the method also has a higher strength, and the flexural strength of the prestressed ceramic obtained by the preparation method of examples 9 to 10 is slightly increased compared with the flexural strength of the prestressed ceramic prepared by the preparation method of examples 1 to 8.
Examples 11 to 12
The raw material formulation and the preparation method of the first pre-stress layer in example 11 are the same as those in example 1, except that in example 12, a second pre-stress layer is disposed at the bottom of the green body, the formulation ratio of the raw materials in the second pre-stress layer is the same as that of the raw materials in the first pre-stress layer in example 1, and the second pre-stress layer in example 11 is applied to the bottom of the green body in a glaze pouring manner.
The raw material formula and the preparation method of the first pre-stress layer in the embodiment 12 are the same as those in the embodiment 9, except that the second pre-stress layer is arranged at the bottom of the blank in the embodiment 12, the raw material formula in the second pre-stress layer is the same as that in the embodiment 9 in the ratio of the raw material formula of the first pre-stress layer, before compression molding, a layer of pre-stress powder is paved, then a layer of blank is paved, then a layer of pre-stress powder is paved on the blank, and finally compression molding is carried out.
Specifically, the prestressed ceramic prepared by the raw material formulation and the preparation method is tested to obtain the prestressed ceramic with the flexural strength of 82.04 in the example 11 and 83.72 in the example 12, so that the flexural strength of the prestressed ceramic can be further improved in the examples 11 and 12 by arranging the second prestressed layer on the bottom of the green body.
Comparative examples 1 to 8
The preparation methods of the pre-stressed ceramics of comparative examples 1 to 7 were the same as those of example 1 except that the formulation ratios of raw materials and firing temperatures and times of the first pre-stressed layers of comparative examples 1 to 7 were different as shown in table 2 below.
Specifically, the raw material formulation ratio of the first pre-stress layer in table 2 and the preparation method are adopted to prepare the pre-stress ceramic, and the flexural strength of the obtained pre-stress ceramic is detected as shown in table 2 below.
TABLE 2 raw material formulation ratio of the first pre-stressed layer, process parameters of the pre-stressed ceramic, and flexural strength of the pre-stressed ceramic in comparative examples 1 to 7
As can be seen from table 2, as shown in comparative examples 1 to 4, when the contents of calcite, quartz, spodumene and frit are too large or too small, the flexural strength of the prepared prestressed ceramics is greatly reduced; as shown in comparative examples 5-7, when the sintering temperature is too high or too low and the sintering holding time is reduced, the flexural strength of the prepared prestressed ceramic is also reduced; from the test results of comparative example 8, it can be seen that when no frit is added to the formulation, the flexural strength of the prepared prestressed ceramic is greatly reduced to only 43.72 MPa.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (6)
1. The prestressed ceramic is characterized by comprising a blank body and a first prestressed layer positioned on the surface of the blank body, wherein the thermal expansion coefficient of the first prestressed layer is smaller than that of the blank body;
according to parts by weight, the raw materials of the first pre-stress layer comprise 30-40 parts of calcite, 5-15 parts of kaolin, 15-20 parts of quartz, 10-20 parts of spodumene, 2-5 parts of zinc oxide, 5-10 parts of barium carbonate and 10-20 parts of frit;
the frit comprises the following raw materials, by weight, 10-20 parts of kaolin, 10-20 parts of quartz, 5-20 parts of talc, 10-25 parts of dolomite, 5-10 parts of alumina, 1-4 parts of zinc oxide, 10-15 parts of wollastonite and 5-10 parts of spodumene;
a second pre-stress layer is arranged on the bottom surface of the blank body, and the formula ratio of the second pre-stress layer is the same as that of the first pre-stress layer;
the prestressed ceramic is architectural ceramic.
2. The pre-stressed ceramic of claim 1, wherein the first and second pre-stressed layers have a thickness of 200-300 μm.
3. A method for preparing a pre-stressed ceramic, for preparing a pre-stressed ceramic according to claim 1 or 2, comprising the steps of:
(1) sintering the frit;
(2) mixing the fired frit with other raw materials of the pre-stress layer, adding water, ball milling to obtain pre-stress glaze slurry,
(3) applying the pre-stress glaze slip to the surface and the bottom surface of the blank body to form a first pre-stress layer on the surface of the blank body and form a second pre-stress layer on the bottom surface of the blank body, or preparing the pre-stress glaze slip into pre-stress powder by adopting a spray drying tower, applying the pre-stress powder to the surface and the bottom surface of the blank body, performing compression molding to obtain the blank body, forming the first pre-stress layer on the surface of the blank body and forming the second pre-stress layer on the bottom surface of the blank body;
(4) and (4) firing the semi-finished ceramic obtained in the step (3) to obtain the prestressed ceramic.
4. The method for preparing prestressed ceramic as claimed in claim 3, wherein in said step (3), said prestressed glaze slurry is granulated by spray drying tower and passed through 250-mesh screen to obtain prestressed powder.
5. The method of claim 3, wherein in the step (1), the temperature of the frit is 1520 ℃ and the holding time is 30 min.
6. The method for preparing the prestressed ceramic as claimed in claim 3, wherein in the step (4), the firing of the semi-finished ceramic includes maintaining at 570-575 ℃ for 20min and 1175-1185 ℃ for 1 h.
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