CN115340413B - Porous ceramic plate, porous composite ceramic plate and preparation method thereof - Google Patents
Porous ceramic plate, porous composite ceramic plate and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of ceramics, in particular to a porous ceramic plate, a porous composite ceramic plate and a preparation method thereof. The porous ceramic plate comprises a glaze decorative layer and a porous ceramic layer with a multilayer structure; in the porous ceramic layers with the multilayer structure, the porous ceramic layer adjacent to the glaze decoration layer is marked as a layer a, the porous ceramic layer adjacent to the layer a is marked as a layer b, and the pore diameter of the open pore of the layer a is larger than that of the layer b; the firing temperature of the porous ceramic plate is 1000-1100 ℃. The porous composite ceramic plate is obtained by compounding the organic resin material and the inorganic porous ceramic in a micron-sized manner, the defects of high brittleness and poor toughness inherent in the ceramic are overcome under the condition of keeping the decoration of the surface of the ceramic, and the porous ceramic layer with the multilayer structure has higher strength and toughness while considering the permeation efficiency.
Description
Technical Field
The invention relates to the technical field of ceramics, in particular to a porous ceramic plate, a porous composite ceramic plate and a preparation method thereof.
Background
With the development of ceramic industry technology, ceramic large plates have come to bear and are closely related to the fields of furniture, kitchen cabinets, daily necessities and the like, such as full-house customization by using the ceramic large plates. With the requirements of resource saving and environmental protection in manufacturing industry and the pursuit of large ceramics by people, the thickness of the large plate is reduced and the size is increased. The strength and toughness of the large and thin ceramic plate are difficult to meet the requirements of cross-boundary application, and the composite material is an effective method for solving the difficulty. The method for compounding the ceramic and the building material mainly comprises the following steps: 1. in the field of special ceramics, the composite material with high strength and high toughness is applied to the fields of medicine, aviation and the like by using a method of compounding resin and porous ceramic/ceramic-based materials; 2. in the field of artificial marble, there is also a method of preparing a building material by compounding a resin with an inorganic filler.
The above methods for compounding ceramics and building materials have advantages, but they are not effectively applied to the reinforcement and toughening of ceramic plates with decorative/glazed effects. The reinforcing and toughening technology of the method 1 can be applied to obtain a composite material with excellent performance, but experiments show that when the technology is applied to porous ceramic composite reinforcement with decoration/glaze effect, resin permeation is prevented due to decoration/glaze (such as a glaze layer), so that a porous space close to a resin layer part cannot be completely permeated with the resin, structural defects are generated, and the product performance is unstable; application method 2 the composite method of artificial marble is widely applied to the field of building materials, but the strength and toughness of the composite material are not substantially improved compared with the architectural ceramic plate because interconnected grid structures are not formed between the organic resin and the inorganic filler particles.
Disclosure of Invention
Based on the above, the invention aims to overcome the defects of the prior art and provide a porous ceramic plate, a porous composite ceramic plate and a preparation method thereof. Specifically, the porous ceramic plate with the facing and the porous ceramic layer of the multilayer structure is obtained by adopting double-layer or multilayer cloth and adopting a partial sintering mode, and then the porous composite ceramic plate is obtained by adopting a porous ceramic composite resin mode, so that the problems of high brittleness and poor toughness of the ceramic plate in the prior art are solved, and the strength and the toughness of the ceramic plate are obviously improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a porous ceramic plate comprises a glaze decorative layer and a porous ceramic layer with a multi-layer structure; in the porous ceramic layers of the multilayer structure, the porous ceramic layer adjacent to the glaze decoration layer is marked as a layer a, the porous ceramic layer adjacent to the layer a is marked as a layer b, and the pore diameter of the open pore of the layer a is larger than that of the layer b; the firing temperature of the porous ceramic plate is 1000-1100 ℃.
As a preferred embodiment of the porous ceramic plate according to the present invention, the ceramic slurry for forming the layer a has a particle size D50 of 10 to 15 μm, and the ceramic slurry for forming the layer b has a particle size D50 of 6 to 9 μm.
As a preferred embodiment of the porous ceramic plate of the present invention, the glazed decorative layer comprises a glaze layer and a decorative layer, and the glaze layer is adjacent to the porous ceramic layer of the multilayer structure.
As a preferable embodiment of the porous ceramic plate according to the present invention, the thickness of the porous ceramic layer of the multilayer structure is 3 to 12mm.
In a preferred embodiment of the porous ceramic plate according to the present invention, in the porous ceramic layers of the multilayer structure, a single-layer thickness ratio of the porous ceramic layers is 1 to 2.
As a preferable embodiment of the porous ceramic plate of the present invention, the porous ceramic layer of the multilayer structure has an open pore size of 0.5 to 10 μm and a porosity of 20 to 40%. The invention also aims to provide a porous composite ceramic plate, which is obtained by permeating and curing the porous ceramic plate through resin.
The invention also aims to provide a preparation method of the porous composite ceramic plate, which comprises the following steps:
(1) Weighing ceramic raw materials according to a proportion, adding a dispersing agent and a reinforcing agent, then carrying out ball milling to obtain ceramic slurry, and carrying out spray drying to obtain ceramic powder;
(2) Distributing ceramic powder in proportion, pressing and drying to obtain a green body of the porous ceramic layer with a multilayer structure;
(3) Glazing and firing the porous ceramic layer with the multilayer structure to obtain the porous ceramic plate;
(4) And (3) placing the porous ceramic plate in a closed container filled with resin, performing resin infiltration in vacuum, and curing to obtain the porous composite ceramic plate.
As a preferable embodiment of the method for preparing the porous composite ceramic plate according to the present invention, in the step (1), the dispersant is at least one of water glass, sodium tripolyphosphate and sodium metasilicate; the reinforcing agent is at least one of sodium carboxymethylcellulose and sodium lignosulfonate; the ball milling medium is water, and the ball milling time is 4-24 hours.
As a preferable embodiment of the method for preparing the porous composite ceramic plate of the present invention, in the step (3), the firing temperature is 1000 to 1100 ℃ and the firing time is 50 to 120min.
As a preferable embodiment of the method for manufacturing a porous composite ceramic plate according to the present invention, in the step (4), the resin is a thermosetting resin; the infiltration pressure is less than 20Kpa, the infiltration time is 0.5-10h, and the infiltration temperature is 15-30 ℃; the curing temperature is 60-200 deg.C, and the curing time is 30-300min.
Compared with the prior art, the invention has the beneficial effects that:
(1) The porous composite ceramic plate prepared by the invention has high strength and high toughness, and simultaneously has the surface decoration of the ceramic material. The composite of organic resin material and inorganic porous ceramic in micron level has maintained the decoration of ceramic surface, and the gradient structure of porous ceramic has high strength and toughness while maintaining the permeating efficiency. Compared with the conventional building ceramic, the strength (75-135 MPa) of the porous composite ceramic plate prepared by the invention is 1.65-3 times that of the conventional building ceramic (35 MPa), and the toughness is 4.5-9 times that of the conventional building ceramic (100-200 KJ/m) 3 ）；
(2) The porous composite ceramic plate prepared by the invention has light weight (density of 2.1 g/cm) 3 Left and right) and easy processing, can be applied to diversified household and household appliance designs, and has wider application range;
(3) According to the invention, different ball milling times are utilized to obtain D50 ceramic slurry with different particle sizes, incomplete sintering is combined to obtain the porous ceramic layer with the gradient pore structure, no foaming agent is required to be added, the production process is consistent with the conventional ceramic building production process, and industrial production can be carried out only by putting resin permeation equipment.
Drawings
FIG. 1 is a structural view of a porous ceramic plate; wherein, 1 is a gradient pore structure, 2 is a finishing layer, 3 is a glaze layer, a is a porous ceramic layer with D50=10-15 μm, and b is a porous ceramic layer with D50=6-9 μm.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments. In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
A porous ceramic plate comprises a glaze decorative layer and a porous ceramic layer with a multi-layer structure; in the porous ceramic layers of the multilayer structure, the porous ceramic layer adjacent to the glaze decoration layer is marked as a layer a, the porous ceramic layer adjacent to the layer a is marked as a layer b, and the pore diameter of the open pore of the layer a is larger than that of the layer b; the firing temperature of the porous ceramic plate is 1000-1100 ℃.
The porous ceramic plate provided by the invention comprises a glaze decoration layer and a porous ceramic layer with a multilayer structure, and can greatly improve the mechanical property of ceramic under the condition of keeping the decoration of the ceramic surface, wherein the structural diagram of the porous ceramic plate is shown in figure 1.
More specifically, the glazed decorative layer comprises a glaze layer and a finishing layer, and the porous ceramic layer (a layer) is adjacent to the glaze layer.
More specifically, the porous ceramic layer of the multilayer structure is realized by two or more layers of cloth.
Preferably, the ceramic slurry for preparing the layer a has a particle size D50 of 10-15 μm, and the ceramic slurry for preparing the layer b has a particle size D50 of 6-9 μm.
More specifically, after a great deal of experimental research, the inventors of the present application found that the larger the pore size of the open pore of the porous ceramic layer, the higher the permeation efficiency; the smaller the pore size of the open pore is, the better the performance of the composite ceramic tile after complete penetration is, but the part close to the glaze decoration layer is not easy to penetrate. Therefore, the invention adopts the porous ceramic layer with the multilayer structure, and the grain diameter D50 of the ceramic slurry of the layer a is larger than the grain diameter D50 of the ceramic slurry of the layer b, thereby ensuring the permeation efficiency under the condition of virtually complete permeation.
Preferably, the thickness of the porous ceramic layer of the multilayer structure is 3 to 12mm.
Preferably, in the porous ceramic layers of the multilayer structure, the monolayer thickness ratio of the porous ceramic layers is 1-2.
Further, in the practical experiment process, the matching of the D50 layers with different grain diameters is carried out according to the thickness of the porous ceramic layer of the multilayer structure, generally, when the thickness of the porous ceramic layer of the multilayer structure is 6-12mm, the preparation embodiment is preferably a multilayer cloth, and the single-layer thickness of the porous ceramic layer is not less than 2mm.
Preferably, the porous ceramic layer of the multilayer structure has an open pore size of 0.5 to 10 μm and a porosity of 20 to 40%.
The invention also provides a porous composite ceramic plate, which is obtained by permeating and curing the porous ceramic plate with resin.
Specifically, the porous ceramic plate is placed in resin, permeation is carried out in a vacuum closed container, and the porous ceramic after permeation is cured and post-treated to obtain the porous composite ceramic plate.
The invention also provides a preparation method of the porous composite ceramic plate, which comprises the following steps:
(1) Weighing ceramic raw materials according to a proportion, adding a dispersing agent and a reinforcing agent, then carrying out ball milling to obtain ceramic slurry, and carrying out spray drying to obtain ceramic powder;
(2) Distributing ceramic powder in proportion, pressing and drying to obtain a green body of the porous ceramic layer with a multilayer structure;
(3) Glazing and firing the porous ceramic layer with the multilayer structure to obtain the porous ceramic plate;
(4) And (3) placing the porous ceramic plate in a closed container filled with resin, performing resin infiltration in vacuum, and curing to obtain the porous composite ceramic plate.
Preferably, in the step (1), the ceramic raw material is a formula of a conventional ceramic raw material, and may include, by weight, 20 to 40 parts of clay, 10 to 19 parts of bauxite, 0 to 15 parts of diopside, 0 to 10 parts of wollastonite, 15 to 35 parts of potash-sodalite water abrasive, and 1 to 3 parts of talc.
Preferably, in the step (1), the dispersant is at least one of water glass, sodium tripolyphosphate and sodium metasilicate; the reinforcing agent is at least one of sodium carboxymethylcellulose and sodium lignosulfonate; the ball milling medium is water, and the ball milling time is 4-24 hours.
Specifically, the total dosage of the dispersing agent and the reinforcing agent is 0.5-2% of the total weight of the ceramic raw material.
Preferably, in the step (3), the firing temperature is 1000-1100 ℃, and the firing time is 50-120min. More specifically, the firing temperature is 1000 to 1100 ℃ lower than the sintering temperature of the conventional ceramic large plate, which is the incomplete sintering temperature defined when the porous ceramic plate is prepared according to the present invention, and the internal open pores of the porous ceramic layer are obtained by the incomplete sintering (1000 to 1100 ℃). The blank body is not sintered completely to obtain the porosity required by resin permeation, the resin permeation condition is closely related to the size of communicating holes in the ceramic blank body, the larger the size of the communicating holes in the ceramic blank body is, the higher the permeation efficiency is and the higher the strength of the resin after permeation is; the smaller the size of the interconnected pores of the ceramic body is, the lower the permeation efficiency is, but the better the toughness of the resin after permeation is.
Preferably, in the step (4), the resin is a thermosetting resin; the infiltration pressure is less than 20Kpa, the infiltration time is 0.5-10h, and the infiltration temperature is 15-30 ℃; the curing temperature is 60-200 deg.C, and the curing time is 30-300min.
More preferably, the thermosetting resin includes, but is not limited to, epoxy resins and unsaturated polyester resins.
More preferably, the water absorption of the porous composite ceramic plate after curing is less than 0.2%, and preferably, the water absorption is less than 0.1%.
Further, in the step (4), a wax layer or a protective film may be coated according to whether the surface needs subsequent treatment, and after curing, the porous composite ceramic plate may be obtained after removal of the protective film or the wax layer, edging treatment, and the like.
More specifically, the preparation of the porous composite ceramic plate comprises two parts: (1) preparing a porous ceramic plate; and (2) resin infiltration of the porous ceramic.
(1) And preparing the porous ceramic plate: weighing raw materials according to a formula of a conventional ceramic raw material, controlling ball milling variables (the particle size of ceramic slurry is controlled by controlling ball milling time in an actual experimental process by an inventor and is reduced along with the increase of the ball milling time), classifying the slurry according to the particle size distribution of the ceramic slurry after ball milling, respectively drying, distributing (double layers or multiple layers) powder after drying in sequence, pressing into a blank, drying, firing after glazing, obtaining internal openings through incomplete sintering, and finally obtaining the porous ceramic plate with the glazed surface and the porous ceramic layer with the multilayer structure.
(2) Resin infiltration of porous ceramics: and (3) placing the porous ceramic plate in resin, permeating the resin in a vacuum closed container, and curing and post-treating the permeated porous ceramic to obtain the porous composite ceramic plate.
In the test of preparing the porous composite ceramic plate, the blank is found to be incompletely sintered to obtain the porosity required by resin permeation, the resin permeation condition is closely related to the size of the intercommunicating pores in the ceramic blank, the larger the size of the intercommunicating pores in the ceramic blank is, the higher the permeation efficiency is and the higher the strength of the resin after permeation is; the smaller the size of the communicating pores of the ceramic body is, the lower the permeation efficiency is, but the better the toughness after the resin is permeated is. According to mercury intrusion tests for compacting ceramic blanks by powder with different particle size distributions, under the condition of the same water absorption rate, the larger the particle size of the powder is, the larger the size of the intercommunicating pores is, so that the particle size of the powder can be adjusted by ball milling time to control the size of the intercommunicating pores of the ceramic blanks, and the porous ceramic layer with a multilayer structure is obtained by utilizing powder double-layer or multilayer distribution with different ball milling time. In the porous ceramic layer with the multilayer structure, the porous ceramic layer adjacent to the glaze decoration layer is marked as an a layer, the porous ceramic layer adjacent to the a layer is marked as a b layer, the pore diameter of the opening of the a layer is larger than that of the b layer, the porous ceramic plate is prepared under the condition, and then the porous ceramic plate is permeated by resin to obtain the porous composite ceramic plate. In the actual process of manufacturing the glazed composite ceramic board, the glaze is a compact surface, so that resin permeation can only be performed in a single direction, the porous ceramic layer a adjacent to the glazed decorative layer is difficult to permeate, and the pore diameter of the open pore on the layer a is limited to be larger than that of the layer b in order to improve the resin permeability. Because the ceramic powder with different grain diameters is prepared by the same ceramic formula, the difference in firing performance is very small, and the pressed ceramic blank body does not deform due to different water absorption and different thermal expansion coefficients after sintering. In order to explain the technical solution of the present invention more clearly and in detail, the following examples and comparative examples are provided for further explanation.
The materials used in the examples and comparative examples of the present invention were as follows: the resin is E51 resin, the curing agent is methyl hexahydrophthalic anhydride, and the manufacturers are all Hongxiang chemical industry Co.
Example 1
A preparation method of a porous composite ceramic plate comprises the following steps:
(1) Weighing ceramic raw materials according to a proportion, adding a dispersing agent and a reinforcing agent, then carrying out ball milling to obtain ceramic slurry, and carrying out spray drying to obtain ceramic powder;
wherein the ceramic raw material comprises the following components: 35% of clay, 15% of bauxite, 10% of diopside, 5% of wollastonite, 32% of potassium-sodium feldspar water abrasive and 3% of talc; sodium tripolyphosphate accounting for 0.6 percent of the total weight of the raw materials and sodium lignosulfonate accounting for 0.3 percent of the total weight of the raw materials;
the ball milling mode is wet ball milling, the ball milling time is 5 hours, the material A is obtained, the grain diameter D50 of the slurry is 13.65 mu m, and the flow rate is 43S; the moisture content of the powder obtained after the slurry is dried is 6.7 percent; ball-milling for 13 hours to obtain B slurry, wherein the particle size D50 of the slurry is 8.73 microns, and the flow rate is 48S; the water content of the powder obtained after the slurry is dried is 6.5 percent;
(2) Distributing ceramic powder in proportion, pressing and drying to obtain a porous ceramic layer with a gradient pore structure;
wherein, the thickness of the upper layer and the lower layer is as follows: b material =1, double-layer material distribution is carried out, and a 4mm ceramic layer is pressed;
(3) Glazing and firing the porous ceramic layer with the gradient pore structure to obtain a porous ceramic plate comprising a glaze decoration layer and the porous ceramic layer with the gradient pore structure;
wherein the firing temperature is 1060 ℃, the firing time is 106min, and the porous ceramic plate with the glaze surface, the porosity of which is 36 percent, and the flexural strength of which is 17MPa, is obtained;
(4) Placing the porous ceramic plate in a closed container filled with resin, performing resin infiltration under the condition of vacuumizing, and then performing edge grinding treatment to obtain a porous composite ceramic plate;
wherein the mass ratio of the resin monomer to the curing agent is as follows: epoxy resin monomer: curing agent (methylhexahydrophthalic anhydride) =100:80; the infiltration pressure is less than 15Kpa, and the infiltration time is 5h; the curing temperature is 120 ℃, and the curing time is 180min.
Example 2
Example 2 compared to example 1, the thickness ratio of material a and material B in step (2) alone was different, material a: material B =2, and the rest of the preparation method is completely the same as in example 1.
Example 3
Example 3 compared with example 1, only the steps (3) and (4) are different, in the step (3), the firing temperature is 1100 ℃, the firing time is 118min, and the porous ceramic plate with the glaze surface, the porosity of which is 20 percent, and the breaking strength of which is 27MPa, is obtained; in the step (4), the resin permeation time was 9.5 hours, and the remaining preparation method was completely the same as in example 1.
Example 4
Example 4 compared with example 1, the firing temperature is 1040 ℃, the firing time is 93min, the porous ceramic plate with the glaze surface, the porosity of which is 40%, and the breaking strength of which is 14 MPa, is obtained; the resin penetration time was 4h and the rest of the preparation was exactly the same as in example 1.
Example 5
Compared with the example 1, the example 5 has different material distribution modes in the step (2), the thickness of a green body is 9mm, and the thicknesses of an upper layer, a middle layer and a lower layer of ceramic powder are according to the material A: b, material B: the material A = 1; the permeation time in the step (4) is 7 hours; the rest of the preparation method is completely the same as the example 1.
Example 6
Compared with the example 1, the ball milling time is different, the material A is obtained by ball milling for 4 hours, the grain diameter D50 of the slurry is 14.86 μm, and the flow speed is 41S; the water content of the powder obtained after the slurry is dried is 5.6 percent; ball-milling for 12h to obtain B slurry, wherein the particle size D50 of the slurry is 8.93 mu m, and the flow rate is 44S; the moisture content of the powder obtained after the slurry is dried is 6.7 percent; the rest of the preparation method is the same as that of example 1.
Example 7
Compared with the example 1, the ball milling time of the material A is different, the particle size D50 of the slurry is 10.06 mu m, and the flow rate is 49S, wherein the ball milling time of the material A is 10 hours; the water content of the powder obtained after the slurry is dried is 6.3 percent; b, ball milling the material for 23h, wherein the particle size D50 of the slurry is 6.08 mu m, and the flow rate is 52S; the water content of the powder obtained after the slurry is dried is 6.5 percent; the resin penetration time was 8h (the smaller the particle size, the longer the penetration time) and the rest of the preparation was the same as in example 1.
Example 8
Compared with the example 6, the ball milling time is different, the material A is obtained after 3.5h of ball milling, the particle size D50 of the slurry is 15.2 mu m, and the flow rate is 44S; the water content of the powder obtained after the slurry is dried is 6.2 percent; ball-milling for 12h to obtain B slurry, wherein the particle size D50 of the slurry is 8.93 mu m, and the flow rate is 44S; the moisture content of the powder obtained after the slurry is dried is 6.7 percent; the rest of the preparation method is the same as example 6.
Example 9
Compared with the example 7, the ball milling time of the material A is different, the particle size D50 of the slurry is 10.06 mu m, and the flow rate is 49S, wherein the ball milling time of the material A is 10 hours; the moisture content of the powder obtained after the slurry is dried is 6.3 percent; b, ball-milling the material for 25h, wherein the particle size D50 of the slurry is 5.78 mu m, and the flow rate is 47S; the water content of the powder obtained after the slurry is dried is 6.5 percent; the resin penetration time was 8h (the smaller the particle size, the longer the penetration time) and the rest of the preparation was the same as in example 7.
Example 10 this example was compared to example 1 with a green thickness of 3mm, and the rest was the same as example 1.
Example 11
In this example, compared to example 1, the green thickness was 12mm and the ratio of material A: b, material B: a material: material B =1:1, and the permeation time is 10 hours, and the rest is the same as that of the example 1.
Example 12
Compared with the embodiment 5, the embodiment has the advantages that only the material distribution mode in the step (2) is different, the thickness of the green body is 9mm, and the thicknesses of the upper layer, the middle layer and the lower layer of the ceramic powder are as follows: b, material B: material B =1, three-layer material distribution was performed, and a 9mm ceramic layer was pressed.
Example 13
This example compares to example 1 with a green thickness of 3mm and a penetration time of 30 minutes, all the same as example 1.
Example 14
Example 14 compares to example 13 with a green thickness of 3mm and a penetration time of 20 minutes, all the same as example 13.
Comparative example 1
Compared with the example 1, the firing mode in the step (3) is different, the firing temperature is 1180 ℃, and the firing time is 94min; and (5) preparing the ceramic plate containing the glaze decoration layer without the step (4).
Comparative example 2
Comparative example 2 compared with example 1, the material distribution method in step (2) is different, and the ceramic A material in example 1 is subjected to single-layer material distribution and pressed into a 4mm ceramic layer.
Comparative example 3
Comparative example 3 compared with example 1, the material distribution method in step (2) is different, and the ceramic material B in example 1 is subjected to single-layer material distribution and pressed into a 4mm ceramic layer.
Comparative example 4
Compared with the example 1, in the comparative example 4, the sintering temperature in the step (3) is different, the sintering temperature is 1120 ℃, the sintering time is 106min, and the porosity of the porous ceramic blank is 17%.
Comparative example 5
Compared with the example 1, the sintering temperature in the step (3) is different, the sintering temperature is 980 ℃, the sintering time is 106min, the green body is not sintered completely, the strength is too low, and the subsequent resin infiltration process cannot be carried out.
Comparative example 6
Compared with the example 5, the comparative example 6 has the advantages that the material distribution mode is different in the step (2), the thickness of a green body is 9mm, and the thicknesses of an upper layer, a middle layer and a lower layer of ceramic powder are according to the material B: a material: material B =1, three-layer material distribution was performed, and a 9mm ceramic layer was pressed.
Performance testing
Test example 1
And (4) testing standard:
(1) Water absorption and density test methods: according to GB/T3810.3-2016 ceramic tile test method part 3: the method is characterized in that the method comprises the following steps of (1) testing the measurement of water absorption, apparent porosity, apparent relative density and volume weight [ ]: the water absorption is tested by a vacuum method, the brick is placed in a drying oven at the temperature of (110 +/-5) DEG C and dried to constant weight, namely the difference between two continuous masses every 24 hours is less than 0.1%, and m1 is weighed and recorded. Vertically placing the bricks into a vacuum container, enabling the bricks not to contact with each other, vacuumizing to (10 +/-1) KPa, keeping the vacuum for 30min, stopping vacuumizing, adding enough water to cover the bricks and to be higher than the bricks by 5cm, soaking the bricks for 15min, taking out, wiping off surface moisture, immediately weighing and recording m2v, and calculating by a formula EV = (m 2v-m 1)/m 1 multiplied by 100% to obtain the water absorption rate, wherein EV is the water absorption rate measured by m2 v. The volume weight B is represented by dividing the dry weight m1 of the sample by the apparent volume V, and is calculated by the formula B = m 1/V.
(2) The flexural strength test method comprises the following steps: according to GB/T3810.4-2016 ceramic tile test method part 4: the test is carried out according to the determination of modulus of rupture and breaking strength, and the specific test method is as follows: using three-point method, by formula R =3Fl 2 /2bh 2 Calculating to obtain the modulus of rupture, namely the breaking strength, wherein R is the modulus of rupture, F is the breaking load, l 2 Is the span between two support rods, b is the width of the sample, and h is the minimum thickness of the fracture surface of the sample measured along the fracture edge after the test.
(3) The pore diameter testing method comprises the following steps: determination of solid material pore size distribution and porosity fraction 1 according to GBT 21650.1-2008 mercury porosimetry and gas adsorption: mercury intrusion test was performed.
(4) Fracture toughness test method: fracture ofToughness testing method comprises obtaining stress-strain curve of sample by three-point bending measurement method with microcomputer controlled universal material testing machine, and evaluating toughness of composite plate (unit: KJ/m) by calculating area under stress-strain curve (representing energy consumed by material from bearing to breaking) 3 ) The calculation formula is as follows:
wherein, 1013is strain and dimensionless,
is the strain at which the specimen breaks; σ is the stress, in MPa.
The performance test data of the porous ceramics prepared in the examples and the comparative examples of the invention are shown in table 1;
as can be seen from the above table, the porous composite ceramic plates prepared in examples 1 to 7 and examples 10 to 13 of the present invention have high strength and high toughness, and also have the surface decoration property of the ceramic material.
The ball milling time of the A material of example 8 was too short, resulting in a slurry particle diameter D50 of 15.2 μm, which was not within the preferred range, the pore size of the porous ceramic layer was somewhat larger than that of example 6, and the strength and toughness of the porous composite ceramic plate were inferior to those of example 6, but still higher than those of the conventional ceramics. The B-material ball milling time of example 9 was longer than that of example 7, resulting in a slurry particle diameter D50 of 5.78 μm, which was not in the preferred range, and the pore size of the porous ceramic layer was too small, so that the resin penetration was incomplete, and the strength and toughness of the porous composite ceramic plate were also inferior to those of example 7, but still higher than those of the conventional ceramics. (conventional ceramics: according to the regulations of national standard GB/T4100-2015 ceramic bricks, dry-pressed ceramics have the average value of the strength with the water absorption rate less than or equal to 0.5% of more than 35MPa, and the strength with the water absorption rate more than 10% of more than or equal to 15 MPa).
The porous composite ceramic plate prepared in example 14 had a resin penetration time of 20 minutes, which is less than the minimum value of the preferred range of resin penetration times mentioned in the present invention of 30 minutes, resulting in the porous composite ceramic plate prepared in example 14 having inferior strength and toughness to those of example 13, but still higher strength and toughness than those of conventional ceramics.
Comparative example 1 is a ceramic plate without resin infiltration, and the strength and toughness are significantly lower than those of example 1; the results of comparative examples 2-3 compared to example 1 show that the strength and toughness of the ceramics prepared in the single-layer cloth mode are obviously reduced.
The porous composite ceramic plates prepared in comparative examples 4 to 5 were fired at temperatures outside the firing temperature range (1000 to 1100 ℃) of the porous composite ceramic plates according to the present invention, resulting in porosity of the porous composite ceramic plates of comparative examples 4 and 5 outside the protection range of the present invention, increased water absorption, and significantly decreased strength and toughness. The results of comparative example 6 compared with example 5 show that the porous ceramic layer with a multilayer structure provided by the invention is a porous ceramic layer with a large particle size adjacent to the overglaze layer, so that the permeation efficiency can be improved, and the mechanical properties of the ceramic can be greatly improved under the condition of maintaining the decorative property of the surface of the ceramic. Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The porous ceramic plate is characterized by comprising a glaze decorative layer and a porous ceramic layer with a multilayer structure; in the porous ceramic layers of the multilayer structure, the porous ceramic layer adjacent to the glaze decoration layer is marked as a layer a, the porous ceramic layer adjacent to the layer a is marked as a layer b, and the pore diameter of the open pore of the layer a is larger than that of the layer b; the grain diameter D50 of the ceramic slurry for preparing the layer a is 10-15 mu m, and the grain diameter D50 of the ceramic slurry for preparing the layer b is 6-9 mu m; the porosity of the porous ceramic layer of the multilayer structure is 20-40%, and the firing temperature of the porous ceramic plate is 1000-1100 ℃.
2. The porous ceramic plate according to claim 1, wherein the thickness of the porous ceramic layer of the multi-layered structure is 3 to 12mm.
3. The porous ceramic plate according to claim 2, wherein the ratio of the individual layer thicknesses of the porous ceramic layers in the multilayer structure is 1-2.
4. The porous ceramic plate according to any one of claims 1 to 3, wherein the porous ceramic layers of the multilayer structure have an open pore size of 0.5 to 10 μm.
5. A composite ceramic plate, which is obtained by impregnating the porous ceramic plate according to any one of claims 1 to 4 with a resin and curing the resin.
6. A method for preparing a composite ceramic plate, which is characterized in that the composite ceramic plate is the composite ceramic plate of claim 5, and the method comprises the following steps:
(1) Weighing ceramic raw materials according to a proportion, adding a dispersing agent and a reinforcing agent, then carrying out ball milling to obtain ceramic slurry, and carrying out spray drying to obtain ceramic powder;
(2) Distributing ceramic powder in proportion, pressing and drying to obtain a green body of the porous ceramic layer with a multilayer structure;
(3) Glazing and firing the green body of the porous ceramic layer with the multilayer structure to obtain the porous ceramic plate material as claimed in any one of claims 1 to 4;
(4) And (3) placing the porous ceramic plate in a closed container filled with resin, performing resin infiltration in vacuum, and curing to obtain the composite ceramic plate.
7. The method according to claim 6, wherein in the step (1), the dispersant is at least one of water glass, sodium tripolyphosphate and sodium metasilicate; the reinforcing agent is at least one of sodium carboxymethylcellulose and sodium lignosulfonate; the ball milling medium is water, and the ball milling time is 4-24 hours.
8. The method according to claim 6, wherein in the step (3), the firing temperature is 1000 to 1100 ℃ and the firing time is 50 to 120min.
9. The method according to claim 6, wherein in the step (4), the resin is a thermosetting resin; the infiltration pressure is less than 20KPa, the infiltration time is 0.5-10h, and the infiltration temperature is 15-30 ℃; the curing temperature is 60-200 deg.C, and the curing time is 30-300min.
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