A porous functional ceramic material with high plasticity and a preparation method and application thereof

Abstract

The application discloses a porous functional ceramic material with high plasticity and a preparation method and application thereof, and belongs to the technical field of ceramic preparation. The ceramic material is prepared by firing a ceramic slurry. The ceramic slurry comprises, in parts by mass, 2090-2190 parts of red clay, 1100-1200 parts of feldspar powder, 2580-2680 parts of kaolin, 1000-1100 parts of white sand, 1300-1400 parts of flower soil, 540-640 parts of red clay, 10-15 parts of manganese dioxide, 100-140 parts of a plasticizer, and 3600-4000 parts of water. Modified bentonite is used as the plasticizer of the ceramic. The water-retention capacity of bentonite is enhanced by modifying the water-absorbing organic polymer structure on the surface of the bentonite, and the water evaporation of the bentonite is prevented from being too fast, so that the uneven shrinkage of the green body is avoided. The hydroxyl and carboxyl structures on the surface can enhance the combination between the soil bodies, and can effectively prevent cracking. The ceramic with a porous structure is obtained by releasing a certain gas during calcination of the organic polymer structure. The surface of the bentonite is modified by using organic molecules with different thermal stabilities, so that the gas is slowly released, and thus the ceramic material with uniform pores is obtained.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of ceramic preparation, and particularly relates to a porous functional ceramic material with high plasticity and a preparation method and application thereof. BACKGROUND

[0002] Ceramic products are made of clay as raw material and are fired at high temperature, and have both practicality and artistry. Ceramic clay body raw material is an essential raw material in ceramic production, and the plasticity of ceramic raw material is a key technology in ceramic production, and the plasticity directly affects the subsequent production, such as forming, slip casting, sintering and product production quality. Plasticizers are usually a class of chemicals used to increase the flexibility, ductility and processability of materials.

[0003] Bentonite is a natural clay mineral with montmorillonite as the main component, and has the following properties: (1) high water absorption, bentonite can absorb water and expand to form a colloidal structure; (2) high plasticity, good flexibility and viscosity when containing water, and hardening after drying; (3) suspensibility and lubricity, which can increase the fluidity of the system after dispersion in water. Bentonite is often added to the formula of pottery clay or porcelain clay, especially the body of porcelain and pottery, and its main function is to enhance the plasticity, making the clay more easily shaped and reducing cracking. However, bentonite also has the following shortcomings: after swelling by absorbing water, it is prone to cracking during the drying stage, and the main reason for cracking is that the evaporation rate inside and outside the soil body is different, resulting in a water gradient in the soil body, and the greater the water gradient, the more uneven the shrinkage of the body, and when the shrinkage force of the soil body exceeds its tensile strength, the soil body will crack. Organic plasticizers, such as carboxymethyl cellulose and polyvinyl alcohol, have good plasticity and adhesion, and can improve the plasticity of pottery clay, making it easier to shape. However, the organic molecules may decompose too early during calcination, causing gas to escape too quickly, and the gas cannot be discharged in time, which may form cracks in the body, affecting the quality of the finished product. SUMMARY

[0004] In order to overcome the shortcomings of the prior art, the application provides a porous functional ceramic material with high plasticity, which uses modified bentonite as a plasticizer for ceramics, and modifies the water-absorbing organic polymer structure on the surface of bentonite to enhance its water retention capacity and prevent rapid evaporation of water, which leads to uneven shrinkage of the body, and the hydroxyl and carboxyl structures on the surface can enhance the bonding between the soil bodies, effectively preventing cracking; the organic polymer structure releases a certain amount of gas during calcination to obtain a porous ceramic; and different heat-resistant organic molecular structures are used to modify the surface of bentonite, so that the gas is released slowly, thereby obtaining a ceramic material with uniform pores.

[0005] The technical scheme for achieving the object of the present application is as follows: a porous functional ceramic material with high plasticity, which is prepared by firing a ceramic slurry, the ceramic slurry comprising, in parts by mass, 2090-2190 parts of red clay, 1100-1200 parts of feldspar powder, 2580-2680 parts of kaolin, 1000-1100 parts of white sand, 1300-1400 parts of flower soil, 540-640 parts of red clay, 10-15 parts of manganese dioxide, 100-140 parts of plasticizer, and 3600-4000 parts of water; and the plasticizer is prepared by the following method.

[0006] S1. Purification of bentonite: wet purification, drying, crushing, and screening;

[0007] S2. Silane-modified bentonite: modification of bentonite with an epoxy-based silane coupling agent;

[0008] S3. Initiator-modified bentonite: reaction of the epoxy group in the silane-modified bentonite with the amino group in the initiator to introduce an initiating group;

[0009] S4. Polymer modification: 3-6 parts of tert-butyl acrylate monomer, 24-48 parts of initiator-modified bentonite, 0.004-0.008 parts of cuprous bromide, and 40-50 parts of anhydrous N,N-dimethylformamide are added to a reaction kettle under an inert gas atmosphere, freeze-thaw degassing is performed, then 0.04-0.08 parts of N,N,N',N'',N''-pentamethyldiethylenetriamine is added, stirring is performed at 50-80°C for 10-24 h, 3-6 parts of hydroxy acrylate monomer and 0.004-0.008 parts of cuprous bromide are added for continued stirring for 10-24 h, oxygen is introduced to terminate the reaction after the reaction is completed, the reaction liquid is centrifuged to separate out the precipitate, which is washed with deionized water and alcohol at least twice, the precipitate is dispersed in a mixed solvent of dichloromethane and trifluoroacetic acid, stirring is performed at room temperature for 16-24 h, after the organic solvent is removed, the pH is adjusted to 9-11, the precipitate is centrifuged and separated out, and is washed and dried to obtain the polymer-modified bentonite;

[0010] The initiator has the following molecular structure:

[0011] .

[0012] Preferably, the purification step in step S1 is as follows:

[0013] The bentonite and water are stirred at a mass ratio of 1:(5-7) for 1-2 hours, and the lower layer of sand is removed after standing for 16-24 hours; 10-30 minutes of continuous stirring is followed by adding water to prepare a feed liquid with a mass ratio of bentonite ore powder to water of 1:(9-12), stirring for 20-30 minutes, and standing for 5-6 hours to recover the supernatant, taking the upper layer of fine soil from the sediment, discarding the lower layer of sand, and filtering the upper layer of fine soil, which is then dried in an electric thermostatic drying oven, crushed, and sieved using a 200-mesh screen.

[0014] Preferably, the detailed steps of the silane-modified bentonite in step S2 are as follows:

[0015] The bentonite obtained in step S1 is dispersed in a mixed solvent of alcohol and water, and then a silane coupling agent containing an epoxy group is added, and stirring is performed at a temperature of 40-60 ℃ for 8-12 hours; the precipitate is separated by centrifugation, and the silane-modified bentonite is obtained by washing and drying; the mass ratio of the bentonite, the silane coupling agent, and the mixed solvent is (4-6):(0.5-1):(30-50); the volume ratio of the alcohol to water is (1-10):1; the alcohol is at least one of methanol and ethanol; and the silane coupling agent containing an epoxy group is at least one of 3-glycidyloxypropyl triethoxysilane and 3-glycidyloxypropyl trimethoxysilane.

[0016] Preferably, the detailed steps of the initiator-modified bentonite in step S3 are as follows:

[0017] The 4-6 parts of the silane-modified bentonite obtained in step S2 are dispersed in 30-50 parts of dry tetrahydrofuran, and 0.5-1 part of an initiator is added under a nitrogen atmosphere; the temperature is raised to 50-60 ℃, and the reaction is performed for 10-16 hours; the precipitate is separated by centrifugation, and the initiator-modified bentonite is obtained by washing and vacuum drying.

[0018] Preferably, in step S4, the tert-butyl acrylate monomer is at least one of tert-butyl acrylate and tert-butyl methacrylate; the hydroxyethyl acrylate monomer is at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; and the pH adjustment is performed using an aqueous solution of one or more of sodium hydroxide, sodium carbonate, and sodium bicarbonate.

[0019] Preferably, the bentonite is at least one of sodium-based bentonite and calcium-based bentonite.

[0020] A method for preparing a porous functional ceramic material with high plasticity, comprising the following steps:

[0021] mud preparation, molding, water application, biscuit firing, glazing, kiln glaze firing, and colored porcelain;

[0022] The mud making is that: the ceramic slurry is ground into mixed mud by a ball mill, the particulate matter is filtered by a vibrating filter screen device, the excess moisture is squeezed out by a mud pressing bed equipment, finally, the air in the mud is further discharged by a mud refining machine, and finally, a mud strip is formed;

[0023] The forming is selected from rolling forming or slip casting forming, and a soil culture is obtained.

[0024] The water application is that the soil culture is polished clean by using a water-soaked sponge to polish the burrs and particles of the soil culture;

[0025] The final temperature of the biscuit firing is 600-1000 DEG C, and the steps are that the temperature is increased from room temperature to 200 DEG C at a rate of 50-100 DEG C / h, the temperature is increased from 200 DEG C to 600 DEG C at a rate of 30-60 DEG C / h, and the temperature is increased from 600 DEG C to 1000 DEG C at a rate of 90-110 DEG C / h; after the temperature is increased to the final temperature, the temperature is kept for 1-2 h;

[0026] The final temperature of the kiln glaze firing is 900-1200 DEG C, and the steps are that the temperature is increased from room temperature to 500 DEG C at a rate of 100-150 DEG C / h, the temperature is increased from 500 DEG C to 900 DEG C at a rate of 50-100 DEG C / h, and the temperature is increased from 900 DEG C to 1200 DEG C at a rate of 50-80 DEG C / h; after the temperature is increased to the final temperature, the temperature is kept for 1-2 h; the temperature is decreased at a rate of 50-100 DEG C / h, and after the temperature is decreased to 600 DEG C, the temperature is naturally cooled;

[0027] The colored porcelain is at least one of a powder spraying process or a color drawing process; and the ceramic material is the ceramic material described above.

[0028] The application also protects the application of the obtained ceramic material in a ceramic flowerpot, which is prepared by the method of the porous functional ceramic material with high plasticity, and the flowerpot soil culture is obtained by using a flowerpot-shaped rolling forming or slip casting forming mold. Advantages

[0029] The present application comprises the following beneficial effects: 1, the polymer modified bentonite is used as the plasticizer of ceramic slurry, and the ceramic slurry has good plasticity. The water absorption organic polymer structure is modified on the surface layer of the bentonite, the water evaporation is too fast in the drying stage, the uneven shrinkage of the body is caused, the hydrogen bond structure is enhanced, the combination between the soil bodies is further prevented, the cracking is prevented, the organic polymer is the block copolymer, the inner layer close to the bentonite is the carboxylate structure, the outer layer is the hydroxyl ester structure, the thermal stability is different, the thermal stability of the inner layer is higher than that of the outer layer, the decomposition temperature intervals of the outer layer and the inner layer are different in the calcination, the gas is slowly released, the cracks caused by the too fast gas escape are prevented, and the ceramic material with uniform pores is obtained; the carboxylate of the inner layer and the hydroxyl of the outer layer are both hydrophilic groups, the organic polymer is the dendritic structure, compared with the linear structure, the water retention is more excellent, and the dispersion is uniform, the lubricating performance is more excellent; the modified bentonite can form a more uniform hydration film after water absorption, the flexibility of the mud is enhanced, and the excellent plasticizing effect is achieved.

[0030] The organic polymer structure releases certain gas in the calcination process, and the ceramic flowerpot with a porous structure is obtained. The porous structure makes the flowerpot have good air permeability, is conducive to the discharge and evaporation of excess water in the flowerpot, and the porous ceramic has certain moisture absorption and moisture retention. When the air humidity is relatively high, the flowerpot can absorb the water in the air and store it, and when the air is dry, the stored water can be released, thereby adjusting the soil humidity in the flowerpot and creating a relatively stable humidity environment for plant growth. The porous structure can bring a unique appearance effect to the ceramic flowerpot, increase the aesthetic and artistic feeling thereof, reduce the weight of the flowerpot, and make the soil environment in the flowerpot more healthy, which is not conducive to the breeding and reproduction of harmful microorganisms.

[0031] The organic molecular structure with different thermal stabilities is used for modifying the surface of the bentonite, gas is slowly released, and the ceramic flowerpot with uniform pores is obtained. The uniform pores can make the soil in each part of the flowerpot and the outside air fully and evenly exchange gas, and can make the structure of the flowerpot more stable, so that the performance of each part when bearing external force tends to be consistent, thereby making the overall strength of the flowerpot more uniform and reducing the risk of cracks or breakage. In the firing process, the uniform pores are conducive to uniform heat transfer, so that each part of the flowerpot is uniformly heated, thereby ensuring that the color of the final product is uniform, reducing the color difference caused by local overheating or overcooling, and improving the appearance quality and commodity value of the flowerpot. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 It is a schematic diagram of the plasticizer synthesis, structure and mechanism of the present application;

[0033] Figure 2 It is an XRD spectrum of the calcium-based bentonite and the plasticizer 3 of the present application. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0035] Unless otherwise specified, the experimental methods used in the embodiments are conventional methods, and the materials and reagents used are commercially available unless otherwise specified.

[0036] The raw materials and equipment used in the embodiments and comparative examples are described below:

[0037] Red clay: Dezhou Mineral Products Processing Plant, Lingshou County;

[0038] Feldspar powder: Lingshou County Dezhou Mineral Products Processing Plant;

[0039] Kaolin: Lingshou County Dezhou Mineral Products Processing Plant;

[0040] White sand: Dezhou Mineral Products Processing Plant, Lingshou County;

[0041] Potting soil: Dezhou Mineral Products Processing Plant, Lingshou County;

[0042] Red clay: Dezhou Mineral Products Processing Plant, Lingshou County;

[0043] Manganese dioxide: Nantong Runfeng Petrochemical Co., Ltd.;

[0044] Calcium-based bentonite: Liangyou Bentonite Processing Plant;

[0045] Glycidyl etheroxypropyltriethoxysilane: Guangdong Wengjiang Chemical Reagent Co., Ltd.;

[0046] tert-butyl acrylate: Shanghai Maclean;

[0047] Hydroxyethyl acrylate: Shanghai Maclean;

[0048] [2-Hydroxy-1,1-bis(hydroxymethyl)-ethyl]carbamate tert-butyl ester: Bide Pharmaceuticals;

[0049] Bromoisobutyryl bromide: Shanghai Maclean;

[0050] (tert-butyloxycarbonyl)ethanolamine: Shanghai Maclean;

[0051] Poly(2-hydroxyethyl methacrylate): average molecular weight 20,000, Guangdong Wengjiang Chemical Reagent;

[0052] Poly sodium methacrylate: obtained by treating poly methacrylic acid (Shaanxi Lide Medicine Chemical) with an average molecular weight of 20000 with sodium hydroxide;

[0053] Initiator 1

[0054] 1 eq of N-[2-hydroxy-1,1-bis(hydroxymethyl)-ethyl] tert-butyl carbamate was cooled with an ice water bath together with 5 eq of triethylamine, and 3.2 eq of 2-bromoisobutyryl bromide was added dropwise, the mixture was stirred at low temperature for 3 h, 1.5 eq of 2-bromoisobutyryl bromide was added dropwise, and stirring was continued for 1 h, the reaction was filtered, the precipitate was washed with a small amount of dichloromethane, the combined organic phases were washed with saturated sodium bicarbonate, and then dried with sodium sulfate, filtered and concentrated to obtain a residue, which was recrystallized in n-hexane after column chromatography, filtered and dried to obtain product 1;

[0055] 1 eq of product 1 was dispersed in 15 eq of dichloromethane solvent, an equal volume of trifluoroacetic acid solution was added, and stirring was carried out at room temperature for 2 h, 20 eq of dichloromethane was added, the organic phase was washed with saturated sodium bicarbonate, the combined organic phases were removed, and initiator 1 was dried in vacuum.

[0056] Initiator 2

[0057] Compared with the preparation method of initiator 1, the difference is that N-[2-hydroxy-1,1-bis(hydroxymethyl)-ethyl] tert-butyl carbamate is replaced by N-(tert-butoxycarbonyl) ethanolamine.

[0058] Plasticizer 1

[0059] S1. Purification of bentonite: bentonite ore powder and water were stirred at a mass ratio of 1:6 for 1 h, and the lower layer of sand was removed after standing for 18 h; after continuing to stir for 20 min, water was added to prepare a feed liquid with a mass ratio of bentonite ore powder to water of 1:10, and stirring was carried out for 30 min, and the supernatant was recovered after standing for 6 h, the upper layer of fine soil was taken out from the sediment, and the lower layer of sand was discarded, the upper layer of fine soil was filtered, dried in an electric heating constant temperature drying oven, crushed, and sieved with a 200 mesh screen;

[0060] S2. Silane modified bentonite: 5 parts of bentonite obtained in step S1 were dispersed in a mixed solvent of 30 parts of methanol and 10 parts of water, then 0.6 parts of 3-glycidyl ether oxypropyl triethoxysilane was added, and stirring was carried out at a temperature of 60 ℃ for 10 h, the precipitate was separated by centrifugation, washed and dried to obtain silane modified bentonite;

[0061] S3. Initiator modified bentonite: 5 parts of silane modified bentonite obtained in step S2 was added into 40 parts of dry tetrahydrofuran, 1 part of initiator 1 was added under nitrogen atmosphere, the temperature was raised to 60 ℃, and the reaction was carried out for 14 h. The precipitate was separated by centrifugation, washed, and vacuum dried to obtain the initiator modified bentonite.

[0062] S4. Polymer modification: 3 parts of tert-butyl acrylate monomer, 24 parts of initiator modified bentonite, 0.006 parts of cuprous bromide, and 50 parts of anhydrous N,N-dimethylformamide were added into a reaction kettle under an inert gas atmosphere, degassed by freeze-thaw, and then 0.06 parts of N,N,N',N'',N''-pentamethyldiethylenetriamine was added. The mixture was stirred at 80 ℃ for 24 h. Then 3 parts of hydroxy acrylate monomer and 0.06 parts of cuprous bromide were added, and the stirring was continued for another 24 h. After the reaction was completed, the reaction was terminated by introducing oxygen. The precipitate was separated by centrifugation, washed with deionized water and alcohol twice, dispersed in a mixed solvent of dichloromethane and trifluoroacetic acid, stirred at room temperature for 22 h, and then the organic solvent was removed. A saturated sodium chloride solution was added to prepare a 1 mol / L sodium hydroxide saturated sodium chloride solution. The pH was adjusted to 10, the precipitate was separated by centrifugation, washed, and dried to obtain the polymer modified bentonite.

[0063] Plasticizer 2

[0064] Compared with the preparation method of plasticizer 1, the difference lies in that in step S4, “3 parts of tert-butyl acrylate monomer, 24 parts of initiator modified bentonite,... 3 parts of hydroxy acrylate monomer” is replaced by “6 parts of tert-butyl acrylate monomer, 48 parts of initiator modified bentonite,... 6 parts of hydroxy acrylate monomer”.

[0065] Plasticizer 3

[0066] Compared with the preparation method of plasticizer 1, the difference lies in that in step S4, “24 parts of initiator modified bentonite” is replaced by “30 parts of initiator modified bentonite”.

[0067] Plasticizer 4

[0068] Compared with the preparation method of plasticizer 3, the difference lies in that in step S4, “3 parts of tert-butyl acrylate monomer,... 3 parts of hydroxy acrylate monomer” is replaced by “5 parts of tert-butyl acrylate monomer,... 5 parts of hydroxy acrylate monomer”.

[0069] Plasticizer 5

[0070] Compared with the preparation method of plasticizer 3, the difference lies in that the "3 parts of t-butyl acrylate monomer" in step S4 is replaced by "3 parts of hydroxy acrylate monomer".

[0071] Plasticizer 6

[0072] Compared with the preparation method of plasticizer 3, the difference lies in that the "3 parts of hydroxy acrylate monomer" in step S4 is replaced by "3 parts of t-butyl acrylate monomer".

[0073] Plasticizer 7

[0074] Compared with the preparation method of plasticizer 3, the difference lies in that in step S4, 3 parts of hydroxy acrylate monomer are added at the beginning together with 3 parts of t-butyl acrylate monomer, and the rest of the operation remains unchanged.

[0075] Plasticizer 8

[0076] Compared with the preparation method of plasticizer 3, the difference lies in that in step S3, 1 part of initiator 1 is replaced by initiator 2.

[0077] Plasticizer 9

[0078] Compared with the preparation method of plasticizer 3, the difference lies in that only steps S1 and S2 are performed.

[0079] Plasticizer 10

[0080] Compared with the preparation method of plasticizer 3, the difference lies in that only step S1 is performed.

[0081] The following are the test methods related to performance parameters in the present application:

[0082] Water retention performance: prepare a ring knife sample with a diameter of 60 mm and a height of 40 mm, place it in a PVC pipe cap with good heat insulation effect, only the upper surface is in the air, then place it in an oven at the same time, evaporate and dry at a temperature, take out the sample randomly every 6 h, take an appropriate amount of soil body on the upper layer and the middle part for determination of water content at 0 h, 6 h and 12 h, and the water retention performance is obtained by the following formula:

[0083] Water retention performance Water retention performance , wherein the water content n is the water content evaporated and dried for 6 h and 12 h, and the water content 0 is the initial water content.

[0084] Thermal stability test: using a thermal gravimetric analyzer, the same molecular weight of poly(2-hydroxyethyl methacrylate) and poly(sodium methacrylate) is heated from room temperature to 700℃ under air atmosphere, and the heating rate is 10 ℃ / min.

[0085] Porosity test: after the soil culture is burned, the sample to be tested is cleaned by ultrasonic for 0.5 h, the sample is taken out and dried at 110 DEG C until the weight is constant, the dry weight of the sample is weighed by an electronic balance, the sample is completely immersed in the immersion liquid under the condition that the vacuum degree is less than 20 Torr, the sample is hung on the balance hook immersed in the immersion liquid, and the mass M2 of the sample in the immersion liquid is measured, that is, the apparent mass M2 of the sample; distilled water is used as the immersion liquid, and the density D L ; the bulk density D b (g / cm 3 ) is calculated according to formula 1:

[0086]

[0087] Pore size distribution test: the sample is subjected to mercury injection test, the slurry is prepared according to the formula, and then the slurry is treated, and then the slurry is injected into a cubic grid with a side length of 1 cm to obtain the soil culture, the sample is taken out after the soil culture is burned, and the porosity of the sample is tested by using a mercury porosimeter.

[0088] A method for preparing a porous functional ceramic material with high plasticity, comprising the following steps:

[0089] The ceramic slurry is ground into mixed soil by a ball mill, the particulate matter is filtered by a vibrating filter screen device, the excess water is squeezed out by a mud pressing bed equipment, and finally the air in the soil is further discharged by adding a mud refining machine to form a mud strip, the slurry is formed by grouting, the burrs and particles of the soil culture are polished clean by using a water-soaked sponge, and the soil culture is burned, the room temperature is increased to 200 DEG C at a rate of 60 DEG C / h; 200-600 DEG C, the rate of temperature rise is 45 DEG C / h; 600-900 DEG C, the rate of temperature rise is 100 DEG C / h; after the temperature is increased to the final temperature of 900 DEG C, the temperature is kept for 1 h; after glazing, the kiln glaze is fired, the room temperature is increased to 500 DEG C at a rate of 120 DEG C / h; 500-900 DEG C, the rate of temperature rise is 70 DEG C / h; 900-1100 DEG C, the rate of temperature rise is 70 DEG C / h; after the temperature is increased to the final temperature of 1100 DEG C, the temperature is kept for 2 h; the temperature is decreased to 600 DEG C at a rate of 80 DEG C / h, and then the temperature is naturally cooled down; the colored porcelain operation is performed by using the color drawing process.

[0090] It can be seen from Figure 2 that the interlayer spacing is reduced after modification, which is because the ionic radius of Na + is smaller than that of Ca 2+ , the hydrogen bond between the carboxyl and hydroxyl groups in the polymer and the groups in the interlayer of bentonite occurs, so that the structure of the plasticizer is more compact and regular, and the interlayer spacing is reduced.

[0091] Table 1 thermal stability test

[0092]

[0093] Table 2 Ceramic slurry formulation of Examples 1-6 (kg)

[0094]

[0095] Table 3 Ceramic slurry formulation of Comparative Examples 1-6 (kg)

[0096]

[0097] Table 4 Performance test of materials prepared by the formulation of Examples and Comparative Examples

[0098]

[0099] From the data in Table 4, it can be seen that the plasticizer prepared by the present application can obtain ceramic material with uniform water evaporation and uniform porosity distribution of the green body within a reasonable range, and by adjusting the content of volatile organic matter, the porosity of the flowerpot is greater than 10%, which meets the definition of porous ceramic.

[0100] From the data of Examples 1-6, the water retention performance of the surface layer and the interior during drying after ceramic forming is relatively small, which has good water retention performance, and can effectively prevent cracks caused by uneven shrinkage of the green body during the drying stage; during calcination of the obtained green body, the gas is uniformly discharged, and the obtained pore size distribution is uniform. From the data of Comparative Examples 1-2, the obtained plasticizers 5-6 by using sodium acrylate or hydroxyethyl acrylate alone to modify the ceramic surface have relatively small water retention performance compared with the examples, but the porosity after biscuiting is low and the pore size distribution is wide, which is because the gas escapes too fast, resulting in the combination of some pores to form larger pores. From the data of Comparative Example 3, the performance of plasticizer 7 using an alternating copolymer to modify bentonite is not as good as that of the block copolymer used in plasticizers 1-4 of the examples, the block copolymer has poor thermal stability of polyhydroxyacrylate outside, which is preferentially decomposed, and the internal thermal stability of sodium acrylate is good, which is decomposed, which can achieve a gradual decomposition process. From the data of Comparative Example 4, the effect of plasticizer 8 using a linear polymer to modify bentonite is not as good as that of the bentonite modified with a dendritic structure, and the water retention and pore size distribution effects are not as good as those of the examples. From the data of Comparative Examples 5-6, the effects of plasticizers 9 and 10 using bentonite modified by silane or not are not as good as those of plasticizers 1-4 used in Examples 1-6.

[0101] The preferred embodiments of the application disclosed above are only to facilitate the elucidation of the application. The preferred embodiments do not describe all the details of the application and limit the application to the specific embodiments described. Obviously, many modifications and variations can be made in light of the teachings above. The description is chosen and described in order to best explain the principles of the application and its practical application to thereby enable others skilled in the art to best utilize the application and get the best results from the application. The application is only limited by the claims and their full scope and equivalents.

Claims

1. A ceramic material having a high plasticity, characterized in that, The ceramic material is fired after treatment of a ceramic slurry, the ceramic slurry comprises, in parts by mass, 2090-2190 parts of red clay, 1100-1200 parts of feldspar powder, 2580-2680 parts of kaolin, 1000-1100 parts of white sand, 1300-1400 parts of flower soil, 540-640 parts of red clay, 10-15 parts of manganese dioxide, 100-140 parts of plasticizer, and 3600-4000 parts of water; the plasticizer is prepared by the following method: S1. Purification of bentonite: wet purification, drying, crushing, and screening; S2. Silane modified bentonite: bentonite is modified by using an epoxy-based silane coupling agent; S3. Initiator modified bentonite: the epoxy group in 4-6 parts of the silane modified bentonite reacts with the amino group in 0.5-1 part of the initiator to introduce an initiating group; S4. Polymer modified: 3-6 parts of tert-butyl acrylate monomer, 24-48 parts of initiator modified bentonite, 0.004-0.008 parts of cuprous bromide, and 40-50 parts of anhydrous N,N-dimethylformamide are added to a reaction kettle under an inert gas atmosphere, frozen and degassed, then 0.04-0.08 parts of N,N,N',N'',N''-pentamethyldiethylenetriamine is added, stirred at 50-80 ℃ for 10-24 h, 3-6 parts of hydroxy acrylate monomer and 0.004-0.008 parts of cuprous bromide are added and continue to stir for 10-24 h, the reaction is terminated by passing oxygen after the reaction is completed, the precipitate is separated by centrifugation, washed with deionized water and alcohol at least twice, the precipitate is dispersed in a mixed solvent of dichloromethane and trifluoroacetic acid, stirred at room temperature for 16-24 h, after removing the organic solvent, the pH is adjusted to 9-11, the precipitate is separated by centrifugation, washed and dried to obtain the polymer modified bentonite; The initiator has the following molecular structure: ； The mass ratio of the bentonite to the silane coupling agent is (4-6):(0.5-1).

2. A ceramic material according to claim 1, wherein the ceramic material has a plasticity of at least 0.5 mm. The purification step in step S1 is as follows: The bentonite and water are stirred at a mass ratio of 1:(5-7) for 1-2 h, and then left to stand for 16-24 h to remove the lower layer of sand; after continuing to stir for 10-30 min, water is added to prepare a liquid with a mass ratio of bentonite ore powder to water of 1:(9-12), and then stirred for 20-30 min, left to stand for 5-6 h, and the supernatant is recovered, the upper layer of fine soil is taken out from the sediment, the lower layer of sand is discarded, the upper layer of fine soil is filtered, dried in an electric heating constant temperature drying oven, crushed, and screened by using a 200 mesh screen.

3. The ceramic material of claim 1, wherein The detailed steps for the silane modified bentonite in step S2 are as follows: The bentonite obtained in step S1 is dispersed in a mixed solvent of alcohol and water, then a silane coupling agent containing an epoxy group is added, stirring at a temperature of 40-60 ℃ for 8-12 h, the precipitate is separated by centrifugation, washed and dried to obtain silane-modified bentonite; the mass ratio of the bentonite, the silane coupling agent and the mixed solvent is (4-6):(0.5-1):(30-50); the volume ratio of the alcohol and water is (1-10):1; the alcohol is at least one of methanol and ethanol; the silane coupling agent containing an epoxy group is at least one of 3-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl trimethoxysilane.

4. The ceramic material of claim 1, wherein the ceramic material has a plasticity of at least 0.5 mm. The detailed steps for preparing the initiator-modified bentonite in step S3 are as follows: The 4-6 parts of silane-modified bentonite obtained in step S2 is dispersed in 30-50 parts of dry tetrahydrofuran, 0.5-1 part of initiator is added under a nitrogen atmosphere, the temperature is raised to 50-60 ℃, and the reaction is carried out for 10-16 h, the precipitate is separated by centrifugation, washed and vacuum dried to obtain the initiator-modified bentonite.

5. The ceramic material of high plasticity according to claim 1, characterized in that, In step S4, the tert-butyl acrylate monomer is at least one of tert-butyl acrylate and tert-butyl methacrylate; the hydroxyethyl acrylate monomer is at least one of hydroxyethyl acrylate and hydroxyethyl methacrylate; the pH adjustment is carried out using an aqueous solution of one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.

6. A ceramic material according to claim 1, wherein the ceramic material has a plasticity of at least 0.5 mm. The bentonite is at least one of sodium-based bentonite and calcium-based bentonite.

7. A method for preparing a ceramic material with high plasticity, comprising the following steps: mud making, shaping, water application, bisque firing, glazing, kiln glaze firing, and colored porcelain; The mud making is: the ceramic slurry is ground into mixed mud by a ball mill, the particulate matter is filtered by a vibrating filter screen device, the excess water is squeezed out by a mud pressing bed equipment, and finally the air in the mud is further discharged by a mud refining machine, and finally a mud strip is formed; The shaping is to select roll forming or slip casting to obtain a soil culture; The water application is to polish the burrs and particles of the soil culture to clean with a water-soaked sponge; The final temperature of the bisque firing is 600-1000 ℃, and the steps are: the temperature is raised from room temperature to 200 ℃ at a rate of 50-100 ℃ / h; 200-600 ℃ at a rate of 30-60 ℃ / h; 600-1000 ℃ at a rate of 90-110 ℃ / h; after the temperature is raised to the final temperature, the temperature is kept for 1-2 h; The final temperature of the kiln glaze firing is 900-1200 ℃, and the steps are: the temperature is raised from room temperature to 500 ℃ at a rate of 100-150 ℃ / h; 500-900 ℃ at a rate of 50-100 ℃ / h; 900-1200 ℃ at a rate of 50-80 ℃ / h; after the temperature is raised to the final temperature, the temperature is kept for 1-2 h; the temperature is lowered at a rate of 50-100 ℃ / h, and after the temperature is lowered to 600 ℃, the temperature is naturally cooled; The colored porcelain is at least one of a powder spraying process or a color drawing process; and the ceramic material is the ceramic material of any one of claims 1-6.

8. Use of a ceramic material obtainable by the process according to claim 7 in ceramic flower pots.

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