CN113045288A - Ceramic slurry, ceramic prepared from ceramic slurry and having low deformation rate and preparation process of ceramic - Google Patents
Ceramic slurry, ceramic prepared from ceramic slurry and having low deformation rate and preparation process of ceramic Download PDFInfo
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- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
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Abstract
The application relates to the technical field of ceramic production, and particularly discloses ceramic slurry, ceramic with low deformation rate and a preparation process of the ceramic. The ceramic slurry is prepared by stirring and mixing the following raw materials in parts by weight: 35-40 parts of ball stone, 75-80 parts of Qinyang soil and other ceramic pug, 5-10 parts of amino phosphoric acid type resin and 370 parts of water 350-; the ceramic with low deformation rate is prepared from the ceramic slurry, and the preparation process comprises the following steps: the ceramic slurry is subjected to slip casting to obtain a ceramic green body, and the ceramic green body is subjected to the working procedures of drying, glazing, firing and the like to obtain the ceramic with low deformation rate. The ceramic with low deformation rate can be used for ceramic production, and has the advantages of low deformation rate and high strength.
Description
Technical Field
The application relates to the technical field of ceramic production, in particular to ceramic slurry, ceramic with low deformation rate and a preparation process of the ceramic.
Background
With the rapid development of ceramic production technology, ceramic products are various in types and different in performance, traditional ceramic products comprise daily ceramics, building sanitary ceramics, industrial art ceramics, chemical engineering ceramics, electrical ceramics and the like, and the ceramic products are widely applied to various fields of national economy.
At present, the existing preparation process of ceramics comprises the following steps:
s1, putting the ceramic pug into a ball mill for ball milling for 16-22h, and sieving to obtain ceramic slurry;
s2, injecting the ceramic slurry into a gypsum mould, and performing grouting forming to obtain a ceramic green body;
s3, drying the ceramic green body for 4-7 days and then glazing;
and S4, placing the glazed ceramic green body into a kiln for high-temperature sintering to obtain the ceramic product.
In view of the above-mentioned related technologies, the inventors believe that during the drying process of the ceramic green body, the drying shrinkage of the green body is inconsistent due to the non-uniform moisture content of the green body, so that the deformation rate of the fired ceramic product is high.
Disclosure of Invention
In order to reduce the deformation rate of the ceramic, the present application provides a ceramic slurry.
In order to obtain a ceramic having a low deformation ratio, the present application provides a ceramic having a low deformation ratio.
In order to obtain the ceramic with low deformation rate, the application provides a preparation process of the ceramic with low deformation rate.
The application provides a ceramic slurry adopts following technical scheme:
in a first aspect, the present application provides a ceramic slurry, which adopts the following technical scheme:
the ceramic slurry is prepared by stirring and mixing the following raw materials in parts by weight:
ceramic pug: 35-40 parts of ball stone, 75-80 parts of Qinyang soil, 50-55 parts of Japanese sea-buckthorn wood knots, 130 parts of ball soil 123-containing material, 110 parts of Xuanhua soil 100-containing material, 58-65 parts of Funing porcelain stone, 70-75 parts of Chengdu soil, 155 parts of Chancura soil 148-containing material, 28390, 170 parts of county sandstone 178-containing material, 75-85 parts of white mud, 5-10 parts of dolomite, 40-48 parts of porcelain powder and 105 parts of black gangue 100-containing material;
5-10 parts of amino phosphoric acid type resin;
350 portions and 370 portions of water.
By adopting the technical scheme, as the ceramic slurry is a colloid system with mud suspended in water, mud particles are negatively charged and can attract cations in water to form micelles such as calcium ions, magnesium ions and the like, and a large amount of H is adsorbed on the mud particles+Due to H+The ionic radius is small, the charge density is large, the acting force with negatively charged mud particles is also large, the mud particles can easily enter a colloid adsorption layer, most charges of the mud particles are neutralized, the repulsive force between adjacent charge particles with the same number is reduced, the particles are easy to adhere and agglomerate, and the fluidity of slurry is reduced; and among particles of the pug due to higher electrovalence of calcium ionsThe electrostatic attraction is large, and the slurry is easy to enter a micelle adsorption layer, so that the fluidity of the slurry is also reduced.
The preparation method comprises the steps of mixing ceramic mud according to a preparation proportion, ensuring that the ceramic mud can be formed into a ceramic green body by grouting, introducing amino phosphoric acid type resin into the ceramic mud, wherein the amino phosphoric acid type resin is used as an electrolyte with a diluting and dispersing effect, and the amino phosphoric acid type resin can complex calcium ions and magnesium ions in the mud to form a stable complex compound, so that a mud system has the diluting and dispersing effect.
Under the high-temperature condition of firing the ceramic green body, phosphate radicals in the amino phosphoric acid type resin react with calcium ions in a slurry system to generate calcium phosphate precipitates, and the generated calcium phosphate can be filled in ceramic air holes and cannot volatilize along with water, so that the density of the ceramic product is increased, the loss on firing of the ceramic product is reduced, the fired ceramic product is more densified, and the strength is increased.
Preferably, 3-6 parts of a cross-linking agent is also included.
By adopting the technical scheme, the cross-linking agent is added into the ceramic slurry, so that the cracking of the ceramic green body in the drying process is reduced, the bonding property between ceramic pugs is enhanced, and the ceramic deformation caused by cracking is reduced.
Preferably, the cross-linking agent is methylcellulose.
By adopting the technical scheme, the methyl cellulose is nonionic cellulose ether, the methyl cellulose has thermal gelation property, the methyl cellulose is completely dissolved in water at low temperature to form transparent aqueous solution, the methyl cellulose can generate sol gelation reaction along with the rise of temperature, and the temperature of a mould is raised in the process of carrying out grouting forming on ceramic slurry, so that the viscosity of the methyl cellulose is increased along with the rise of temperature to lose fluidity, the shape of a ceramic green body is more stable, and the ceramic green body is not easy to deform.
Preferably, the methylcellulose has a particle size of 45 to 55 microns.
By adopting the technical scheme, the particle size of the methyl cellulose is smaller than that of the ceramic mud, so that the methyl cellulose can be better dissolved in water to form a transparent aqueous solution, the methyl cellulose is better dispersed in a ceramic slurry system, the condition that ceramic green bodies crack due to the fact that the shrinkage rate is too high during drying is reduced, and deformation of ceramic is reduced.
Preferably, the detergent also comprises 2-4 parts of a surfactant.
By adopting the technical scheme, the surfactant can enable the ceramic pug and the amino phosphoric acid type resin to be better dispersed in the ceramic slurry, and simultaneously, the condition of sticking a die is reduced when the ceramic green body is demoulded, so that the deformation of the ceramic green body is reduced, and the deformation rate of the ceramic product is lower.
Preferably, the surfactant is cetyltrimethylammonium bromide.
By adopting the technical scheme, the hexadecyl trimethyl ammonium bromide is an ionic surfactant, and can be aggregated around the hexadecyl trimethyl ammonium bromide to form micelle-like aggregates through the interaction of hydrophobic groups carried by the hexadecyl trimethyl ammonium bromide and methyl groups on a methyl cellulose chain, so that a network structure is formed among different methyl celluloses, and the ceramic green body is not easy to crack in the drying process, and is more stable in shape and not easy to deform.
Preferably, the detergent also comprises 2-4 parts of sodium chloride.
By adopting the technical scheme, sodium chloride is used as soluble salt electrolyte to adjust the performance of the ceramic slurry, and the sodium chloride can induce cetyl trimethyl ammonium bromide to form free spherical micelles in a slurry system and reduce the free energy, so that the sol gelation transformation of methyl cellulose is promoted, the methyl cellulose after the sol gelation transformation is better crosslinked with the ceramic slurry, the viscosity of the methyl cellulose is reduced to form gel under the temperature rise condition of ceramic slip casting, the shrinkage force in the ceramic drying process is resisted in the subsequent drying process of ceramic green bodies, and the ceramic deformation is reduced.
In a second aspect, the present application provides a low deformation ratio ceramic, comprising the ceramic slurry as described above.
By adopting the technical scheme, the amino phosphoric acid type resin is introduced into the ceramic mud, the amino phosphoric acid type resin can complex calcium ions and magnesium ions in a mud system, the performance of the slurry is improved, the uniform water content of a green body is ensured, the drying shrinkage is consistent, the deformation is reduced, phosphate radicals on the amino phosphoric acid type resin and the calcium ions form calcium phosphate, pores in the ceramic green body can be effectively filled under the high-temperature condition of ceramic firing, the loss on firing is reduced, the density is increased, and the strength of the ceramic product is improved; adding methyl cellulose into ceramic slurry, wherein the methyl cellulose is nonionic cellulose ether, the methyl cellulose has thermal gelation property, the methyl cellulose is completely dissolved in water at low temperature to form a transparent aqueous solution, the methyl cellulose can generate sol gelation reaction along with the rise of temperature, and a mold is heated in the process of grouting and forming the ceramic slurry, so that the viscosity of the methyl cellulose is increased along with the rise of temperature, the fluidity of the methyl cellulose is lost, the shape of a ceramic green body is more stable, and the ceramic green body is not easy to deform;
cetyl trimethyl ammonium bromide is added into the ceramic slurry and can be aggregated around the ceramic slurry to form an aggregate similar to micelle through the interaction of hydrophobic groups carried by the cetyl trimethyl ammonium bromide and methyl groups on a methyl cellulose chain, so that a network structure is formed among different methyl celluloses, the ceramic green body is ensured not to crack easily in the drying process, and the ceramic green body is more stable in shape and not easy to deform; sodium chloride is added into the ceramic slurry to serve as soluble salt electrolyte, and the existence of the sodium chloride can induce cetyl trimethyl ammonium bromide to form free spherical micelles in a slurry system, so that the sol gelation transformation of the methyl cellulose is promoted, the methyl cellulose after the sol gelation transformation is better crosslinked with the ceramic slurry, and the ceramic deformation is reduced.
In a third aspect, the present application provides a process for preparing a ceramic with a low deformation rate, which adopts the following technical scheme: a preparation process of ceramic with low deformation rate comprises the following steps,
s1, injecting the ceramic slurry into a gypsum mould, and performing grouting forming at the temperature of 45-65 ℃ to obtain a ceramic green body;
s2, drying the ceramic green body for 4-7 days and then glazing;
and S3, placing the glazed ceramic green body into a kiln for high-temperature sintering to obtain the ceramic product.
By adopting the technical scheme, the ceramic slurry is subjected to slip casting, drying, glazing, high-temperature sintering and other steps to prepare the ceramic with low deformation rate.
In summary, the present application has the following beneficial effects:
1. because the amido phosphate type resin is adopted in the method, the amido phosphate type resin can complex calcium ions and magnesium ions in the slurry to form a stable complex, the effect of diluting and dispersing a slurry system is achieved, meanwhile, the cation dissociation degree of the amido phosphate type resin is large, the amido phosphate type resin can enter a diffusion layer of micelle, the electric potential is increased, the repulsive force among particles is increased, the fluidity of the slurry is improved, the ceramic slurry is better dispersed in water, the water content of the prepared ceramic green body is uniform, the drying and shrinking consistency of the green body is ensured, and the deformation of the ceramic is reduced. Under the high-temperature condition of ceramic firing, phosphate radicals in the amino phosphoric acid type resin react with calcium ions in a slurry system to generate calcium phosphate, the generated calcium phosphate can be filled in ceramic air holes and cannot volatilize along with water, the loss on firing of the ceramic product is reduced, the density of the ceramic product is increased, and the strength of the fired ceramic product is better;
2. preferably, methyl cellulose is adopted in the application, the methyl cellulose is nonionic cellulose ether, the methyl cellulose has thermal gelation property, the methyl cellulose is completely dissolved in water at low temperature to form a transparent aqueous solution, the methyl cellulose can generate sol gelation reaction along with the rise of temperature, and a mold is heated in the process of grouting and forming ceramic slurry, so that the viscosity of the methyl cellulose is increased along with the rise of temperature, the fluidity of the methyl cellulose is lost, the shape of a ceramic green body is more stable, and the ceramic green body is not easy to deform; 3. according to the method, the ceramic slurry is subjected to slip casting to obtain the ceramic green body, and the ceramic green body is subjected to the working procedures of drying, glazing, firing and the like to obtain the ceramic product, so that the ceramic with low deformation rate is obtained.
Detailed Description
The raw material sources are as follows:
the chemical components of the raw materials of ceramic pug, glaze and the like are as follows
Example 1
The ceramic slurry is prepared by stirring and mixing the following raw materials in mass:
ceramic pug: 38kg of ball stone, 77kg of Qinyang soil, 52kg of shanxi son wood knot, 126kg of ball soil, 106kg of Xuanhua soil, 60kg of funing porcelain stone, 72kg of Chengde soil, 149kg of Zhangcun soil, 28390, 174kg of county sandstone, 80kg of white mud, 8kg of dolomite, 44kg of porcelain powder and 103kg of black gangue;
7kg of amino phosphoric acid type resin;
360kg of water;
5kg of cross-linking agent;
3kg of surfactant;
3kg of sodium chloride.
Wherein the cross-linking agent is methyl cellulose with the grain diameter of 50 microns;
the surfactant is cetyl trimethyl ammonium bromide;
the ceramic with low deformation rate is prepared from the ceramic slurry.
The preparation process of the ceramic with low deformation rate prepared by the ceramic slurry comprises the following steps:
s1, placing the ceramic pug and water in a ball mill for ball milling for 20 hours, adding the amino phosphoric acid resin, the methyl cellulose, the hexadecyl trimethyl ammonium bromide and the sodium chloride after ball milling, and sieving with a 250-mesh sieve to obtain ceramic slurry;
s2, injecting the ceramic slurry into a gypsum mould, and performing slip casting at 65 ℃ for 2h to obtain a ceramic green body, wherein the thickness of the slip casting is 10 mm;
s3, drying the ceramic green body for 6 days, and then glazing, wherein the glazing thickness is 0.8 +/-0.2 mm;
s4, placing the glazed ceramic green body into a tunnel kiln for firing at the low temperature stage of 490 +/-5 ℃, the medium temperature stage of 1000 +/-5 ℃, the high temperature stage of 1155 +/-5 ℃, the quenching stage of 685 +/-5 ℃, the slow cooling stage of 509 +/-5 ℃ and the tail cooling stage of 224 +/-5 ℃ for 14h to obtain the ceramic product.
The glaze slip added in the glazing process is obtained by grinding and sieving 30kg of quartz, 25kg of feldspar, 4kg of zinc oxide, 13kg of calcite, 7.5kg of dolomite, 8kg of barium carbonate, 2kg of aluminum oxide, 6kg of Suzhou soil, 3kg of frit and 60kg of mixed water through a ball mill.
Examples 2 to 5
A ceramic slurry is prepared according to example 1, wherein the amount of raw materials is different.
The amounts of the raw materials used in examples 1 to 5 are shown in the table below.
TABLE 1 raw material amounts for examples 1 to 5
Example 6
A ceramic slurry was prepared in accordance with example 1 except that the amount of the phosphoramidate type resin was 0 kg.
The ceramics of examples 1-5 and example 6 were tested.
The test comprises the following steps:
1. deformation rate test
The ceramics were measured according to the method specified in GB/T3300 + 2008 "method for testing deformation of domestic ceramics". The method comprises the steps of respectively testing 100 ceramic samples, taking the average value of the outer diameter difference and the average value of the height difference of the edge of the opening of the tested ceramic as reference values, and representing the deformation degree of the ceramic by multiples of the reference values.
2. Ceramic Strength test
The ceramics were tested according to the method specified in GB/T4740-1999 test method for compressive Strength of ceramic materials.
The test results are given in the table below.
TABLE II, ceramic test results for examples 1-5 and example 6
The deformation rate test of the examples 1-5 is superior to that of the example 6, so that the phosphoramidate resin is introduced into the ceramic slurry in the application, the phosphoramidate resin is used as an electrolyte for diluting and dispersing, the phosphoramidate resin can complex calcium ions and magnesium ions in the slurry to form a stable complex, and plays a role in diluting and dispersing a slurry system, and simultaneously, as the cationic dissociation degree of the phosphoramidate resin is large, the phosphoramidate resin can enter a diffusion layer of micelle, the electromotive potential is increased, the repulsive force among particles is increased, so that the fluidity of the slurry is improved, the ceramic slurry is better dispersed in water, the water content of the prepared ceramic green body is uniform, the drying shrinkage of the green body is consistent, and the deformation of the ceramic is reduced.
The compressive strength of examples 1 to 5 is superior to that of example 6, so that phosphate in the phosphoramidate resin reacts with calcium ions in the slurry system to form calcium phosphate, the formed calcium phosphate melts after reaching its own melting point, and the melted calcium phosphate automatically fills pores generated by water volatilization in the ceramic firing process, so that the density of the ceramic product is increased, the loss on firing of the ceramic product is reduced, and the fired ceramic product is more densified and has increased strength.
Example 7
A ceramic slip as described in example 1, except that 0kg of a crosslinking agent was used.
Example 8
A ceramic slip as described in example 1, except that the cross-linking agent is N, N-methylenebisacrylamide.
Example 9
A ceramic slurry according to example 1, except that the cross-linking agent is hydroxypropyl methylcellulose.
Example 10
A ceramic slip as described in example 1, except that the methylcellulose has a particle size of 100 microns.
The ceramics of examples 7-10 were tested.
The test results are given in the table below.
TABLE III test results for ceramics of examples 7-10
| Example 7 | Example 8 | Example 9 | Example 10 | |
| Multiple of outer diameter difference | 1.64 | 1.58 | 1.53 | 1.42 |
| Multiples of the height difference of the mouth edge | 1.74 | 1.69 | 1.62 | 1.48 |
By combining example 1 and example 7 and combining tables two and three, it can be seen that the deformation rate test of example 1 is better than that of example 7, so that the addition of the cross-linking agent into the ceramic slurry reduces the occurrence of cracking during the drying process of the ceramic green body, enhances the bonding performance between the ceramic slurries, and reduces the ceramic deformation caused by cracking.
Combining example 1 and examples 8-9 and combining tables two and three, it can be seen that the deformation rate test of example 1 is better than that of examples 8-9, so that methylcellulose in the application is a nonionic cellulose ether, methylcellulose has thermal gel property, methylcellulose is completely dissolved in water at low temperature to form a transparent aqueous solution, the methylcellulose can generate sol gelation reaction along with the increase of temperature, the temperature of a mold is increased in the process of grouting and forming ceramic slurry, the viscosity of the methylcellulose is increased along with the increase of temperature to lose fluidity, the shape of a ceramic green body is more stable, and deformation is not easy to occur.
Combining example 1 and example 10 and combining tables two and three, it can be seen that the deformation rate test of example 1 is better than that of example 10, so that the particle size of methylcellulose in the application is finer than that of the ceramic slurry, so that the methylcellulose can be better dissolved in water to form a transparent aqueous solution, and thus the methylcellulose is better dispersed in the ceramic slurry system, the cracking of the ceramic green body caused by too fast shrinkage rate during drying is reduced, and the deformation of the ceramic is reduced.
Example 11
A ceramic slip as described in example 1, except that the amount of the surfactant used was 0 kg.
Example 12
A ceramic slurry according to example 1, except that the surfactant is sodium dodecylbenzenesulfonate.
Example 13
A ceramic slurry according to example 1, except that the surfactant is dodecyltrimethylammonium bromide.
Example 14
A ceramic slip as described in example 1, except that 0kg of sodium chloride was used.
Example 15
A ceramic slip as described in example 1, with the exception that 10kg of sodium chloride was used.
The ceramics of examples 11-15 were tested.
The test results are given in the table below.
TABLE IV, ceramic test results for examples 11-15
Combining example 1 and example 11 with tables two and four, it can be seen that the deformation rate test of example 1 is better than that of example 11, so the surfactant in the present application can make the ceramic mud and the amino phosphoric acid type resin better dispersed in the ceramic slurry, and at the same time, reduce the sticking of the die when the ceramic green body is demolded, thereby reducing the deformation of the ceramic green body and making the deformation rate of the ceramic article lower.
As can be seen by combining example 1 and examples 12-13 and combining tables two and four, the deformation rate test of example 1 is better than that of examples 12-13, so that cetyl trimethyl ammonium bromide is an ionic surfactant in the application, and the cetyl trimethyl ammonium bromide can be aggregated around the cetyl trimethyl ammonium bromide to form micelle-like aggregates through the interaction of hydrophobic groups carried by the cetyl trimethyl ammonium bromide and methyl groups on methyl cellulose chains, so that a network structure is formed among different methyl celluloses, thereby ensuring that ceramic green bodies are not easy to crack in the drying process, and the ceramic green bodies are more stable in shape and not easy to deform.
Combining example 1 and examples 14-15 and combining table two and table four, it can be seen that the deformation rate test of example 1 is better than examples 14-15, so sodium chloride in the present application is used as a soluble salt electrolyte to adjust the performance of the ceramic slurry, and the presence of sodium chloride can induce hexadecyl trimethyl ammonium bromide to form free spherical micelles in the slurry system, reduce the free energy, thereby promoting the sol gelation transformation of methyl cellulose, better crosslinking the methyl cellulose after the sol gelation transformation and the ceramic slurry, under the temperature rising condition of ceramic slip casting, the viscosity of methyl cellulose is reduced to form gel, and the shrinkage force in the ceramic drying process is resisted in the subsequent drying process of the ceramic green body, and the ceramic deformation is reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (9)
1. The ceramic slurry is characterized by being prepared by stirring and mixing the following raw materials in parts by weight:
ceramic pug: 35-40 parts of ball stone, 75-80 parts of Qinyang soil, 50-55 parts of Japanese sea-buckthorn wood knots, 130 parts of ball soil 123-containing material, 110 parts of Xuanhua soil 100-containing material, 58-65 parts of Funing porcelain stone, 70-75 parts of Chengdu soil, 155 parts of Chancura soil 148-containing material, 28390, 170 parts of county sandstone 178-containing material, 75-85 parts of white mud, 5-10 parts of dolomite, 40-48 parts of porcelain powder and 105 parts of black gangue 100-containing material;
5-10 parts of amino phosphoric acid type resin;
350 portions and 370 portions of water.
2. A ceramic slurry as claimed in claim 1, wherein: also comprises 3-6 parts of cross-linking agent.
3. A ceramic slurry according to claim 2, wherein: the cross-linking agent is methyl cellulose.
4. A ceramic slurry according to claim 3, wherein: the particle size of the methyl cellulose is 45-55 microns.
5. A ceramic slurry as claimed in claim 1, wherein: also comprises 2-4 parts of surfactant.
6. A ceramic slurry according to claim 5, wherein: the surfactant is cetyl trimethyl ammonium bromide.
7. A ceramic slurry as claimed in claim 1, wherein: also comprises 2-4 parts of sodium chloride.
8. A low deformation ceramic, characterized by: prepared from a ceramic slurry according to any one of the preceding claims 1 to 7.
9. A process for preparing a low deformation ceramic according to claim 8, comprising the steps of,
s1, injecting the ceramic slurry into a gypsum mould, and performing grouting forming at the temperature of 45-65 ℃ to obtain a ceramic green body;
s2, drying the ceramic green body for 4-7 days and then glazing;
and S3, placing the glazed ceramic green body into a kiln for high-temperature sintering to obtain the ceramic product.
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