CN115849865B - Preparation method of high-performance ball clay for ceramic sanitary ware - Google Patents
Preparation method of high-performance ball clay for ceramic sanitary ware Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 60
- 239000010427 ball clay Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000004927 clay Substances 0.000 claims abstract description 18
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 14
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 14
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000001110 calcium chloride Substances 0.000 claims abstract description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 230000018044 dehydration Effects 0.000 claims abstract description 7
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000003825 pressing Methods 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 79
- 239000000835 fiber Substances 0.000 claims description 73
- 239000002121 nanofiber Substances 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 239000002131 composite material Substances 0.000 claims description 38
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000004964 aerogel Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- 238000010041 electrostatic spinning Methods 0.000 claims description 11
- 238000003837 high-temperature calcination Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 4
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008093 supporting effect Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 230000000087 stabilizing effect Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes
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- Silicon Compounds (AREA)
- Porous Artificial Stone Or Porous Ceramic Products (AREA)
Abstract
The invention discloses a preparation method of high-performance ball clay for ceramic sanitary wares, which comprises the following steps: 1) Preparing raw materials; 2) Mixing kaolin, raw ore mud and secondary clay in the raw materials, adding water to form slurry, removing impurities, and adding calcium chloride to obtain high-purity slurry; 3) Adding the dispergation compound into the high-purity slurry, uniformly mixing, and then carrying out filter pressing and dehydration. The high-performance ball clay has a nano skeleton structure with supporting and stabilizing functions, so that the ball clay can keep stable structure when being subjected to external force, has good strength, can promote the fluidity of ceramic slurry to be increased when being applied to ceramic products, achieves the aim of high-resolution effect, and can enable the moisture in the ceramic slurry to be easily absorbed under the action of capillary force, so that the ceramic slurry has good slurry absorbing capacity, thereby being beneficial to improving the quality of ceramic products and promoting the rapid high-quality development of ceramic industry.
Description
Technical Field
The invention relates to the technical field of ceramic raw materials, in particular to a preparation method of high-performance ball clay for ceramic sanitary ware.
Background
The ceramic sanitary ware ball clay is specially applied to the production of ceramic sanitary ware, and has the advantages that the ball clay has finer particles, so that the natural particle shape is maintained, and meanwhile, the ceramic sanitary ware ball clay has stronger ion exchange capability, and the performance of slurry can be improved; these meet the grouting requirements of large and complex products, and have high strength, good plasticity and relatively low sintering temperature. With these characteristics, the ball clay plays a very critical role in ceramic sanitary wares.
For example, the invention patent with publication number CN101844913A discloses a preparation method of ball clay for high-grade sanitary ware, which takes black mud, plaster and kaolin as raw materials to prepare ball clay, overcomes the defect caused by the change of raw material components of ball clay due to organic impurities and sand content, and has stable whiteness, strength and viscosity and good grouting fluidity, thus being widely applied to the high-grade ceramic industry; the ball clay obtained by the process method has good fluidity, but the formed ball clay has poor slurry absorption performance, can not obviously improve the strength of ceramics when being applied to ceramics, and has poor comprehensive performance because particles in raw materials have different charges and have adsorption agglomeration trend, so that the fluidity of the ball clay can not meet the development requirement of the modern ceramic industry, and the fluidity can be further improved by externally adding a deflocculant, but the electrostatic repulsion force among the ceramic particles is weak because the adsorption amount of the deflocculant on the ceramic particles is limited, and the high-efficiency dispersion of the ceramic particles can not be promoted, so that the comprehensive performance of the ball clay is poor, and the requirement of increasingly developed high-grade ceramics on the quality of the ball clay can not be met.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the high-performance ball clay for the ceramic sanitary ware, wherein the high-performance ball clay is internally provided with the nano skeleton structure with supporting and stabilizing functions, so that the ball clay can keep the stability of the structure when being acted by external force, thereby having good strength, meeting the requirement of high strength, and being capable of promoting the disintegration of the flocculation structure of ceramic slurry to release the wrapped moisture when being applied to ceramic products, so that the fluidity of the ceramic slurry is increased, thereby achieving the aim of high-resolution effect, and the structure of the ceramic slurry is loose, the moisture in the ceramic slurry is easily absorbed under the action of capillary force, so that the ceramic slurry has good slurry absorbing capability, thereby being beneficial to improving the quality of ceramic products and promoting the rapid high-quality development of ceramic industry.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the high-performance ball clay for the ceramic sanitary ware specifically comprises the following steps:
1) Preparing raw materials, weighing kaolin, raw ore mud, secondary clay, calcium chloride, a dispergation compound and water;
2) Mixing kaolin, raw ore mud and secondary clay, adding water, fully stirring and mixing to form slurry, removing impurities through a vibrating screen, adding calcium chloride, and settling to obtain high-purity slurry;
3) Adding the dispergation compound into the high-purity slurry, uniformly mixing, and carrying out filter pressing dehydration on the uniformly mixed material to obtain the required high-performance ball clay.
As a further preferable scheme of the invention, the raw materials comprise, by weight, 15-30 parts of kaolin, 10-16 parts of raw ore mud, 8-12 parts of secondary clay, 0.4-0.8 part of calcium chloride, 2-4 parts of a dispergation compound and 20-28 parts of water.
As a further preferable embodiment of the present invention, the preparation method of the dispergation complex is as follows:
adding sodium bisulfate into deionized water, fully stirring and dissolving, heating, adding acrylic acid, sodium methallyl sulfonate and ammonium persulfate, uniformly mixing, adding porous fiber composite gel, performing heat preservation reaction for 2-5h, naturally cooling after the reaction is finished, and regulating the pH to 7.5-8.0 by using sodium hydroxide solution to obtain a dispergate compound.
As a further preferable scheme of the invention, the dosage proportion of the sodium bisulfite, the deionized water, the acrylic acid, the sodium methacrylate sulfonate, the ammonium persulfate and the porous fiber composite gel is (3-6) g: (150-260) mL: (38-45) g: (8-13) g: (0.3-0.8) g: (8-15) g;
the heating temperature is 50-56 ℃;
Naturally cooling to 40-43 ℃;
the concentration of the sodium hydroxide solution is 30-35wt%.
As a further preferable scheme of the invention, the preparation method of the porous fiber composite gel comprises the following steps:
1) Mixing and stirring tetraethoxysilane, water, ethanol and anhydrous oxalic acid until the mixture is clarified to obtain silica sol, crushing a silica fiber film, dispersing the crushed silica fiber film in a polyethylene oxide solution, adding the silica sol, homogenizing the mixture to obtain a silica fiber dispersion liquid, and carrying out freeze drying and high-temperature calcination for 2-5 hours to obtain silica fiber aerogel;
2) Adding anhydrous oxalic acid into a mixed solution composed of dimethyl sulfoxide and water, stirring until the anhydrous oxalic acid is completely dissolved, adding methyltrimethoxysilane, stirring for 30-50min, dropwise adding ammonia water, uniformly mixing, adding porous nano fibers, and uniformly dispersing to obtain mixed sol;
3) Adding silica fiber aerogel into the mixed sol, fully stirring, sealing in a container, placing in an oven for heat preservation, taking out a product, replacing with ethanol, drying, transferring to a calciner, calcining at high temperature, and crushing to obtain the porous fiber composite gel.
As a further preferable mode of the present invention, in the step 1), the silica sol contains ethyl orthosilicate, water, ethanol and anhydrous oxalic acid in a proportion of (1-5) g: (4-15) g: (10-30) g: (0.01-0.05) g;
The dosage proportion of the silicon dioxide fiber film, the polyethylene oxide solution and the silicon dioxide sol is (1-3) g: (200-500) g: (0.26-0.32) g;
the concentration of the polyethylene oxide solution is 0.01-0.03wt%;
the high-temperature calcination temperature is 800-900 ℃.
As a further preferable mode of the present invention, in the step 2), the ratio of the anhydrous oxalic acid, dimethyl sulfoxide, water, methyltrimethoxysilane, ammonia water and porous nanofiber is (0.34-0.45) g: (170-190) g: (52-60) g: (2-5) g: (1-3) mL: (5-10) g;
The concentration of the ammonia water is 22-25wt%.
As a further preferred embodiment of the present invention, in step 3), the mass-to-volume ratio of the silica fiber aerogel to the mixed sol is 1g: (10-20) mL;
the heat preservation time in the oven is 2-5h, and the temperature is 70-75 ℃;
the high-temperature calcination temperature is 950-1000 ℃.
As a further preferred embodiment of the present invention, the preparation method of the porous nanofiber comprises the following steps:
1) Adding polyacrylonitrile into N, N-dimethylformamide, fully stirring to obtain a dispersion solution, carrying out electrostatic spinning on the dispersion solution, and drying to obtain nanofibers;
2) Heating and preserving heat of the nanofiber for 2-5h in an air atmosphere, then heating and preserving heat for 4-9h in a nitrogen atmosphere, and cooling to room temperature to obtain the porous nanofiber.
As a further preferable mode of the invention, the dosage ratio of polyacrylonitrile to N, N-dimethylformamide in the dispersion solution is (6-8) g: (50-80) mL;
the parameters of the electrostatic spinning are as follows: the receiving distance is 15-20cm, the voltage is 8-10kV, and the flow rate is 0.02-0.05mL/min;
heating to 260-300 ℃ under the air atmosphere, wherein the heating rate is 1-3 ℃/min;
Heating to 750-800 ℃ under the nitrogen atmosphere, wherein the heating rate is 3-6 ℃/min.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, silica fiber is taken as a construction element, freeze-drying and high-temperature calcination are combined to prepare the silica fiber aerogel with a stable fiber network structure, the fiber network structure can effectively transmit and disperse acting force, so that the silica fiber aerogel has good mechanical property and good resistance to external force, the silica fiber aerogel is taken as a supporting framework, a sol impregnation method is adopted to obtain composite gel with a double-network structure, the multistage network structure of the silica fiber aerogel is reserved in the composite gel, the material is endowed with good mechanical property, meanwhile, the structure stability of the silica fiber aerogel is not easily damaged due to the fact that the silica fiber aerogel is taken as the supporting framework, and the material has good structural stability due to the fact that the nano framework structure of the silica fiber aerogel is introduced, so that the spherical soil has better supporting and stabilizing effects, and can keep the structural stability when the spherical soil is subjected to external force, so that the spherical soil has good strength and can meet the requirement of high strength; meanwhile, in order to further improve the porosity of the composite gel and the structural stability of the composite gel, the porous nano fiber is added into the sol to obtain the porous fiber composite gel, and the porous nano fiber is introduced, so that on one hand, the porosity of the porous fiber composite gel can be further increased, the ball clay has a loose structure, the structure of ceramic slurry is loose, the internal moisture is easily absorbed under the action of capillary force, so that the ceramic slurry has good absorbing capacity, and meanwhile, the cross-linking density of the multi-stage network structure in the porous fiber composite gel is increased by the cross-linking of the porous nano fiber, so that the stability of the nano skeleton structure can be further improved, the resistance of the porous fiber composite gel to external force can be further improved, and the strength of the ball clay is obviously improved.
In the invention, porous fiber composite gel is used as a matrix, acrylic acid and sodium methacrylate are used as monomers, ammonium persulfate and sodium bisulfate are used as redox initiation systems, and a copolymer is formed by deposition on the porous fiber composite gel through copolymerization reaction, wherein-COO - and-SO 3 - groups contained in the formed copolymer are ionized to lead the surface of clay particles in ceramic to carry the same charge, and a diffusion double-electron layer is formed, and along with the increase of the adsorption quantity of a dispersoid compound on the surface of the clay particles, the formed double-electron layer structure is gradually thickened, SO that the electrostatic repulsion between the clay particles is enhanced, the formed electrostatic steric hindrance effect is enhanced, the mutual dispersion is promoted, the flocculation structure of the ceramic slurry is disintegrated, and the wrapped moisture is released, SO that the fluidity of the ceramic slurry is increased, and the aim of high dispersoid effect is achieved.
In order to promote the deposition of the copolymer on the porous fiber composite gel, the invention obtains the nanofiber based on electrostatic spinning and obtains the porous nanofiber through high-temperature calcination under the air atmosphere and the nitrogen atmosphere, and nitrogen atoms are introduced into a carbon matrix through the high-temperature calcination in the preparation process of the porous nanofiber, so that more defect structures are generated in the porous nanofiber, and although the mechanical properties of the porous nanofiber are reduced to a certain extent, more irregular holes are generated in the porous nanofiber, and more active sites are exposed in the porous nanofiber due to the formation of the irregular holes, thereby being beneficial to improving the activity of the porous fiber composite gel, so that more copolymer can be deposited on the porous fiber composite gel to form a dispersoid; by depositing the copolymer with the debonding capability on the porous fiber composite gel, the contact area between the porous fiber composite gel and the clay particles can be increased by utilizing the high specific surface area of the porous fiber composite gel, so that the adsorption of the debonding composite on the surfaces of the clay particles can be promoted, the thickness of the double-electronic-layer structure is increased, and the high fluidity of the ceramic slurry is realized.
The high-performance ball clay has a nano skeleton structure with supporting and stabilizing functions, so that the ball clay can keep stable structure when being subjected to external force, has good strength, can meet the requirement of high strength, can promote the disintegration of a flocculation structure of ceramic slurry and release wrapped moisture when being applied to ceramic products, so that the fluidity of the ceramic slurry is increased, the aim of high dispergation effect is fulfilled, the structure of the ceramic slurry is loose, and the moisture in the ceramic slurry is easily absorbed under the action of capillary force, so that the ceramic slurry has good slurry absorbing capacity, thereby being beneficial to improving the quality of ceramic products and promoting the rapid high-quality development of ceramic industry.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the high-performance ball clay for the ceramic sanitary ware specifically comprises the following steps:
1) Preparing raw materials in parts by weight, weighing 15 parts of kaolin, 10 parts of raw mineral mud, 8 parts of secondary clay, 0.4 part of calcium chloride, 2 parts of dispergation compound and 20 parts of water;
2) Mixing kaolin, raw ore mud and secondary clay, adding water, fully stirring and mixing to form slurry, removing impurities through a vibrating screen, adding calcium chloride, and settling to obtain high-purity slurry;
3) Adding the dispergation compound into the high-purity slurry, uniformly mixing, and carrying out filter pressing dehydration on the uniformly mixed material to obtain the required high-performance ball clay.
The preparation method of the dispergation compound comprises the following steps:
Adding 3g of sodium bisulphite into 150mL of deionized water, fully stirring and dissolving, heating to 50 ℃, adding 38g of acrylic acid, 8g of sodium methallyl sulfonate and 0.3g of ammonium persulfate, uniformly mixing, adding 8g of porous fiber composite gel, carrying out heat preservation reaction for 2h, naturally cooling to 40 ℃ after the reaction is finished, and regulating the pH to 7.5 by using 30wt% of sodium hydroxide solution to obtain a dispergation compound.
The preparation method of the porous fiber composite gel comprises the following steps:
1) 1g of tetraethoxysilane, 4g of water, 10g of ethanol and 0.01g of anhydrous oxalic acid are mixed and stirred until the mixture is clarified, so as to obtain silica sol, 1g of silica fiber membrane is crushed and then dispersed in 200g of polyethylene oxide solution with the concentration of 0.01wt%, 0.26g of silica sol is added, the silica sol is homogenized, so as to obtain silica fiber dispersion liquid, and the silica fiber dispersion liquid is subjected to freeze drying and then is calcined at the high temperature of 800 ℃ for 2 hours, so that the silica fiber aerogel is obtained;
2) Adding 0.34g of anhydrous oxalic acid into a mixed solution consisting of 170g of dimethyl sulfoxide and 52g of water, stirring until the anhydrous oxalic acid is completely dissolved, adding 2g of methyltrimethoxysilane, stirring for 30min at 150r/min, dropwise adding 1mL of 22wt% ammonia water, uniformly mixing, adding 5g of porous nanofiber, and uniformly dispersing to obtain mixed sol;
3) The mass volume ratio is 1g:10mL, adding silica fiber aerogel into the mixed sol, fully stirring, sealing in a container, placing in a 70 ℃ oven for heat preservation for 2h, taking out the product, replacing the product with ethanol, drying, transferring to a calciner, calcining at a high temperature of 950 ℃ for 3h, and crushing to obtain the porous fiber composite gel.
The preparation method of the porous nanofiber comprises the following steps:
1) Adding 6g of polyacrylonitrile into 50mLN, N-dimethylformamide, fully stirring to obtain a dispersion solution, carrying out electrostatic spinning on the dispersion solution, setting the receiving distance to be 15cm, carrying out electrostatic spinning at the flow rate of 8kV and 0.02mL/min, and drying the obtained fiber in a baking oven at 60 ℃ for 15h to obtain nanofiber;
2) Heating the nanofiber to 260 ℃ in an air atmosphere, controlling the heating rate to be 1 ℃/min, preserving heat for 2 hours, then heating to 750 ℃ in an argon atmosphere, controlling the heating rate to be 3 ℃/min, preserving heat for 4 hours, and cooling to room temperature to obtain the porous nanofiber.
Example 2
The preparation method of the high-performance ball clay for the ceramic sanitary ware specifically comprises the following steps:
1) Preparing raw materials in parts by weight, weighing 25 parts of kaolin, 12 parts of raw mineral mud, 10 parts of secondary clay, 0.5 part of calcium chloride, 3 parts of a dispergation compound and 24 parts of water;
2) Mixing kaolin, raw ore mud and secondary clay, adding water, fully stirring and mixing to form slurry, removing impurities through a vibrating screen, adding calcium chloride, and settling to obtain high-purity slurry;
3) Adding the dispergation compound into the high-purity slurry, uniformly mixing, and carrying out filter pressing dehydration on the uniformly mixed material to obtain the required high-performance ball clay.
The preparation method of the dispergation compound comprises the following steps:
adding 5g of sodium bisulphite into 200mL of deionized water, fully stirring and dissolving, heating to 53 ℃, adding 42g of acrylic acid, 10g of sodium methallyl sulfonate and 0.5g of ammonium persulfate, uniformly mixing, adding 12g of porous fiber composite gel, carrying out heat preservation reaction for 3 hours, naturally cooling to 42 ℃ after the reaction is finished, and regulating the pH to 7.5 by using 32wt% of sodium hydroxide solution to obtain a dispergation compound.
The preparation method of the porous fiber composite gel comprises the following steps:
1) 3g of tetraethoxysilane, 10g of water, 20g of ethanol and 0.03g of anhydrous oxalic acid are mixed and stirred until the mixture is clarified, so as to obtain silica sol, 2g of silica fiber membrane is crushed and then dispersed in 400g of polyethylene oxide solution with the concentration of 0.02wt%, 0.3g of silica sol is added, the silica fiber dispersion is obtained after homogenization, and the silica fiber aerogel is obtained after freeze drying and high-temperature calcination for 3 hours at 850 ℃;
2) Adding 0.42g of anhydrous oxalic acid into a mixed solution composed of 180g of dimethyl sulfoxide and 58g of water, stirring until the anhydrous oxalic acid is completely dissolved, adding 3g of methyltrimethoxysilane, stirring for 40min at 200r/min, dropwise adding 2mL of 23wt% ammonia water, uniformly mixing, adding 8g of porous nanofiber, and uniformly dispersing to obtain mixed sol;
3) The mass volume ratio is 1g:15mL, adding silica fiber aerogel into the mixed sol, fully stirring, sealing in a container, placing in a 72 ℃ oven for heat preservation for 3h, taking out the product, replacing the product with ethanol, drying, transferring to a calciner, calcining at a high temperature of 980 ℃ for 5h, and crushing to obtain the porous fiber composite gel.
The preparation method of the porous nanofiber comprises the following steps:
1) Adding 7g of polyacrylonitrile into 60mLN, N-dimethylformamide, fully stirring to obtain a dispersion solution, carrying out electrostatic spinning on the dispersion solution, setting the receiving distance to be 18cm, carrying out electrostatic spinning at the flow rate of 9kV and 0.03mL/min, and drying the obtained fiber in a drying oven at 70 ℃ for 16 hours to obtain nanofiber;
2) Heating the nanofiber to 280 ℃ in an air atmosphere, controlling the heating rate to be 2 ℃/min, preserving heat for 3 hours, then heating to 780 ℃ in an argon atmosphere, controlling the heating rate to be 5 ℃/min, preserving heat for 8 hours, and cooling to room temperature to obtain the porous nanofiber.
Example 3
The preparation method of the high-performance ball clay for the ceramic sanitary ware specifically comprises the following steps:
1) Preparing raw materials in parts by weight, weighing 30 parts of kaolin, 16 parts of raw mineral mud, 12 parts of secondary clay, 0.8 part of calcium chloride, 4 parts of a dispergation compound and 28 parts of water;
2) Mixing kaolin, raw ore mud and secondary clay, adding water, fully stirring and mixing to form slurry, removing impurities through a vibrating screen, adding calcium chloride, and settling to obtain high-purity slurry;
3) Adding the dispergation compound into the high-purity slurry, uniformly mixing, and carrying out filter pressing dehydration on the uniformly mixed material to obtain the required high-performance ball clay.
The preparation method of the dispergation compound comprises the following steps:
Adding 6g of sodium bisulphite into 260mL of deionized water, fully stirring and dissolving, heating to 56 ℃, adding 45g of acrylic acid, 13g of sodium methallyl sulfonate and 0.8g of ammonium persulfate, uniformly mixing, adding 15g of porous fiber composite gel, carrying out heat preservation reaction for 5h, naturally cooling to 43 ℃ after the reaction is finished, and regulating the pH to 8.0 by using 35wt% of sodium hydroxide solution to obtain a dispergation compound.
The preparation method of the porous fiber composite gel comprises the following steps:
1) 5g of tetraethoxysilane, 15g of water, 30g of ethanol and 0.05g of anhydrous oxalic acid are mixed and stirred until the mixture is clarified, so as to obtain silica sol, 3g of silica fiber membrane is crushed and then dispersed in 500g of polyethylene oxide solution with the concentration of 0.03 weight percent, 0.32g of silica sol is added, the obtained silica fiber dispersion is homogenized, and the obtained silica fiber dispersion is subjected to freeze drying and then high-temperature calcination for 5 hours at 900 ℃ so as to obtain silica fiber aerogel;
2) Adding 0.45g of anhydrous oxalic acid into a mixed solution consisting of 190g of dimethyl sulfoxide and 60g of water, stirring until the anhydrous oxalic acid is completely dissolved, adding 5g of methyltrimethoxysilane, stirring for 50min at 300r/min, dropwise adding 3mL of ammonia water with the concentration of 25wt%, uniformly mixing, adding 10g of porous nano fibers, and uniformly dispersing to obtain mixed sol;
3) The mass volume ratio is 1g:20mL, adding silica fiber aerogel into the mixed sol, fully stirring, sealing in a container, placing into a 75 ℃ oven for heat preservation for 5h, taking out the product, replacing the product with ethanol, drying, transferring to a calciner, calcining at a high temperature of 1000 ℃ for 6h, and crushing to obtain the porous fiber composite gel.
The preparation method of the porous nanofiber comprises the following steps:
1) Adding 8g of polyacrylonitrile into 80mLN, N-dimethylformamide, fully stirring to obtain a dispersion solution, carrying out electrostatic spinning on the dispersion solution, setting the receiving distance to be 20cm, carrying out electrostatic spinning at the flow rate of 10kV and 0.05mL/min, and drying the obtained fiber in an oven at 80 ℃ for 18 hours to obtain nanofiber;
2) Heating the nanofiber to 300 ℃ in an air atmosphere, controlling the temperature rising rate to be 3 ℃/min, preserving heat for 5 hours, then heating to 800 ℃ in an argon atmosphere, controlling the temperature rising rate to be 6 ℃/min, preserving heat for 9 hours, and cooling to room temperature to obtain the porous nanofiber.
Comparative example 1: this comparative example is essentially the same as example 1, except that no porous fiber composite gel was added during the preparation of the debonded composite.
Comparative example 2: this comparative example is substantially the same as example 1, except that no porous nanofiber was added during the preparation of the porous fiber composite gel.
Comparative example 3: this comparative example is substantially the same as example 1, except that nanofibers are used in place of the porous nanofibers in the preparation of the porous fiber composite gel.
Comparative example 4: this comparative example is substantially the same as example 1 except that no dispergate compound is contained.
Comparative example 5: this comparative example is essentially the same as example 1, except that an equal amount of the debonder agent (water glass selected) is used instead of the debonder complex.
Test:
Materials were obtained by the preparation methods disclosed in examples 1 to 3 and comparative examples 1 to 5, and slurry samples having a concentration of 360g/200mL were obtained by press-filtering and dehydration, and formation tests were performed on the slurry samples, and the results are shown in Table 1.
Fluidity measurement: filling a slurry sample into a coating 4 viscometer (100 mL), pressing a stopwatch while opening an outlet, and recording stopwatch data, namely the fluidity s of slurry;
Pulp suction speed measurement: using gypsum crucible method, using parched semi-hydrated gypsum to make gypsum crucible (height 8cm, inner diameter 4cm, wall thickness 3 cm), and oven drying at 70deg.C; injecting a slurry sample into a crucible, measuring and calculating the initial height mm of the slurry, standing for 45min, measuring the final height mm of the slurry again, performing 5 parallel tests, calculating an average value, and calculating the following formula: pulp suction speed v= (H1-H2)/t; wherein, H1 is the height of the slurry in the gypsum crucible before standing, H2 is the height of the slurry in the gypsum crucible after standing, and t is the standing time s after the slurry is injected into the crucible;
Dry flexural strength: pouring the slurry sample into a test strip by using a gypsum mold, wherein the length of the test strip is 100mm, the width of the test strip is 10mm, the thickness of the test strip is 10mm, putting the test strip into an oven for drying, placing the test strip on a support with the span of 60mm, and measuring data of the test strip when the test strip is bent by using an electronic universal tester, namely, the flexural strength Mpa of the test strip.
As can be seen from Table 1, the ball clay of the invention has excellent comprehensive properties, good fluidity, slurry suction speed and drying flexural strength, thereby being beneficial to improving the quality of ceramic products and promoting the rapid high-quality development of ceramic industry.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. The preparation method of the high-performance ball clay for the ceramic sanitary ware is characterized by comprising the following steps of:
1) Preparing raw materials, weighing kaolin, raw ore mud, secondary clay, calcium chloride, a dispergation compound and water;
2) Mixing kaolin, raw ore mud and secondary clay, adding water, fully stirring and mixing to form slurry, removing impurities through a vibrating screen, adding calcium chloride, and settling to obtain high-purity slurry;
3) Adding the dispergation compound into the high-purity slurry, uniformly mixing, and carrying out filter pressing dehydration on the uniformly mixed material to obtain the required high-performance ball clay;
The preparation method of the dispergation compound comprises the following steps: adding sodium bisulfate into deionized water, fully stirring and dissolving, heating, adding acrylic acid, sodium methallyl sulfonate and ammonium persulfate, uniformly mixing, adding porous fiber composite gel, carrying out heat preservation reaction for 2-5h, naturally cooling after the reaction is finished, and regulating the pH to 7.5-8.0 by using sodium hydroxide solution to obtain a dispergated compound;
the preparation method of the porous fiber composite gel comprises the following steps:
1) Mixing and stirring tetraethoxysilane, water, ethanol and anhydrous oxalic acid until the mixture is clarified to obtain silica sol, crushing a silica fiber film, dispersing the crushed silica fiber film in a polyethylene oxide solution, adding the silica sol, homogenizing the mixture to obtain a silica fiber dispersion liquid, and carrying out freeze drying and high-temperature calcination for 2-5 hours to obtain silica fiber aerogel;
2) Adding anhydrous oxalic acid into a mixed solution composed of dimethyl sulfoxide and water, stirring until the anhydrous oxalic acid is completely dissolved, adding methyltrimethoxysilane, stirring for 30-50min, dropwise adding ammonia water, uniformly mixing, adding porous nano fibers, and uniformly dispersing to obtain mixed sol;
3) Adding silica fiber aerogel into the mixed sol, fully stirring, sealing in a container, placing in an oven for heat preservation, taking out a product, replacing with ethanol, drying, transferring to a calciner, calcining at high temperature, and crushing to obtain the porous fiber composite gel.
2. The method for preparing the high-performance ball clay for the ceramic sanitary ware according to claim 1, wherein the raw materials comprise, by weight, 15-30 parts of kaolin, 10-16 parts of raw mineral mud, 8-12 parts of secondary clay, 0.4-0.8 part of calcium chloride, 2-4 parts of dispergation compound and 20-28 parts of water.
3. The method for preparing the high-performance ball clay for the ceramic sanitary ware according to claim 1, wherein the dosage ratio of the sodium bisulphite, the deionized water, the acrylic acid, the sodium methallyl sulfonate, the ammonium persulfate and the porous fiber composite gel is (3-6) g: (150-260) mL: (38-45) g: (8-13) g: (0.3-0.8) g: (8-15) g;
the heating temperature is 50-56 ℃;
Naturally cooling to 40-43 ℃;
the concentration of the sodium hydroxide solution is 30-35wt%.
4. The method for preparing high-performance ball clay for ceramic sanitary wares according to claim 1, wherein in step 1), the silicon dioxide sol comprises the following components in percentage by weight: (4-15) g: (10-30) g: (0.01-0.05) g;
The dosage proportion of the silicon dioxide fiber film, the polyethylene oxide solution and the silicon dioxide sol is (1-3) g: (200-500) g: (0.26-0.32) g;
the concentration of the polyethylene oxide solution is 0.01-0.03wt%;
the high-temperature calcination temperature is 800-900 ℃.
5. The method for preparing the high-performance ball clay for ceramic sanitary wares according to claim 1, wherein in the step 2), the dosage ratio of the anhydrous oxalic acid, dimethyl sulfoxide, water, methyltrimethoxysilane, ammonia water and porous nano fiber is (0.34-0.45) g: (170-190) g: (52-60) g: (2-5) g: (1-3) mL: (5-10) g;
The concentration of the ammonia water is 22-25wt%.
6. The method for preparing high-performance ball clay for ceramic sanitary wares according to claim 1, wherein in step 3), the mass-to-volume ratio of the silica fiber aerogel to the mixed sol is 1g: (10-20) mL;
the heat preservation time in the oven is 2-5h, and the temperature is 70-75 ℃;
the high-temperature calcination temperature is 950-1000 ℃.
7. The method for preparing the high-performance ball clay for ceramic sanitary wares according to claim 1, wherein the preparation method of the porous nanofiber is as follows:
1) Adding polyacrylonitrile into N, N-dimethylformamide, fully stirring to obtain a dispersion solution, carrying out electrostatic spinning on the dispersion solution, and drying to obtain nanofibers;
2) Heating and preserving heat of the nanofiber for 2-5h in an air atmosphere, then heating and preserving heat for 4-9h in a nitrogen atmosphere, and cooling to room temperature to obtain the porous nanofiber.
8. The method for preparing high-performance ball clay for ceramic sanitary wares according to claim 7, wherein the dosage ratio of polyacrylonitrile to N, N-dimethylformamide in the dispersion solution is (6-8) g: (50-80) mL;
the parameters of the electrostatic spinning are as follows: the receiving distance is 15-20cm, the voltage is 8-10kV, and the flow rate is 0.02-0.05mL/min;
heating to 260-300 ℃ under the air atmosphere, wherein the heating rate is 1-3 ℃/min;
Heating to 750-800 ℃ under the nitrogen atmosphere, wherein the heating rate is 3-6 ℃/min.
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