CN117466618B - Rare earth modified low-deformation-rate sanitary ceramic pug and preparation method and application thereof - Google Patents
Rare earth modified low-deformation-rate sanitary ceramic pug and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 47
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 47
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 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 31
- -1 rare earth compound Chemical class 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 229910052746 lanthanum Inorganic materials 0.000 claims description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 16
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 claims description 14
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 13
- 238000000498 ball milling 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 11
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052656 albite Inorganic materials 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 229910010293 ceramic material Inorganic materials 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 10
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 9
- 229910052863 mullite Inorganic materials 0.000 description 9
- 238000002156 mixing Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- BEDFIBPNPHRGDO-UHFFFAOYSA-N yttrium;hydrate Chemical compound O.[Y] BEDFIBPNPHRGDO-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a rare earth modified low-deformation sanitary ceramic pug and a preparation method and application thereof, wherein the rare earth modified low-deformation sanitary ceramic pug comprises finished porcelain pug, rare earth compound, binder and water, and the addition amount of the rare earth compound accounts for 4-40% of the mass of the finished porcelain pug; the addition amount of the binder accounts for 0.1% -1% of the mass of the finished porcelain clay; the addition amount of water accounts for 0.1-30% of the mass of the finished porcelain clay. The pug can reach the deformation of the calcined product below 20 and mm, has smooth appearance, greatly reduces the consumption of porcelain clay and glaze, and saves the production cost.
Description
Technical Field
The invention belongs to the field of ceramic pug preparation, and particularly relates to a rare earth modified low-deformation-rate sanitary ceramic pug, and a preparation method and application thereof.
Background
Ceramic is a collective name of pottery and porcelain, is also an industrial art product in China, has high quality, beautiful shape and higher artistic value. The traditional ceramics comprise building sanitary ceramics, daily ceramics, industrial art ceramics, chemical ceramics and the like. With the rise of the high and new technology industry, various novel special ceramics are developed, and the ceramics become excellent functional materials to be applied to various fields of life.
Rare earth is the most distinctive dominant resource in China and is widely applied to the fields of metallurgy, machinery, petrifaction, glass, ceramics, textile and the like. Rare earth elements, known as industrial vitamins, are widely used as dopants for enhancing the properties of materials, but few applications have been reported in terms of rare earth element modified porcelain clay properties.
The research and investigation show that the prior ceramic preparation technology has a plurality of defects, such as the complex process greatly increases the production cost of the ceramic, the deformation of the ceramic after high-temperature calcination is larger, and the produced ceramic has dark color. The invention aims to solve the problem of serious ceramic deformation by doping rare earth elements.
Disclosure of Invention
In view of the above, the invention aims to overcome the defects in the prior art and provides a rare earth modified low-deformation-rate sanitary ceramic pug, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
in the first aspect, the rare earth modified low-deformation-rate sanitary ceramic pug comprises finished porcelain pug, rare earth compound, binder and water, wherein the addition amount of the rare earth compound accounts for 4-40% of the mass of the finished porcelain pug; the addition amount of the binder accounts for 0.1% -1% of the mass of the finished porcelain clay; the addition amount of water accounts for 0.1-30% of the mass of the finished porcelain clay; the rare earth compound is prepared by compounding lanthanum zirconate, cerium carbonate and yttrium oxide.
Preferably, the rare earth compound comprises lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of (5-20): (2-10): (1-10).
Preferably, the binder is one or a mixture of several of silica sol, PVA and PVB.
Preferably, the finished porcelain clay is one or a mixture of a plurality of kaolin, albite, potash feldspar and clay.
Preferably, the firing deformation of the rare earth modified low-deformation-rate sanitary ceramic pug is below 20mm.
In a second aspect, the invention also provides a preparation method of the rare earth modified low-deformation-rate sanitary ceramic pug, which comprises the following steps:
and (3) weighing the finished porcelain clay, the rare earth compound, water and the binder, sequentially placing the materials into a ball milling tank, performing ball milling by using a planetary ball mill, setting the parameters of the planetary ball mill to be 350-400 rpm, and rotating for 10-20min to obtain the rare earth modified low-deformation-rate sanitary ceramic clay.
In a third aspect, the invention also provides a low-deformation-rate sanitary ceramic, which is formed by calcining the pug as a raw material.
In the sintering process of the ceramic, the rare earth compound (lanthanum zirconate, cerium carbonate and yttrium oxide) added in the invention reacts with elements such as silicon aluminum and the like in the finished product porcelain clay to generate a low-melting-point solid solution, so that the anisotropism of the growth of mullite grains is limited, the mullite grains grow into mullite crystals in the ceramic, and the shrinkage deformation rate of mullite is further reduced. Specifically, because the ionic radius of lanthanum and cerium is equivalent to that of silicon aluminum, lanthanum and cerium ions are embedded into the framework of the silicon aluminum compound in the process of mixing and sintering with porcelain clay to play a role of supporting the framework, so that the deformation rate of the ceramic during sintering is reduced, the ionic radius of yttrium is slightly smaller, and a proper amount of yttrium can be added to fill gaps among the lattices. In addition, cerium element is beneficial to promoting the generation of mullite crystal phase and reducing the deformation rate of ceramic during calcination. In conclusion, lanthanum zirconate, cerium carbonate and yttrium oxide in the rare earth compound selected by the invention have synergistic interaction in the sintering process, so that the shrinkage rate of the porcelain clay in the sintering process is reduced.
Compared with the prior art, the invention has the following advantages:
the pug can reach the deformation of the calcined product below 20 and mm, has smooth appearance, greatly reduces the consumption of porcelain clay and glaze, and saves the production cost; meanwhile, the final product has no overflow of harmful substances to human bodies, is environment-friendly and healthy, and is a new direction for producing sanitary ceramics.
Drawings
FIG. 1 is an XRD pattern of different rare earth modified porcelain clay;
FIG. 2 is a microscopic electron microscopic image of the ceramic prepared in example 1;
FIG. 3 is a microscopic electron microscopic image of the ceramic manufactured in comparative example 1.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
And mixing lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of 5:5:1 to prepare the rare earth compound. The porcelain clay, the rare earth compound, the water and the silica sol are weighed according to the mass ratio of 100:9:25:0.6, sequentially put into a ball milling tank, and ball-milled by using a planetary ball mill. Setting the parameters of the planetary ball mill to be the rotating speed of 400rpm and the rotating time of 15 min, and obtaining the slurry with low deformation rate. The slurry is slowly poured into a strip-shaped mold and is kept stand for 12h forming. And drying the formed porcelain strips at 110 ℃ for 3 hours, heating to 1150 ℃ at a heating rate of 5 ℃/min for calcination for 3 hours, and slowly cooling to room temperature to obtain the ceramic material. The shrinkage of the sample bar was 4% and the deformation was 10mm. The ceramic material prepared according to the preparation method has the following element contents: la 1.6%, ce 1.4%, Y0.3%, zr 0.9%, si 30.0%, al 22.1%, mg 0.5%, K1.4%, fe 0.9%, ca 0.6% and no exudation of heavy metal ions such as Mn, cr, pb and the like.
Example 2
And mixing lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of 10:2:5 to prepare the rare earth compound. The porcelain clay, the rare earth compound, the water and the PVA are weighed according to the mass ratio of 100:15:28:0.1, are sequentially put into a ball milling tank, and are subjected to ball milling by using a planetary ball mill. Setting the parameters of the planetary ball mill to be the rotating speed of 350-400 rpm and the rotating time of 15 min, so as to obtain the slurry with low deformation rate. Slowly pouring the slurry into a strip-shaped mold, and standing for 12h for molding. And drying the formed porcelain strips at 110 ℃ for 3 hours, heating to 1150 ℃ at a heating rate of 5 ℃/min for calcination for 3 hours, and slowly cooling to room temperature to obtain the ceramic material. The shrinkage of the sample bar was 2% and the deformation was 5mm. The ceramic material prepared according to the preparation method has the following element contents: la 3.3%, ce 0.8%, Y1.2%, zr 1.8%, si 31.0%, al 20.0%, mg 0.4%, K1.2%, fe 1.0%, ca 0.6% and no exudation of heavy metal ions such as Mn, cr, pb and the like.
Example 3
And mixing lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of 20:7:10 to prepare the rare earth compound. The porcelain clay, the rare earth compound, the water and the PVB are weighed according to the mass ratio of 100:30:5:0.8, sequentially put into a ball milling tank, and ball-milled by using a planetary ball mill. Setting the parameters of the planetary ball mill to be the rotating speed of 350-400 rpm and the rotating time of 15 min, so as to obtain the slurry with low deformation rate. Slowly pouring the slurry into a strip-shaped mold, and standing for 12h for molding. And drying the formed porcelain strips at 110 ℃ for 3 hours, heating to 1150 ℃ at a heating rate of 5 ℃/min for calcination for 3 hours, and slowly cooling to room temperature to obtain the ceramic material. The shrinkage of the sample bar was 3% and the deformation was 8mm. The ceramic material prepared according to the preparation method has the following element contents: la 5.4%, ce 2.1%, Y2.8%, zr 3.0%, si 33.2%, al 21.1%, mg 0.3%, K0.9%, fe 1.1%, ca 0.5% and no exudation of heavy metal ions such as Mn, cr, pb, etc.
Example 4
And mixing lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of 15:10:3 to prepare the rare earth compound. And weighing porcelain clay, rare earth compound, water and silica sol according to the mass ratio of 100:10:30:1, sequentially putting the porcelain clay, the rare earth compound, the water and the silica sol into a ball milling tank, and performing ball milling by using a planetary ball mill. Setting the parameters of the planetary ball mill to be the rotating speed of 350-400 rpm and the rotating time of 15 min, so as to obtain the slurry with low deformation rate. Slowly pouring the slurry into a strip-shaped mold, and standing for 12h for molding. And drying the formed porcelain strips at 110 ℃ for 3 hours, heating to 1150 ℃ at a heating rate of 5 ℃/min for calcination for 3 hours, and slowly cooling to room temperature to obtain the ceramic material. The shrinkage of the sample bar was 4% and the deformation was 12mm. The ceramic material prepared according to the preparation method has the following element contents: la 1.6%, Y1.1%, ce 0.4%, zr 1.1%, si 33.1%, al 22.6%, mg 0.4%, K1.3%, fe 0.9%, ca 0.6%, P1.4% and no exudation of heavy metal ions such as Mn, cr, pb, etc.
Example 5
And mixing lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of 4:5:1 to prepare the rare earth compound. The porcelain clay, the rare earth compound, the water and the silica sol are weighed according to the mass ratio of 100:4:10:0.5, are sequentially put into a ball milling tank, and are subjected to ball milling by using a planetary ball mill. Setting the parameters of the planetary ball mill to be the rotating speed of 350-400 rpm and the rotating time of 15 min, so as to obtain the slurry with low deformation rate. The slurry is slowly poured into a strip-shaped mold and is kept stand for 12h forming. And drying the formed porcelain strips at 110 ℃ for 3 hours, heating to 1150 ℃ at a heating rate of 5 ℃/min for calcination for 3 hours, and slowly cooling to room temperature to obtain the ceramic material. The shrinkage of the sample bar was 7% and the deformation was 20mm. The ceramic material prepared according to the preparation method has the following element contents: la 0.58%, ce 0.65%, zr 0.34%, si 33.1%, al 22.6%, mg 0.4%, K1.3%, fe 0.9%, ca 0.6%, P1.4% and no exudation of heavy metal ions such as Mn, cr, pb and the like.
Comparative example 1
The components and proportions of the slurry and the preparation method of the ceramic material of the comparative example are the same as those of comparative example 1, except that the components and proportions of the slurry are as follows: the porcelain clay, lanthanum zirconate, water and silica sol are weighed according to the mass ratio of 100:9:25:0.6. The resulting sample had a shrinkage of 9% and a deformation of 25mm.
Comparative example 2
The components and proportions of the slurry and the preparation method of the ceramic material of the comparative example are the same as those of comparative example 1, except that the components and proportions of the slurry are as follows: the porcelain clay, cerium carbonate, water and silica sol are weighed according to the mass ratio of 100:9:25:0.6. The obtained sample bar had a shrinkage of 8% and a deformation of 22mm.
Comparative example 3
The components and proportions of the slurry and the preparation method of the ceramic material of the comparative example are the same as those of comparative example 1, except that the components and proportions of the slurry are as follows: the porcelain clay, yttrium oxide, water and silica sol are weighed according to the mass ratio of 100:9:25:0.6. The obtained sample bar had a shrinkage of 9% and a deformation of 23mm.
Comparative example 4
The components and proportions of the slurry and the preparation method of the ceramic material of the comparative example are the same as those of comparative example 1, except that the components and the rare earth compound of the slurry are: lanthanum zirconate and cerium carbonate with the mass ratio of 1:1 are mixed to prepare the rare earth compound. And weighing the porcelain clay, the rare earth compound, the water and the silica sol according to the mass ratio of 100:9:25:0.6. The obtained sample bar had a shrinkage of 8% and a deformation of 22mm.
Comparative example 5
The components and proportions of the slurry and the preparation method of the ceramic material of the comparative example are the same as those of comparative example 1, except that the components and proportions of the slurry are as follows: and weighing the porcelain clay, water and silica sol according to the mass ratio of 100:25:0.6. The obtained sample bar had a shrinkage of 11% and a deformation of 30mm.
As can be seen from FIG. 1, the ceramic after co-doping modification of lanthanum zirconate, cerium carbonate and yttrium oxide has a relatively obvious peak of mullite crystal phase, which indicates that when the three substances are co-doped for modifying the ceramic, interaction is generated, and the aluminum in the porcelain clay is more beneficial to be converted into mullite phase. Comparing fig. 2 and fig. 3, it can be seen that under the mixing action of three elements of LaCeY, the calcined ceramic generates rod-shaped mullite whisker, and the mullite whisker has a stabilizing effect on the layered structure of the porcelain clay, so that the shrinkage rate of the ceramic is greatly reduced.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A rare earth modified low-deformation rate sanitary ceramic pug is characterized in that: the ceramic clay comprises finished product ceramic clay, rare earth compound, binder and water, wherein the addition amount of the rare earth compound accounts for 4-40% of the mass of the finished product ceramic clay; the addition amount of the binder accounts for 0.1% -1% of the mass of the finished porcelain clay; the addition amount of water accounts for 0.1-30% of the mass of the finished porcelain clay; the rare earth compound is prepared by compounding lanthanum zirconate, cerium carbonate and yttrium oxide;
the rare earth compound comprises lanthanum zirconate, cerium carbonate and yttrium oxide in a mass ratio of (5-20): (2-10): (1-10);
the finished porcelain clay is one or a mixture of a plurality of kaolin, albite, potassium feldspar and clay;
the firing deformation of the rare earth modified low-deformation-rate sanitary ceramic pug is below 20mm.
2. The rare earth-modified low-deformation-rate sanitary ceramic pug according to claim 1, wherein: the binder is one or a mixture of a plurality of silica sol, PVA and PVB.
3. The method for preparing the rare earth modified low-deformation-rate sanitary ceramic pug according to claim 1 or 2, which is characterized in that: the method comprises the following steps:
and (3) weighing the finished porcelain clay, the rare earth compound, water and the binder, sequentially placing the materials into a ball milling tank, performing ball milling by using a planetary ball mill, setting the parameters of the planetary ball mill to be 350-400 rpm, and rotating for 10-20min to obtain the rare earth modified low-deformation-rate sanitary ceramic pug.
4. A low-deformation-rate sanitary ceramic, characterized in that: the ceramic is formed by calcining the pug as the raw material in claim 1 or 2.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331483A (en) * | 2003-05-12 | 2004-11-25 | Sanyu:Kk | Method for manufacturing negative ion generating ceramic material |
| CN101648791A (en) * | 2009-07-17 | 2010-02-17 | 严中飞 | Clay plate prescription |
| CN104671756A (en) * | 2015-02-05 | 2015-06-03 | 安徽青花坊瓷业股份有限公司 | Multi-color ceramic bowl and preparation technology thereof |
| CN109279871A (en) * | 2018-10-17 | 2019-01-29 | 厦门佳浴智能卫浴有限公司 | A kind of ceramic sanitary ceramic body and preparation method thereof |
| CN113004027A (en) * | 2021-03-26 | 2021-06-22 | 福建安溪马斯特陶瓷有限公司 | Wear-resistant high-performance ceramic roller and preparation method thereof |
| CN115254070A (en) * | 2022-06-30 | 2022-11-01 | 广东韩研活性炭科技股份有限公司 | Composite honeycomb adsorption material capable of being desorbed at high temperature and preparation method and application thereof |
| CN115504803A (en) * | 2022-09-14 | 2022-12-23 | 浙江天地环保科技股份有限公司 | Fly ash based cordierite honeycomb ceramic and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6906232B2 (en) * | 2002-08-09 | 2005-06-14 | Exxonmobil Chemical Patents Inc. | Molecular sieve compositions, catalysts thereof, their making and use in conversion processes |
-
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- 2023-12-28 CN CN202311823972.6A patent/CN117466618B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004331483A (en) * | 2003-05-12 | 2004-11-25 | Sanyu:Kk | Method for manufacturing negative ion generating ceramic material |
| CN101648791A (en) * | 2009-07-17 | 2010-02-17 | 严中飞 | Clay plate prescription |
| CN104671756A (en) * | 2015-02-05 | 2015-06-03 | 安徽青花坊瓷业股份有限公司 | Multi-color ceramic bowl and preparation technology thereof |
| CN109279871A (en) * | 2018-10-17 | 2019-01-29 | 厦门佳浴智能卫浴有限公司 | A kind of ceramic sanitary ceramic body and preparation method thereof |
| CN113004027A (en) * | 2021-03-26 | 2021-06-22 | 福建安溪马斯特陶瓷有限公司 | Wear-resistant high-performance ceramic roller and preparation method thereof |
| CN115254070A (en) * | 2022-06-30 | 2022-11-01 | 广东韩研活性炭科技股份有限公司 | Composite honeycomb adsorption material capable of being desorbed at high temperature and preparation method and application thereof |
| CN115504803A (en) * | 2022-09-14 | 2022-12-23 | 浙江天地环保科技股份有限公司 | Fly ash based cordierite honeycomb ceramic and preparation method thereof |
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