CN105272189A - Microporous mullite ceramic separation membrane support and preparation method thereof - Google Patents

Microporous mullite ceramic separation membrane support and preparation method thereof Download PDF

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Publication number
CN105272189A
CN105272189A CN201510841038.6A CN201510841038A CN105272189A CN 105272189 A CN105272189 A CN 105272189A CN 201510841038 A CN201510841038 A CN 201510841038A CN 105272189 A CN105272189 A CN 105272189A
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alumina
raw material
ceramic separation
mullite ceramic
micro
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郭会师
叶方保
李文凤
张卫华
宋聪聪
叶航
高洁
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Zhengzhou University
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Zhengzhou University
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Abstract

The invention discloses a microporous mullite ceramic separation membrane support and a preparation method thereof. The preparation method comprises the following steps of firstly, uniformly mixing 40-97wt% of aluminum-silicon raw materials, 1-50wt% of aluminum oxide raw materials, 1-20wt% of cementing materials and an additive, then, additionally adding water, and stirring to prepare uniform slurry, wherein the weight percentage of the additive accounts for 0.05-5wt% of the sum of the weight percentages of the raw materials, and the weight percentage of water accounts for 20-100wt% of the sum of the weight percentages of the raw materials; pouring the slurry into a die, and standing in a room-temperature environment until solidifying and forming to obtain a blank body; and after demolding the blank body, drying and sintering to obtain the microporous mullite ceramic separation membrane support. Compared with the prior art, the microporous mullite ceramic separation membrane support has the following advantages of high porosity, high strength, small aperture, good permeability and application at high temperature. The raw materials are nontoxic and cheap; the process is simple and easy to control; products with complex shapes can be prepared; and the preparation method is suitable for industrial production. The physical and chemical indicators of the obtained microporous mullite ceramic separation membrane support are superior to the national standard.

Description

A kind of micro-pore mullite ceramic separation film supporter and preparation method thereof
Technical field
The invention belongs to technical field of ceramic material, be specifically related to a kind of micro-pore mullite ceramic separation film supporter and preparation method thereof.
Background technology
Porous Ceramic Separation Membrane has that filtration efficiency is high, chemical stability good, high temperature resistant, easy cleaning and the advantage such as renewable, is widely used in the fields such as petrochemical complex, food medicine, metallurgical and environmental engineering.Porous Ceramic Separation Membrane can regard a kind of gradient porous material as, be made up of supporter, middle layer and rete three part, wherein supporter is the basis of porous Ceramic Separation Membrane preparation and application, can be the support strength that rete provides necessary, and to the filtration efficiency of gas or liquid, there is material impact, the intensity of supporter and filtration efficiency etc. then depend primarily on its open porosity, the size of pore, shape and distribution etc., and these stomatal parameters effectively regulate by changing firing temperature, raw material composition and preparation technology etc. again.At present, porous Ceramic Separation Membrane supporter is prepared both at home and abroad mainly with Al 2o 3, ZrO 2or SiC etc. is raw material, but all there is the problems such as the high and hard-to-sinter of raw materials cost, limit its application in industrial circle and expansion.
In recent years, in order to reduce costs, some researchers start the research being devoted to mineral base porous Ceramic Separation Membrane supporter, namely directly adopt cheap natural mineral to be raw material.Mullite has the advantages such as physical strength is high, high temperature resistant, resistant to corrosion, makes it be suitable for preparation porous Ceramic Separation Membrane supporter, support of the catalyst and refractory materials etc.And the clay pit of China and bauxite etc. to have aboundresources, quality better, price low and the advantage such as easily to burn till, be the high quality raw material preparing mullite stupalith.In addition, add the content that alumina raw material effectively can improve mullite in goods in right amount in alumina-silica raw material, and alumina raw material at high temperature with the SiO in Silicon-rich glass 2reaction generates secondary mullite and consumes glassy phase, and the void content of sample can be made to raise further.In addition, the many employings of porous Ceramic Separation Membrane supporter of prior art are added pore-forming material and are carried out pore-creating as starch, hard coal, graphite or organism etc. burn lost article, and adopt machine to press or the method such as to extrude shaping, but this method exists, and raw materials cost is high, goods void content is low, surface irregularity, because easily introducing the defects such as crackle, its intensity is reduced again, and be difficult to prepare complex-shaped goods.
Summary of the invention
Object of the present invention provide for weak point existing in above-mentioned prior art just a kind of prepare have that void content is high, aperture is little, physical strength is high, high temperature resistant, resistant to corrosion and micro-pore mullite ceramic separation film supporter of the advantages such as good penetrability and preparation method thereof.
The object of the invention is to be achieved through the following technical solutions:
Micro-pore mullite ceramic separation film supporter of the present invention mainly comprises alumina-silica raw material, the alumina raw material of 1 ~ 50wt%, the gelling material of 1 ~ 20wt% that weight percent is 40 ~ 97wt%, and the additive of 0.05 ~ 5wt% of above-mentioned raw materials weight percent sum.
The particle diameter of the alumina-silica raw material described in the present invention and alumina raw material all≤0.075mm.
Alumina-silica raw material described in the present invention is one or more the mixture in kyanite, andaluzite, sillimanite, coal gangue, bauxitic clay or kaolin; Alumina raw material is α-Al 2o 3, β-Al 2o 3, γ-Al 2o 3, ρ-Al 2o 3, white fused alumina, commercial alumina, one or more mixture in aluminium hydroxide or boehmite; Described gelling material is aluminous cement, white cement, ρ-Al 2o 3, Alumina gel, alumina gel, silicon sol, one or more mixture in Silica hydrogel or aluminium Silica hydrogel; Described additive is sodium carbonate, tripoly phosphate sodium STPP, sodium hexametaphosphate, Tai-Ace S 150, carboxymethyl cellulose, Natvosol, polyacrylamide, ammonium polyacrylate, ZrO 2, CaO, MgO or TiO 2in one or more mixture; Al in described kyanite, andaluzite and sillimanite raw material 2o 3content is 25 ~ 61wt%, Al in described bauxitic clay raw material 2o 3content is 45 ~ 91wt%, Al in described kaolin starting material 2o 3content is 30 ~ 45wt%, Al in described coal shale in brick making 2o 3content is 15 ~ 45wt%; Al in described white fused alumina raw material 2o 3content>=98wt%, Al in described commercial alumina 2o 3content>=95wt%, described ρ-Al 2o 3middle Al 2o 3content>=82wt%, Al in described aluminium hydroxide 2o 3content is 65 ~ 68wt%, Al in described boehmite 2o 3content is 65 ~ 85wt%.
Micro-pore mullite ceramic separation film supporter of the present invention adopts following step to be prepared from:
(1) the alumina-silica raw material of 40 ~ 97wt%, the alumina raw material of 1 ~ 50wt%, the gelling material of 1 ~ 20wt% is got by weight percentage, and the additive of 0.05 ~ 5wt% of above-mentioned raw materials weight percent sum, mix in agitator;
(2) add the water of 20 ~ 100wt% of above-mentioned raw material weight per-cent sum in the compound China and foreign countries of step (1), stir and make uniform slip;
(3) slip of step (2) is injected mould, in room temperature environment, leave standstill 24 ~ 72h make its curing molding obtain base substrate;
(4) by the base substrate demoulding that step (3) obtains, and in the loft drier of 110 DEG C dry 24 ~ 48h, put into sintering oven and be warming up to 1300 ~ 1600 DEG C with the temperature rise rate of 3 DEG C/min, and after being incubated 3 ~ 5h, obtain micro-pore mullite ceramic separation film supporter.
Present method adopts slip casting method shaping, and can prepare complex-shaped goods as required, article shape can be tabular, tubulose or other complicated shape.Because the present invention is pore-forming material with water, therefore during slurrying, amount of water is relatively large, and the water drying of adding also leaves more open pore after evaporation in sample, is conducive to sample apparent porosity and infiltrative raising.Again because the water in the present invention is also dispersion medium, raw material through wet mixing each component can be made to mix more even, be conducive to the raising of burning rear probe intensity.This preparation method's process is simple and easy to control, cost is low, and product defect is few, intensity is high.
The apparent porosity of the micro-pore mullite ceramic separation film supporter prepared by the present invention is 20 ~ 65%, and cold crushing strength is 10 ~ 120MPa, pore mean pore size is 0.1 ~ 30 μm, is that under the condition of 0.1 ~ 0.4MPa, its nitrogen flux is 330 ~ 9870m at nitrogen pressure 3m -2h -1, be that under the condition of 0.1 ~ 0.3MPa, its pure water flux is 5.0 ~ 130m at hydraulic pressure 3m -2min -1.
In micro-pore mullite ceramic separation film supporter prepared by the inventive method, the pattern of mullite mostly is needle-like or column.Mullite due to this pattern has higher physical strength and larger length-to-diameter ratio, and easily forms staggered chain network structure, can play toughened and reinforced effect to ceramic matrix.
Beneficial effect of the present invention is as follows:
The present invention with alumina-silica natural mineral raw (as kyanite, bauxitic clay, kaolin etc.) and alumina raw material for main raw material, adopt injection forming technology and reaction in－situ sintering process to combine and prepare micro-pore mullite ceramic separation film supporter, have that raw material sources are wide, firing temperature is low and the void content of goods is high, physical strength is high, good penetrability, the advantage such as acidproof, alkaline-resisting, high temperature resistant.Raw material mostly is pottery, refractories industry commonly uses material, with low cost and environmental protection, and technological process is simple and easy to control, is applicable to suitability for industrialized production.
Embodiment
The present invention is described further below with reference to specific embodiment:
The particle diameter of the alumina raw material described in following examples of the present invention and alumina-silica raw material all≤0.075mm fine powder; Described alumina-silica raw material is one or more the mixture in kyanite, andaluzite, sillimanite, coal gangue, bauxitic clay or kaolin; Alumina raw material is α-Al 2o 3, β-Al 2o 3, γ-Al 2o 3, ρ-Al 2o 3, white fused alumina, commercial alumina, one or more mixture in aluminium hydroxide or boehmite; Described gelling material is aluminous cement, white cement, ρ-Al 2o 3, Alumina gel, alumina gel, silicon sol, one or more mixture in Silica hydrogel or aluminium Silica hydrogel; Described additive is sodium carbonate, tripoly phosphate sodium STPP, sodium hexametaphosphate, Tai-Ace S 150, carboxymethyl cellulose, Natvosol, polyacrylamide, ammonium polyacrylate, ZrO 2, CaO, MgO or TiO 2in one or more mixture; Al in described kyanite, andaluzite and sillimanite raw material 2o 3content is 25 ~ 61wt%, Al in described bauxitic clay raw material 2o 3content is 45 ~ 91wt%, Al in described kaolin starting material 2o 3content is 30 ~ 45wt%, Al in described coal shale in brick making 2o 3content is 15 ~ 45wt%; Al in described white fused alumina raw material 2o 3content>=98wt%, Al in described commercial alumina 2o 3content>=95wt%, described ρ-Al 2o 3middle Al 2o 3content>=82wt%, Al in described aluminium hydroxide 2o 3content is 65 ~ 68wt%, Al in described boehmite 2o 3content is 65 ~ 85wt%.
Embodiment 1
Get by weight percentage: the kyanite (Al of 80wt% 2o 3content is 50wt%), the commercial alumina of 17wt% and 3wt% aluminous cement be raw material, the sodium carbonate of the 0.5wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; The water of the 50wt% of additional above-mentioned raw materials weight percent sum again, stirs and prepares uniform slip; Slip is injected mould, in room temperature environment, leaves standstill 24h make its curing molding obtain base substrate; Put into the dry 12h of electric drying oven with forced convection of 110 DEG C after the base substrate demoulding, dried sample is put into sintering oven, is warming up to 1500 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 56%, compressive strength is 35MPa, mean pore size is 3.2 μm, and nitrogen flux is 402m 3m -2h -1(nitrogen pressure is 0.1MPa), pure water flux is 21m 3m -2min -1(hydraulic pressure is 0.1MPa).
Embodiment 2
Get by weight percentage: the kyanite (Al of 55wt% 2o 3content is 50wt%), the α-Al of 25wt% 2o 3ρ-the Al of micro mist, 20wt% 2o 3for raw material, the Tai-Ace S 150 of 0.2wt%, the tripoly phosphate sodium STPP of 0.3wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; Again additional above-mentioned raw materials weight percent sum 45% water, stir make uniform slip; Slip is injected mould, in room temperature environment, leaves standstill 24h make its curing molding obtain base substrate; The dry 24h of electric drying oven with forced convection of 110 DEG C is put into after the base substrate demoulding; Dried sample is put into sintering oven, is warming up to 1550 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 38.4%, compressive strength is 78.2MPa, mean pore size is 12.1 μm, and nitrogen flux is 702m 3m -2h -1(nitrogen pressure is 0.1MPa), pure water flux is 28m 3m -2min -1(hydraulic pressure is 0.1MPa).
Embodiment 3
Get by weight percentage: the bauxitic clay (Al of 70wt% 2o 3content is 70wt%), the commercial alumina fine powder of 20wt% and the silicon sol of 10wt% be raw material, the Natvosol of the 0.5wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; The water of the 70wt% of additional above-mentioned raw materials weight percent sum again, stirs and makes uniform slip; Slip is injected mould, in room temperature environment, leaves standstill 48h make its curing molding obtain base substrate; The dry 24h of electric drying oven with forced convection of 110 DEG C is put into after the base substrate demoulding; Dried sample is put into sintering oven, is warming up to 1550 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 56.3%, compressive strength is 48.2MPa, mean pore size is 7.3 μm, and nitrogen flux is 6530m 3m -2h -1(nitrogen pressure is 0.4MPa), pure water flux is 95.2m 3m -2min -1(hydraulic pressure is 0.3MPa).
Embodiment 4
Get by weight percentage: the coal gangue (Al of 45wt% 2o 3content is 45wt%), the Alumina gel of the fused white corundum of 44wt%, the white cement of 3wt% and 8wt% is raw material, the sodium carbonate of the 0.2wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; The water of the 40wt% of additional above-mentioned raw materials weight percent sum again, stirs and makes uniform slip; Slip is injected mould, in room temperature environment, leaves standstill 24h make its curing molding obtain base substrate; The dry 24h of electric drying oven with forced convection of 110 DEG C is put into after the base substrate demoulding; Dried sample is put into sintering oven, is warming up to 1550 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 45.3%, compressive strength is 62.3MPa, mean pore size is 14.3 μm, and nitrogen flux is 736m 3m -2h -1(nitrogen pressure is 0.1MPa), pure water flux is 47.3m 3m -2min -1(hydraulic pressure is 0.1MPa).
Embodiment 5
Get by weight percentage: the bauxitic clay (Al of 70wt% 2o 3content is 80wt%), the commercial alumina of 25wt% and the white cement of 5wt% be raw material, then the Tai-Ace S 150 of the 0.3wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; The water of the 60wt% of additional above-mentioned raw materials weight percent sum again, stirs and makes uniform slip; Slip is injected mould, in room temperature environment, leaves standstill 24h make its curing molding obtain base substrate; The dry 24h of electric drying oven with forced convection of 110 DEG C is put into after the base substrate demoulding; Dried sample is put into sintering oven, is warming up to 1550 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 49.7%, compressive strength is 58.2MPa, and mean pore size is 8.4 μm, and nitrogen flux is 653m 3m -2h -1(nitrogen pressure is 0.1MPa), pure water flux is 26.4m 3m -2min -1(hydraulic pressure is 0.1MPa).
Embodiment 6
Get by weight percentage: the kyanite (Al of 40wt% 2o 3content is 25wt%), the bauxitic clay (Al of 40wt% 2o 3content is 80wt%), the commercial alumina of 10wt% and the Alumina gel of 10wt% be raw material, then the titanium oxide of the 1wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; The water of the 50wt% of additional above-mentioned raw materials weight percent sum again, stirs and makes uniform slip; Slip is injected mould, in room temperature environment, leaves standstill 48h make its curing molding obtain base substrate; The dry 24h of electric drying oven with forced convection of 110 DEG C is put into after the base substrate demoulding; Dried sample is put into sintering oven, is warming up to 1300 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 31.7%, compressive strength is 58.4MPa, mean pore size is 17.5 μm, and nitrogen flux is 716m 3m -2h -1(nitrogen pressure is 0.1MPa), pure water flux is 42.1m 3m -2min -1(hydraulic pressure is 0.1MPa).
Embodiment 7
Get by weight percentage: the kyanite (Al of 90wt% 2o 3content is 50wt%), the commercial alumina of 5wt% and 1wt% aluminous cement, 4wt% ρ-Al 2o 3for raw material, the carboxymethyl cellulose of the 0.5wt% of additional above-mentioned raw materials weight percent sum, even in stirrer for mixing; The water of the 70wt% of additional above-mentioned raw materials weight percent sum again, stirs and prepares uniform slip; Slip is injected mould, leaves standstill 48h in room temperature environment and treat that its curing molding obtains base substrate; Put into the dry 48h of electric drying oven with forced convection of 110 DEG C after the base substrate demoulding, dried sample is put into sintering oven, is warming up to 1500 DEG C with 3 DEG C/min and is incubated 3h, obtain micro-pore mullite ceramic separation film supporter.
After testing, the apparent porosity of the micro-pore mullite ceramic separation film supporter obtained by the present embodiment is 64%, compressive strength is 37MPa, mean pore size is 25 μm, and nitrogen flux is 8730m 3m -2h -1(nitrogen pressure is 0.4MPa), pure water flux is 107m 3m -2min -1(hydraulic pressure is 0.3MPa).

Claims (7)

1. a micro-pore mullite ceramic separation film supporter, it is characterized in that: it mainly comprises alumina-silica raw material, the alumina raw material of 1 ~ 50wt%, the gelling material of 1 ~ 20wt% that weight percent is 40 ~ 97wt%, and the additive of 0.05 ~ 5wt% of above-mentioned raw materials weight percent sum.
2. micro-pore mullite ceramic separation film supporter according to claim 1, is characterized in that: described alumina-silica raw material and the particle diameter of alumina raw material all≤0.075mm.
3. micro-pore mullite ceramic separation film supporter according to claim 1, is characterized in that: described alumina-silica raw material is one or more the mixture in kyanite, andaluzite, sillimanite, coal gangue, bauxitic clay or kaolin; Described alumina raw material is α-Al 2o 3, β-Al 2o 3, γ-Al 2o 3, ρ-Al 2o 3, white fused alumina, commercial alumina, one or more mixture in aluminium hydroxide or boehmite; Described gelling material is aluminous cement, white cement, ρ-Al 2o 3, Alumina gel, alumina gel, silicon sol, one or more mixture in Silica hydrogel or aluminium Silica hydrogel; Described additive is sodium carbonate, tripoly phosphate sodium STPP, sodium hexametaphosphate, Tai-Ace S 150, carboxymethyl cellulose, Natvosol, polyacrylamide, ammonium polyacrylate, ZrO 2, CaO, MgO or TiO 2in one or more mixture.
4. micro-pore mullite ceramic separation film supporter according to claim 3, is characterized in that: Al in described kyanite, andaluzite and sillimanite raw material 2o 3content is 25 ~ 61wt%, Al in described bauxitic clay raw material 2o 3content is 45 ~ 91wt%, Al in described kaolin starting material 2o 3content is 30 ~ 45wt%, Al in described coal shale in brick making 2o 3content is 15 ~ 45wt%; Al in described white fused alumina raw material 2o 3content>=98wt%, Al in described commercial alumina 2o 3content>=95wt%, described ρ-Al 2o 3middle Al 2o 3content>=82wt%, Al in described aluminium hydroxide 2o 3content is 65 ~ 68wt%, Al in described boehmite 2o 3content is 65 ~ 85wt%.
5. be applicable to the preparation method preparing micro-pore mullite ceramic separation film supporter according to claim 1, it is characterized in that: described method adopts following step to realize:
(1) the alumina-silica raw material of 40 ~ 97wt%, the alumina raw material of 1 ~ 50wt%, the gelling material of 1 ~ 20wt% is got by weight percentage, and the additive of 0.05 ~ 5wt% of above-mentioned raw materials weight percent sum, mix in agitator;
(2) add the water of 20 ~ 100wt% of above-mentioned raw material weight per-cent sum in the compound China and foreign countries of step (1), stir and make distributed slurry;
(3) slip of step (2) is injected mould, in room temperature environment, leave standstill 24 ~ 72h make its curing molding obtain base substrate;
(4) by the base substrate demoulding that step (3) obtains, and in the loft drier of 110 DEG C dry 24 ~ 48h, put into sintering oven and be warming up to 1300 ~ 1600 DEG C with the temperature rise rate of 3 DEG C/min, and be incubated 3 ~ 5h, obtain micro-pore mullite ceramic separation film supporter.
6. the preparation method of micro-pore mullite ceramic separation film supporter according to claim 5, is characterized in that: in prepared micro-pore mullite ceramic separation film supporter, the pattern of mullite is needle-like or column; The shape of made supporter is tabular or tubulose.
7. the preparation method of micro-pore mullite ceramic separation film supporter according to claim 5, it is characterized in that: the apparent porosity of prepared micro-pore mullite ceramic separation film supporter is 20 ~ 65%, cold crushing strength is 10 ~ 120MPa, pore mean pore size is 0.1 ~ 30 μm, is that under the condition of 0.1 ~ 0.4MPa, its nitrogen flux is 330 ~ 9870m at nitrogen pressure 3m -2h -1, be that under the condition of 0.1 ~ 0.3MPa, its pure water flux is 5.0 ~ 130m at hydraulic pressure 3m -2min -1.
CN201510841038.6A 2015-11-28 2015-11-28 Microporous mullite ceramic separation membrane support and preparation method thereof Pending CN105272189A (en)

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CN114149276A (en) * 2020-12-31 2022-03-08 郑州轻工业大学 Micro-nano hole heat insulation refractory material containing zirconium oxide and preparation method thereof

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CN106045488A (en) * 2016-06-07 2016-10-26 贵州大学 Method for preparing inorganic ceramic membrane separation device from coal gangue
CN106238056A (en) * 2016-08-22 2016-12-21 王利萍 A kind of preparation method of modified gangue/TiO2 composite
CN108002852A (en) * 2016-10-28 2018-05-08 河南智联寰宇知识产权运营有限公司 Refractory brick containing alumina homogenization material and preparation method thereof
CN107216158B (en) * 2017-06-05 2020-02-14 武汉科技大学 Mullite plastic material and preparation method thereof
CN107216158A (en) * 2017-06-05 2017-09-29 武汉科技大学 A kind of mullite is moldable and preparation method thereof
CN111108077A (en) * 2017-09-26 2020-05-05 德尔塔阀门公司 Hydrogel injection molding formulations for ceramic products
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CN108046788A (en) * 2017-12-08 2018-05-18 刘惠强 A kind of preparation method of self-cleaning ceramic film
CN108610088A (en) * 2018-06-04 2018-10-02 武汉科技大学 A kind of alumina-mullite porous heat-insulating ceramics and preparation method thereof
CN109437864A (en) * 2018-12-10 2019-03-08 新沂北美高科耐火材料有限公司 The wear-resisting super compact high-alumina brick of one kind and its production technology
CN109748597A (en) * 2019-03-20 2019-05-14 苏州北美国际高级中学 A kind of presoma method that mutually gelling prepares mullite porous ceramic
CN114133258A (en) * 2020-12-31 2022-03-04 郑州轻工业大学 Mullite micro-nano-pore heat insulation refractory material and preparation method thereof
CN114149276A (en) * 2020-12-31 2022-03-08 郑州轻工业大学 Micro-nano hole heat insulation refractory material containing zirconium oxide and preparation method thereof
WO2022144014A1 (en) * 2020-12-31 2022-07-07 郑州轻工业大学 Mullite-based micro-nano-porous heat insulating refractory material and preparation method therefor

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