CN101054311B - Process of preparing porous ceramic material by ''freezing-gel forming'' - Google Patents
Process of preparing porous ceramic material by ''freezing-gel forming'' Download PDFInfo
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Abstract
The present invention discloses a 'freezing-gelling molding' process for preparing a porous ceramic material and belongs to the field of ceramic materials. By combining low temperature freezing molding with heat induced gelling solidification molding of ceramic materials and adopting macromolecule polymers, solvents, initiators or chelating agents as well as ceramic powders as raw materials, said process prepares a suspension containing a certain solid phase volume; by adopting a quick continuous heat processing course of 'crystallization melting-gelling solidification-solvent vaporization hole formation' performed inwards from blanks surfaces to obtain ceramic bodies with a microstructure of a frozen sample maintained therein, wherein the appearance of the pores is similar to that of solvents in crystallization state, then a ceramic material having a variety of porous structures and exhibiting excellent mechanical properties is obtained. The process conditions of the present invention is easy to realize, the suitable material system range is broad, and then the process is suitable of a plurality of purposes, such as filters used in high temperature conditions and catalyzer carrier and the like.
Description
Technical field
The present invention relates to the stupalith field, the technique of a kind of " freezing-gel forming " preparation porous ceramic film material is provided.
Background technology
The outstanding feature such as that stupalith has is high temperature resistant, corrosion-resistant, intensity is high, hardness is high, wherein, the stupalith (special porous ceramics) with special hole gap structure then has further specifically functional.Such as, the specific tenacity of high closed porosity stupalith is high, density is little, is applicable to as high temperature insulating material; High open porosity stupalith has flourishing specific surface area, is applicable to as strainer; Orderly directed through hole stupalith has the communicating pores gap structure of long-range order, can be used as support of the catalyst; Air vent content in the gradient gas hole ceramic material and big or small distribution gradient, the combustion chamber that is used for internal combustion turbine can be improved rate of combustion and be guaranteed the parts high strength.This is so that have the stupalith of special vesicular structure and obtained studying widely and using in the numerous areas such as oil, chemical industry, aerospace, biology, metallurgy, the energy, electronics, medicine, environmental protection.
The method for preparing at present porous ceramic film material has a variety of, can be summarized as three classes: template, the pore-forming material method of adding, direct foaming (document 1:J.Am.Ceram.Soc., 2006,89[6]: 1771-1789), but the template that the formed pore shape of these methods and quantity are subject to adopting, pore-forming material and the restriction that generates bubble, the scope of application is generally narrow.Freeze forming technique (the document 2:J.Am.Ceram.Soc. that development in recent years is got up, 2006,89[8]: 2394-2398) embodying advantage aspect the preparation special hole gap structure stupalith, thereby then its dominant mechanism is solvent elder generation freezing and crystallizing volatilizees and forms hole, but the intensity that its main drawback is base substrate to be sloughed behind the solvent is too low, thereby can't prepare large-size components, be difficult to adapt to actual production process.Polymerization occurs by the organic monomer in the ceramic suspension body and realizes the base substrate in-situ solidifying in gel injection molding and forming technology under thermoinducible condition, outstanding advantages (the document 3:Am.Ceram.Soc.Bul. such as the stupalith of preparation has that blank strength is high, near net-shape, organic content are low, 2003,82[4]: 42-46), although also be used in recent years the preparation of porous ceramic film material, but shortcoming is to be difficult to obtain to have complicated shape, the air hole structure of special distribution, the technique underaction is so that its range of application is narrower.Therefore, cryogenic freezing moulding and heat-induced gelation casting are combined, can obtain controlled, complicated air hole structure, can obtain high-intensity base substrate again, have great importance for development and the application of porous ceramic film material.
According to the retrieval, also freeze forming and heat-induced gelation casting are not combined the report for preparing special porous ceramic film material both at home and abroad at present.
Summary of the invention
The technique that the purpose of this invention is to provide a kind of " freezing-gel forming " preparation porous ceramic film material, it is characterized in that, the moulding of stupalith cryogenic freezing and heat-induced gelation curing molding are combined, in a technological process, realize " cold-hot " two links; The concrete technology step is as follows:
1) take organic monomer, solvent, initiator and ceramic powder as raw material, or high molecular polymer, solvent and ceramic powder be raw material, and preparation becomes the suspensoid that solid volume content is 10vol%～40vol%;
2) in suspensoid, add solvent modifier (such as glycerine, water) or other kind kind solvent, change the pattern of solvent low temperature crystallization, control the direction of solvent crystallization by the distribution of control freezing temp field;
When 3) adopting the monomer polymerization system, the suspensoid that step 2 is added solvent modifier is cooled to more than the solvent crystallization temperature, below the monomer polymerization temperature, the initiator that adds therein monomer polymerization, stir, inject mould, place the following environment of solvent crystallization temperature to carry out fully freezing; When adopting the high molecular polymer cross-linking system, then need not add initiator, the suspensoid that directly step 2 is obtained carries out cryogenic freezing and gets final product; In refrigerating process, the solvent crystallization growth in the suspensoid produces push effect to the ceramic powder on next door simultaneously, thereby forms the microtexture of solvent crystallization body (pore template) and high density ceramic particle aggregation district (air vent wall) coexistence;
Freezing base substrate demoulding under the solvent crystallization temperature that 4) will be obtained by step 3, fast transfer is in the environment that is higher than 5 ℃～10 ℃ of solvent boiling points.At first, the solvent of freezing sample surfaces melts fast, and simultaneously the organic monomer polyreaction can occur with very fast speed, realizes gel solidification so that connect by polymer phase between the ceramic powder; Perhaps solvent fast volatilization so that wherein high molecular polymer occur crosslinkedly, ceramic powder is coupled together the realization gel solidification.Solvent evaporates subsequently obtains having the base substrate with the pore of solvent freezing and crystallizing homomorphosis;
5) base substrate of step 4 is further carried out air blast oven dry, high temperature binder removal, pressureless sintering according to universal method after, can finally obtain having the stupalith of many air hole structures.
Described suspensoid organic monomer, solvent, initiator, solvent crystallization conditioning agent and ceramic powder are raw material, or with high molecular polymer, solvent, solvent crystallization conditioning agent and ceramic powder are raw material, under the temperature that is higher than 10 ℃～20 ℃ of solvent crystallization temperature, with organic monomer or high molecular polymerization raw material and solvent according to greater than the ratio of 10wt% prewired be mixing solutions, add ceramic powder according to the solid load that accounts for mixing solutions 5vol%～40vol% again, the condition lower seal ball milling that is higher than 5～10 ℃ of solvent crystallization temperature 24 hours, obtain stable ceramic suspension body.
The dissolving ratio of described organic monomer in solvent＞10% under the condition of heat treated, forms fast the monomer gel polymerisation, or realizes the suspensoid in-situ solidifying in the crosslinked mode of polymer, prepares low density, high-intensity ceramic body.
Described organic monomer polymeric gel system is: take acrylamide (AM) or Methacrylamide (MAM) as monomer, the organogel polymerization system of methylene-bisacrylamide as linking agent, ammonium persulphate as initiator; Acrylic acid series organic monomer gel polymerisation system (such as, hydroxy ethyl methacrylate (HEA), methylacrylic acid (HPMA)); Ethenol system organic monomer gel polymerisation system (such as, vinyl pyrrolidone (NVP), styrene sulfonic acid (SSA)); Described inorganic monomer polymerization system passes through Ca for take sodium alginate as raw material
2+Ion chelating is realized polymerization.
When adopting the monomer polymerization mode, the Tc of described solvent is-20 ℃ to 30 ℃ scope, can realize the fast transition of " solid-liquid-vapour three-phase " under the thermal treatment temp that adopts.
Described solvent is the trimethyl carbinol.
Described high molecular polymer cross linked gel curing system is: can produce molecule crosslinked high molecular polymerization objects system by solvent removal, comprise the high molecular polymer raw materials such as polyvinyl alcohol (PVA), polyvinyl chloride (PVC), polystyrene (PS).
When adopting the polymer crosslinking method, the Tc of described solvent can realize the fast transition of " solid-liquid-vapour three-phase " under the thermal treatment temp that adopts in-20 ℃ to 60 ℃ scope.Described solvent comprises the trimethyl carbinol, amphene, acetoxime.
Described solvent crystallization conditioning agent is G ﹠ W, also the trimethyl carbinol, glycerine, amphene, acetoxime equal solvent can be mixed mutually, changes the xln pattern of solvent when cryocoagulation.
Described ceramic powder raw material does not have particular requirement, and the various stupaliths such as aluminum oxide, zirconium white, mullite, silicon carbide, silicon nitride are all applicable.
The quick continuous heat treatment process of " crystals melt-gel solidification-solvent vaporization pore-forming " that the invention has the beneficial effects as follows this process using, the process of this rapid thermal process is carried out to inside gradually from billet surface, thus obtained ceramic body has kept the microtexture of freezing sample, the pattern of hole is close with the crystalline state of solvent, hole wall between the hole has higher density and is linked to be integral body by organic polymer simultaneously, thereby so that base substrate has excellent mechanical property.
The methods such as composition, temperature field distribution by the control solvent obtain complicated and controlled vesicular structure, make base substrate have excellent mechanical property by gel solidification.Processing condition of the present invention are easy to realize, suitable material system scope is wide, the multiple uses such as the strainer that the stupalith with special hole gap structure of producing is applicable to use under hot conditions, support of the catalyst.
Embodiment
The invention provides the technique of a kind of " freezing-gel forming " preparation porous ceramic film material.The moulding of stupalith cryogenic freezing and heat-induced gelation curing molding are combined, in a technological process, realize " cold-hot " two links; The quick continuous heat treatment process of this process using " crystals melt-gel solidification-solvent vaporization pore-forming ", the process of this rapid thermal process is carried out to inside gradually from billet surface, thus obtained ceramic body has kept the microtexture of freezing sample, the pattern of hole is close with the crystalline state of solvent, hole wall between the hole has higher density and is linked to be integral body by organic polymer simultaneously, thereby so that base substrate has excellent mechanical property.The below enumerates embodiment the present invention is explained.
Embodiment one: high open porosity ceramic component
Under 25 ℃ temperature, acrylamide monomer, methylene-bisacrylamide and the trimethyl carbinol are become prewired solution according to 14.5: 0.5: 85 mass ratio mixed preparing, add dispersion agent citric acid (mass ratio of citric acid and aluminum oxide is 1: 100), with Glacial acetic acid pH is adjusted into 3 simultaneously; Solid volume fraction adding submicron order according to 10vol% is alumina powder jointed, and ball milling is 24 hours under 25～30 ℃ condition, obtains stable ceramic suspension body.The adding massfraction is 40% ammonium persulfate aqueous solution in suspensoid, and the ammonium persulphate consumption is 4% of suspensoid gross weight, injects mould after stirring; Subsequently suspensoid is placed cold compartment of refrigerator (5 ℃) together with mould, freezing and crystallizing can occur and be interconnected in the trimethyl carbinol in the suspensoid from outside to inside at this moment, and this freeze forming forms simultaneously the process of hole template and usually can finish within 30min.With the demoulding in the environment of base substrate about 5 ℃ after freezing, and put into fast 85 ℃ convection oven, after the trimethyl carbinol melts, the rapid polymerization reaction can occur in acrylamide monomer, subsequently trimethyl carbinol volatilization, remain its freezing formed pore in base substrate, the process of this heat-induced gelation is carried out to inside gradually from billet surface, can finish in 3-10min depending on the base substrate size is unusual.The wet base substrate of resulting porous is placed air dry oven, and at 40 ℃ of lower complete dryinies, then the temperature rise rate according to 2 ℃/min rises to 500 ℃ in the heating draft glue discharging furnace, and insulation 2h is to get rid of organism wherein; Taking-up is placed in the pressure less high temperature sintering oven, rises to 1500 ℃ according to the speed of 5 ℃/min, and insulation 2h finally obtains whole void content and is about 85%, and wherein open pore accounts for porous alumina ceramic more than 90%.
Solvent for use also can be deionized water except the trimethyl carbinol, this moment, dispersion agent adopted ammonium citrate (every liter of suspensoid adds 0.2g), suspensoid pH value is adjusted to 10, freezing temp will be below-20 ℃, perhaps adopt liquid nitrogen freezing, the heat-induced gelation temperature is 120 ℃, and drying temperature is 80 ℃.Ceramic raw material also can be selected ZrO except aluminum oxide
2, mullite, SiC, Si
3N
4Deng other multiple ceramic powder, sintering temperature is different or the requirement of final void content changed according to the stupalith characteristic.
Embodiment two: the high porosity ceramic component of holding one's breath
Under 25 ℃ temperature, with acrylamide monomer, methylene-bisacrylamide, the trimethyl carbinol and glycerine according to 14.5: 0.5: 80: 5 mass ratio mixed preparing becomes prewired solution, add dispersion agent citric acid (mass ratio of citric acid and aluminum oxide is 1: 100), with Glacial acetic acid pH is adjusted into 3; Solid volume fraction adding submicron order according to 30vol% is alumina powder jointed, and ball milling is 24 hours under 25～30 ℃ condition, obtains stable ceramic suspension body; Suspensoid stirs 20min at the condition lower magnetic force that vacuumizes and carries out de-bubble.The adding massfraction is 40% ammonium persulfate aqueous solution in suspensoid, and the ammonium persulphate consumption is 4% of suspensoid gross weight, injects mould after stirring; Subsequently mould is placed freezer compartment of refrigerator (approximately-20 ℃) in the lump together with thermal insulation layer, the solvent in this moment slurry forms freezing and crystallizing, and crystallization separate, be not communicated with, the process of this freeze forming pore-creating can be finished within 30min usually.The processes such as the demoulding subsequently, thermal treatment gel solidification, drying, binder removal, sintering and " embodiment one " are similar, finally obtain void content and be about 65%, and wherein closed pore accounts for porous alumina ceramic more than 80%.
Similar with " embodiment one ", solvent for use also can be water, and ceramic raw material also can be selected other various ceramic powders, can adjust suspensoid solid volume content in the scope of 30vol%～50vol% according to the requirement to final void content.
Embodiment three: directed through hole ceramic component
The preparation of suspensoid is similar with " embodiment one ", and the solid load of aluminum oxide is 20vol% in the suspensoid.The suspensoid that has added ammonium persulfate initiator is injected three insulations, the uncovered mould in top after stirring; subsequently mould is placed freezer compartment of refrigerator (approximately-20 ℃) in the lump together with thermal insulation layer; the trimethyl carbinol in the slurry can begin freezing and crystallizing from the top at this moment; thereby realize oriented growth in whole sample, the process of this freeze forming pore-creating can be finished within 30min usually.The processes such as the demoulding subsequently, thermal treatment gel solidification, drying, binder removal, sintering are similar with " embodiment one ", and the whole void content of the final porous ceramics that obtains is about 75%, and wherein the pore more than 95% is directed communicating structure.
Solvent for use also can be deionized water, when freezing mould from top to bottom immersed gradually in the liquid nitrogen (approximately-170 ℃, the speed that immerses is 10mm/min approximately), thereby the suspensoid in the realization mould is by the bottom directed freezing and crystallizing that begins to make progress, heat-induced gelation temperature subsequently is 120 ℃, and drying temperature is 80 ℃.Ceramic raw material also can be selected other various ceramic powders, and sintering temperature changes according to the stupalith characteristic is different.In addition, can also according to the final directed requirement that connects void content, in the scope of 10vol%～30vol%, adjust suspensoid solid volume content.
Embodiment four: gradient gas hole ceramic parts
The preparation of suspensoid is similar with " embodiment one ", and the solid load of aluminum oxide is 40vol% in the suspensoid.Inject the mould that around two ends up and down are, is incubated after the suspensoid that has added ammonium persulfate initiator stirred; subsequently the mould bottom is placed 0 ℃ mixture of ice and water; the top places 50 ℃ of environment; this moment in suspensoid the formation temperature gradient; so that the trimethyl carbinol rapid crystallization of close bottom; and crystallization does not occur in the trimethyl carbinol on close top and acrylamide monomer wherein can be owing to polymerization occurs in thermal induction, and this process can be finished within 30min usually.The bottom is freezing, that solidify on the top base substrate demoulding, and put into fast 85 ℃ convection oven, after the trimethyl carbinol thawing near the bottom, the rapid polymerization reaction can occur in acrylamide monomer wherein, subsequently trimethyl carbinol volatilization remains gradient pore structured in base substrate.The processes such as drying subsequently, binder removal, sintering are similar with " embodiment one ", and the final porous ceramics that obtains is about 75% near the void content of bottom, and the void content on close top only has 10%, and air vent content is distribution gradient in material.
Can change the temperature in cold junction and hot junction, the gradient of gas cell distribution in the control material.Solvent for use also can be deionized water except the trimethyl carbinol, this moment, the temperature of cold junction will (perhaps adopt liquid nitrogen freezing) below-20 ℃, and the temperature in hot junction will be more than 20 ℃, and thermal treatment gelling temp subsequently is 120 ℃, and drying temperature is 80 ℃.Ceramic raw material also can be selected other various ceramic powders, can also according to the requirement to the material void content, adjust suspensoid solid volume content in the scope of 10vol%～50vol%.
Embodiment five: the pottery that has special air hole structure with the preparation of high molecular polymer cross-linking system
1) take PVC/ amphene system, PVC and camphene are formulated as solution according to 1: 9 ratio, the solid volume fraction according to 5%～20% adds ceramic powder, makes suspensoid at 55 ℃～60 ℃ ball millings; Inject mould under same temperature, be cooled to room temperature (approximately 25 ℃), this moment, amphene generation crystallization formed the pore template; The at room temperature demoulding, and put into fast 100 ℃ aeration cabinet, amphene rapidly volatilization removes, and forms therein hole, and simultaneously PVC molecule generation is crosslinked, and base substrate is solidified; Obtain to have subsequently the ceramic component of high open porosity through processes such as binder removal, sintering.The suspensoid solid volume fraction is adjusted into 30%～50%, adds simultaneously the crystal habit that glycerine is regulated amphene, the ceramic component that can obtain to have high closed porosity.The control suspensoid then can form the air hole structure that aligns since an end crystallization in the low temperature crystallization process.One end is set in the low temperature crystallization process is lower than 50 ℃, the other end is higher than 65 ℃ thermograde, then can form the air hole structure of Gradient distribution.Ceramic raw material also can be selected ZrO except aluminum oxide
2, mullite, SiC, Si
3N
4Deng other multiple ceramic powder, sintering temperature is different or the requirement of final void content changed according to the stupalith characteristic.
2) take PS/ acetoxime system, PS and acetoxime are formulated as solution according to 1: 9 ratio, the solid volume fraction according to 5%～20% adds ceramic powder, makes suspensoid at 65 ℃～70 ℃ ball millings; Inject mould under same temperature, be cooled to room temperature (approximately 25 ℃), this moment, acetoxime generation crystallization formed the pore template; The at room temperature demoulding, and put into fast 100 ℃ aeration cabinet, acetoxime rapidly volatilization removes, and forms therein hole, and simultaneously PVC molecule generation is crosslinked, and base substrate is solidified; Obtain to have subsequently the ceramic component of high open porosity through processes such as binder removal, sintering.The suspensoid solid volume fraction is adjusted into 30%～50%, adds simultaneously the crystal habit that glycerine is regulated acetoxime, the ceramic component that can obtain to have high closed porosity.The control suspensoid then can form the air hole structure that aligns since an end crystallization in the low temperature crystallization process.One end is set in the low temperature crystallization process is lower than 50 ℃, the other end is higher than 65 ℃ thermograde, then can form the air hole structure of Gradient distribution.Ceramic raw material also can be selected ZrO except aluminum oxide
2, mullite, SiC, Si
3N
4Deng other multiple ceramic powder, sintering temperature is different or the requirement of final void content changed according to the stupalith characteristic.
Above-described embodiment obtains complicated and controlled vesicular structure by the methods such as composition, temperature field distribution of control solvent, makes base substrate have excellent mechanical property by gel solidification.Processing condition of the present invention are easy to realize, suitable material system scope is wide, the multiple uses such as the strainer that the stupalith with special hole gap structure of producing is applicable to use under hot conditions, support of the catalyst.
Claims (3)
1. one kind " freezing-gel forming " prepares the technique of porous ceramic film material, and take organic monomer, solvent, initiator and ceramic powder as raw material, preparation becomes the suspensoid that solid volume content is 10vol%～40vol%; To add solvent modifier in the suspensoid, to change the pattern of solvent low temperature crystallization, control the direction of solvent crystallization by the distribution of control freezing temp field; When adopting the organic monomer polymerization system, the suspensoid that adds solvent modifier is cooled to more than the solvent crystallization temperature, below the monomer polymerization temperature, adds therein initiator, stir, inject mould, place the following environment of solvent crystallization temperature to carry out fully freezing; Solvent crystallization growth in the suspensoid produces push effect to the ceramic powder on next door simultaneously, thereby forms the microtexture of solvent crystallization body and the coexistence of high density ceramic particle aggregation district; Wherein, the dissolving ratio of the organic monomer that polymeric gel occurs in solvent＞10%, under the condition of heat treated, the effect PhastGel polymerization by initiator links together ceramic powder, obtains high-intensity base substrate; It is characterized in that, the material system of described organic monomer for take acrylamide as monomer, the trimethyl carbinol is solvent; In a technological process, realize " cold-hot " two links, the moulding of stupalith cryogenic freezing and heat-induced gelation curing molding are combined, the freezing base substrate demoulding under the solvent crystallization temperature that obtains, fast transfer is in the environment that is higher than 5 ℃～10 ℃ of solvent boiling points, the solvent of freezing sample surfaces melts fast, simultaneously monomer polymerization reactions can occur with very fast speed, realizes gel solidification so that connect by polymer phase between the ceramic powder; Solvent evaporates subsequently, control solvent crystallization temperature be-20 ℃ to 30 ℃ scope, can realize the fast transition of " solid-liquid-vapour three-phase " under the thermal treatment temp of employing, obtains having the base substrate with the pore of solvent freezing and crystallizing homomorphosis; Then after carrying out air blast oven dry, high temperature binder removal, pressureless sintering according to universal method, finally obtain having the stupalith of many air hole structures.
According to claim 1 described " freezing-gel forming " preparation porous ceramic film material technique, it is characterized in that, described solvent crystallization conditioning agent is glycerine, or two or more solvents in the trimethyl carbinol, amphene, the acetoxime are mixed mutually, changes the xln pattern of solvent when cryocoagulation.
According to claim 1 described " freezing-gel forming " preparation porous ceramic film material technique, it is characterized in that, described ceramic powder raw material is aluminum oxide, zirconium white, mullite or silicon nitride.
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| CN101423380B (en) * | 2008-11-12 | 2011-11-09 | 东南大学 | Method for preparing directional arrangement pore structure porous ceramic |
| CN102295466B (en) * | 2011-06-07 | 2013-05-08 | 西安理工大学 | Method for preparing porous ceramic with crystal of binary solution as template |
| CN102285815B (en) * | 2011-06-07 | 2013-03-13 | 西安理工大学 | Method for preparing double-pore type porous ceramic |
| CN103396123B (en) * | 2013-07-30 | 2014-07-16 | 东北大学 | Method for preparing large-aperture three-dimensional network SiC ceramic material |
| CN104446625A (en) * | 2014-11-28 | 2015-03-25 | 中国科学技术大学先进技术研究院 | High-porosity porous ceramic and preparation method thereof |
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| CN107151149B (en) * | 2017-05-11 | 2020-10-27 | 西安交通大学 | Manufacturing method of ceramic matrix composite part with three-level pores |
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| CN111410540A (en) * | 2020-03-05 | 2020-07-14 | 中国科学院上海硅酸盐研究所 | Preparation method of porous silicon nitride ceramic with directional pore structure |
| CN113320061B (en) * | 2021-05-19 | 2023-01-24 | 华中科技大学 | Flexible piezoelectric composite material with high damping performance and preparation method thereof |
| CN114349519A (en) * | 2022-01-19 | 2022-04-15 | 江苏宝利金材科技有限公司 | Slurry formula and production process of gel-casting ceramic filter |
| CN115041134B (en) * | 2022-06-08 | 2023-09-22 | 中国科学院青海盐湖研究所 | Carbonized gel material with lithium adsorption performance and preparation method and application thereof |
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