CN104163650A - Porous ceramic and preparing method thereof - Google Patents
Porous ceramic and preparing method thereof Download PDFInfo
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- CN104163650A CN104163650A CN201410311168.4A CN201410311168A CN104163650A CN 104163650 A CN104163650 A CN 104163650A CN 201410311168 A CN201410311168 A CN 201410311168A CN 104163650 A CN104163650 A CN 104163650A
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Abstract
Porous ceramic and a preparing method thereof are disclosed. The porous ceramic is prepared by subjecting spontaneously-foaming ceramic slurry to foaming and shaping at room temperature and high-temperature sintering. The main components of the ceramic slurry comprise an organic polymer, a chemical foaming agent and a catalyst. The organic polymer is an uncrosslinked liquid organic polymer adopting a carbon chain or a silicon-containing main chain as a skeleton, and is in a solid state after crosslinking. The chemical foaming agent can generate hydrogen or carbon dioxide. The catalyst is used for catalyzing a crosslinking polymerization reaction. The pore size and porosity of the porous ceramic can be controlled through a formula. The porous ceramic is simple in preparation, and prone to low-cost large-scale production. The preparation process is independent of organic templates. Open-pore type porous materials and close-pore type porous materials can be prepared. The ceramic slurry is liable for pour into various moulds or gaps to prepare parts with complex shapes. The formed porous materials can be cut, processed and converted at high temperature into the porous ceramic.
Description
Technical field
The application relates to ceramic field, particularly relates to a kind of porous ceramics and preparation method thereof.
Background technology
Porous material is a class exotic materials with unique interior three-dimensional structure.Due to the existence of inner void, porous material is compared with dense material, and its peculiar property is mainly reflected in low density and high surface area.If inner void interconnects, porous material can also allow that fluid passes through in inside.Due to the peculiar property of porous material, they have purposes widely in producing and living.What the porous plastics that packed and transported is used and sponge utilized is the low density of porous material and the characteristic of energy-absorbing.The filter core utilization used of gas and liquid filter be that connectedness and the high surface area of the inner void of porous material stops and absorption particle.Industrial heterogeneous catalyst agent carrier has utilized micropore and the high surface area of porous material.
According to the framework material of porous material, porous material can be categorized as porous polymer, porous metal and porous ceramics.Porous polymer taking polyurethane foam as representative has been accomplished scale production and has been applied, and production technique is very ripe.Conventionally organic polymer can fusing or decomposition more than 300 degrees Celsius.The fusing point of common metal, below 1500 degrees Celsius, can start sintering before reaching fusing point, if be exposed in air, and easily oxidation.With polymkeric substance and metallographic phase ratio, ceramic chemical property is more stable, can under higher temperature, use, and can not melt sintering or react.Therefore in a lot of application scenarios, porous ceramics has irreplaceable status.
But, prepare at present porous ceramics, especially the porous ceramics of high porosity does not have a kind of low cost, and controllability is strong, easily the technology of large-scale production.Existing, the method taking polyurethane foam as template is a kind of representational method of preparing porous ceramics.Concrete comprise two kinds of modes, the one, in polyurethane foam, absorb oxide ceramics slurry, then, through drying and burning, obtain the oxide ceramic foam that has copied original polyurethane foam structure.Another kind of mode is that polyurethane foam pyroprocessing is changed into carbon foam, then allows silicon react with carbon by chemical vapour deposition, forms silicon carbide in the outside of carbon skeleton.No matter that mode, mainly there are two deficiencies in this template synthesis porous ceramics: the one, the skeleton of made foam materials be hollow or wrapping carbon core, reduced the physical strength of material; The 2nd, can only prepare in this way the foam materials that hole is communicated with, because must having hole UNICOM structure, template itself can allow ceramic size or ceramic forerunner enter in template, so can not prepare the foam materials of hole obturation.
Summary of the invention
The application's object is to provide a kind of new formula of preparing porous ceramics, and the preparation method of porous ceramics.
To achieve these goals, the application has adopted following technical scheme:
The application's one side discloses a kind of porous ceramics, and this porous ceramics, by the ceramic size certainly foaming, forms through room temperature foaming and high temperature sintering; Main component from the ceramic size foaming includes organic polymer, chemical foaming agent and catalyzer; Organic polymer is for taking carbochain or siliceous main chain as skeleton organic polymer, and organic polymer is in a liquid state, and is solid-state after crosslinked; Chemical foaming agent is the chemical foaming agent that can produce in hydrogen or carbonic acid gas; Catalyzer is at least one in platinic compound or complex compound, titanium compound, tin compound, organo-peroxide.Wherein, the effect of catalyzer is to carry out when can promoting at ambient temperature polyreaction and foamable reaction, and concrete polyreaction and foamable reaction are depended in the selection of catalyzer.
It should be noted that, wherein room temperature foaming refers to, under the effect of linking agent, the organic polymer crosslinking curing moulding of liquid not yet crosslinking polymerization, in this process, utilize the whipping agent adding wherein, in crosslinking curing, produce gas, thereby form vesicular structure in the organic polymer matrix of curing molding; High temperature sintering refers to, the organic polymer matrix of curing molding is carried out to pyroprocessing, makes it change into pottery.Also it should be noted that, the application's key is to adopt the specific ceramic size from foaming, carries out foaming in room temperature, and then high temperature sintering becomes porous ceramics; Being appreciated that can be with reference to existing from foam material from the principle of foaming, and the actual temp of high temperature sintering or other condition are according to different carbon, silicon organic polymer and fixed, are not specifically limited at this.
Preferably, organic polymer is at least one in vinyl polysiloxane, vinyl silica gel resin, hydroxyl polysiloxane, hydroxyl silica gel resin, the poly-silicon-carbon alkane of allyl group, allyl group poly-silazane, allyl group polysiloxane and isocyanic ester.
It should be noted that, organic polymer in the application solidifies by cross-linking polymerization, in organic polymer, contain can polymerization reaction take place functional group, these functional groups are preferably at least one in vinyl, allyl group, hydroxyl and isocyanato, therefore, every taking carbochain or siliceous main chain as skeleton, and contain these functional groups, organic polymer that can crosslinking polymerization may be used to the application; Vinyl polysiloxane, vinyl silica gel resin, hydroxyl polysiloxane, hydroxyl silica gel resin, the poly-silicon-carbon alkane of allyl group, the poly-silazane of allyl group, allyl group polysiloxane and isocyanic ester are the application's preferred version; Wherein, polyreaction can be polyaddition reaction or condensation polymerization reaction, is not specifically limited at this.
Preferably, whipping agent is at least one in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol, water or hydroxyl siloxanes.It should be noted that, the application's whipping agent is to react with organic polymer or linking agent the compound that generates gas, the preferably compound of hydroxyl.
Preferably, certainly foaming ceramic size in also comprise linking agent, in linking agent, contain can with the functional group of organic polymer polymerization reaction take place, these functional groups comprise at least one in silicon hydrogen base, hydroxyl or amino; Preferably, linking agent is at least one in many hydrogen radical siloxane, polyhydroxy siloxane, polyvalent alcohol and polyamine.It should be noted that, the application's linking agent is the one in the various organic compound taking carbochain as skeleton or the various silicoorganic compound taking siliceous main chain as skeleton, and in linking agent, contain can with the functional group of organic polymer polymerization reaction take place, these functional groups comprise at least one in silicon hydrogen base, hydroxyl and amino.Also it should be noted that, the effect of linking agent is to make uncrosslinked organic polymer crosslinking polymerization, be appreciated that, if comprised the functional group that can cause polyreaction in the molecular chain of organic polymer, only need to add catalyzer or just can make under proper condition it crosslinked voluntarily, not need to add in addition linking agent.
Preferably, certainly in the ceramic size of foaming, also comprise filler, filler is at least one in silicon carbide powder, alpha-silicon nitride powders, silicon oxide powder, alumina powder, Zirconium oxide powder, titanium dioxide powder, bio-vitric powder and hydroxyapatite powder.It should be noted that, in the application, directly just can obtain porous ceramics by the ceramic size certainly foaming, therefore can not use filler completely; The effect of filler is the ceramic content increasing in converted product, reduce volumetric shrinkage and crackle, another effect of filler is the bulk material performance that changes porous ceramics, as physical strength, heat conductivity, electrical conductivity etc., filler particles can be also to have the particle of internal structure as glass microsphere of hollow etc., therefore can select according to the need of production of different functions, be not specifically limited at this.
Preferably, the particle diameter of filler is 1 nanometer to 1 millimeter.Be appreciated that, although filler add the physical property that can change porous ceramics, same is also that tool is influential to the cross-linking polymerization of organic polymer, even also can affect the aperture of porous ceramics, and therefore preferred packing material size is between 1 nanometer to 1 millimeter; Preferably, filler shared volume percent in ceramic size is 0% to 30%, and the content of filler can not be too high, in order to avoid cause the viscosity of precursor mixture too high and cannot carry out mechanical stirring.
The application's another side discloses the preparation method of the application's porous ceramics, comprise, (a) preparation ceramic size, utilize the method for chemistry from foaming, at room temperature in liquid ceramic size, generate bubble, meanwhile, utilize chemical crosslink reaction, make liquid precursor solidifying and setting, form the porous material taking organic polymer as matrix; (b) curing porous material is carried out in controlled atmosphere to high-temperature heat treatment, be converted into porous ceramics.
Preferably, controlled atmosphere is the one in vacuum, air, nitrogen, argon gas or ammonia.It should be noted that, in the application, the effect of high-temperature heat treatment is that organic polymer matrix is burnt, or be converted into carbon or pottery, at higher temperature, make non-crystalline state pottery that crystallization and sintering occur, concrete thermal treatment temp can be adjusted according to different ceramic sizes or production object, is not specifically limited at this.Also it should be noted that, wherein air atmosphere refers to, directly in air, carries out sintering, does not need special atmospheric condition.
Layering porous ceramics or gradual change porous material prepared by the application's the preparation method who simultaneously also discloses again the application; Layering porous ceramics refers to the layering porous ceramics that the porous ceramics prepared by least two-layer different starting material is formed by stacking; Gradual change porous material refers to that one end of the porous material to ceramic slurry curing moulding in step (a) heats, and the other end does not heat or keep cooling, the one end forming is the porous ceramics transforming completely, the other end is the organic polymer porous material not transforming completely, and is the gradual change porous material of inorganic ceramic-organic porous material narrow transitional zone in the middle of two ends.
It should be noted that, in layering porous ceramics, every layer of porous material has different material composition or microstructure, has obvious interface between adjacent layers, can realize passage and connect between non-conterminous layer.Be appreciated that, the preparation method of layering porous ceramics specifically can comprise, first, prepare the porous material that one deck organic polymer is matrix, then, on the organic polymer-based porous body material of the first layer, prepare the organic polymer-based porous body material of the second layer, second layer porous material can be made with different formulas, form material composition and the microstructure different with the first layer material, by that analogy, can on the second layer, prepare the 3rd layer of porous material, finally the porous material of layering be heat-treated together and obtained layering porous ceramics.Gradual change porous material be utilize heat gradually pass transmission, one end of porous organo polysilica compound matrix to curing molding or part heat, the other end does not heat or keeps cooling, heat treated effect is gradually delivered to the other end from one end, producing heating one end is the porous ceramics transforming completely, the other end is the porous material not transforming completely, middle be the narrow transitional zone of inorganic ceramic-organic porous material.
Owing to adopting above technical scheme, the application's beneficial effect is:
The application's porous ceramics, its pore size and porosity can be controlled by formula and mixing parametric.And in the application's preparation method, room temperature forming and pyrolytic conversion do not need special equipment, easily realize large-scale production cheaply; And because preparation process does not rely on organic formwork, the microstructure height of porous material is controlled; Because bubble is directly form and grow up in liquid precursor inside, so the method can either be prepared the porous material that open cell type can be prepared again obturator-type, the precursor mixture using is that ceramic size is liquid state, be easy to be poured in various moulds or space, can prepare the parts with complex configuration by one-step moulding, the porous material of the organic polymer matrix after moulding, can also use universal cutter to carry out further cutting processing, and then pyrolytic conversion becomes porous ceramics.
Brief description of the drawings
Fig. 1: the silica gel porous material that the silica gel that is room temperature forming in the embodiment of the present application is matrix, wherein a is pictorial diagram, b is the inner structure for amplifying schematic diagram of porous material;
Fig. 2: be porous silica gel and the volume density of porous ceramics and the relationship analysis curve of foaming agents content in the embodiment of the present application, wherein a is porous silica gel data, b is porous ceramics data, and loose point is actual measurement data, and dashed curve is the variable density trend according to the mathematical model prediction of chemical foaming;
Fig. 3: be the aperture of porous material in the embodiment of the present application and the relationship analysis curve of foaming agents content;
Fig. 4: be the microtexture scanning electron microscope (SEM) photograph of porous ceramics in the embodiment of the present application, wherein a, b is the porous ceramics that does not contain filler, c, d is the porous ceramics containing 18% silicon carbide filler, e, f is the porous ceramics containing 30% silicon carbide filler.
embodiment
The application's porous ceramics, by the ceramic size certainly foaming, forms through room temperature foaming and high temperature sintering; Its liquid ceramic size is precursor mixture, at room temperature first after abundant mechanical stirring, each component mixes, and produces many small bubble seeds in inside simultaneously, now stop stirring, liquid ceramic size is poured in mould and treats that it foams voluntarily.In foaming process, the volumetric expansion of ceramic size and fill up all internal spaces of mould; Between organic molecule, occur to be cross-linked, liquid precursor gradates as solid-state, finally forms the porous material taking organic polymer as matrix simultaneously.Organic polymer is that the porous material of matrix can be the porous single polymers that does not comprise any filler, can be also the porous polymer based composites that evenly comprises filler particles.The organic polymer generating is that the microtexture of the porous material of matrix depends on formula and the blending means as the ceramic size of presoma; According to blowing agent type and consumption, and stirring velocity, the porous material of organic polymer matrix, its porosity can reach more than 70%, and pore size is adjustable within the scope of 10 microns to 10 millimeters.Porous material taking organic polymer as matrix is at the surface with mould and the finer and close smooth epidermis of surperficial self-assembling formation contacting with air, and this porous material can utilize the method for processing thermosetting polymer to carry out cutting processing.Organic polymer is the porous material of matrix, and in controlled atmosphere, carrying out high-temperature heat treatment can be converted into pottery by organic polymer.Controlled atmosphere can be vacuum, air, and nitrogen, argon gas, the one in ammonia, high-temperature heat treatment refers to that top temperature is higher than the thermal treatment of 800 degrees Celsius.Pure carbon organic compound in air, heat-treat after by complete burn off, last material is mainly the porous ceramics that filler sintering forms; The thermal treatment in air of siliceous organic compound generates silicon-dioxide, becomes the porous ceramics taking silicon-dioxide as matrix.Pure carbon organic compound is heat-treated and can be decomposed into carbon in vacuum or rare gas element, generates the porous ceramics taking carbon as matrix; Siliceous organic compound is in vacuum, and nitrogen, heat-treats in argon gas or ammonia, depends on concrete compound and atmosphere, can generate with silicon carbide, and silicon nitride, silicon oxide carbide, a kind of in carbonitride of silicium is the porous ceramics of matrix.Use than 800 degrees Celsius of higher thermal treatment temps, can make the non-crystalline state pottery generating that crystallization and sintering occur.
The application's porous ceramics can be used as filtering molten metal, the particle in filtration and adsorbed gas and liquid, the support of the catalyst of high-temperature chemical reaction, high-temperature structural material, high temperature insulating material, the air electrode of fuel cell, the reparation bone in organizational engineering etc.
By reference to the accompanying drawings the application is described in further detail below by specific embodiment.Following examples are only further described the application, should not be construed as the restriction to the application.
The porous ceramics of embodiment mono-taking porous silica gel as matrix
This example is according to the formula rate preparation ceramic size of table 1, wherein organic polymer be 20% containing vinyl silica gel resin at the suspension containing in vinyl polysiloxane, catalyzer is 2% platinum catalyst, be specially platinum-divinyl tetramethyl disiloxane/xylene solution, chemical foaming agent is ethanol, and linking agent is polymethyl hydrogen siloxane.All material is added to plastic cup, fiercely stir 1-2 minute with agitator, form the even mixed solution that is full of micro-bubble.Stop stir after plastic cup is shelved motionless, wait for 5-10 minute, until liquid foam expansion curing completes.
The porous ceramics of table 1 taking porous silica gel as matrix
| Material | Weight (%) |
| Organic polymer | 10 |
| Catalyzer | 0.01 |
| Chemical foaming agent | 0.1 |
| Linking agent | 1.0 |
Completely crued porous silica gel is taken out from plastic cup, put into atmosphere furnace.Be full of and pass into pure argon gas, being warming up to 1200 degrees Celsius with the speed of 5 degrees/min, being incubated 1 hour, then being down to room temperature with the speed of 5 degrees/min, obtaining this routine porous ceramics.
This routine porous ceramics in the process of preparation because silica gel during to ceramic conversion volume change larger, in heat-processed, easily break, be difficult to obtain the bulk sample that size is greater than 1 centimetre.The porous ceramics volume density of gained is 0.4 gram/cc of left and right, and porosity is 70-80%, is mainly open-celled structure, but includes a small amount of closed pore.This porous ceramics has good physical strength, and its tensile break strength is 5 MPa left and right after tested.It should be noted that, the effect of linking agent is to make organic polymer generation cross-linking polymerization, be appreciated that if organic polymer self with related functional group, can there is crosslinking polymerization in self, also can not use linking agent.In addition, for stable foam structure, prevent lather collapse and subside, this example has also been added tensio-active agent in ceramic size, and for reducing the surface tension of liquid ceramic size, in this example, preferred tensio-active agent is organic silicone oil.
Embodiment bis-adds the porous ceramics that the porous silica gel of filler is matrix
This example is according to the formula rate preparation ceramic size of table 2, wherein organic polymer be 20% containing vinyl silica gel resin at the suspension containing in vinyl polysiloxane, catalyzer is 2% platinum catalyst, be specially platinum-divinyl tetramethyl disiloxane/xylene solution, chemical foaming agent is ethanol, linking agent is polymethyl hydrogen siloxane, and filler is the silicon carbide powder of 5 microns of median sizes.All material is added to plastic cup, fiercely stir 1-2 minute with agitator, form the even mixed solution that is full of micro-bubble.Stop stir after plastic cup is shelved motionless, wait for 5-10 minute, until liquid foam expansion curing completes.The porous material having solidified, as shown in Figure 1, porous material has elasticity, and available blade cuts, and there is the comparatively fine and close smooth epidermis of one deck on the surface of porous material, and inside is vesicular structure.
Table 2 adds the porous ceramics taking porous silica gel as matrix of filler
| Material | Weight (%) |
| Organic polymer | 10 |
| Catalyzer | 0.01 |
| Chemical foaming agent | 0.1 |
| Linking agent | 1.0 |
| Filler | 7.5 |
Completely crued porous silica gel is taken out from plastic cup, put into atmosphere furnace.Be full of and pass into pure argon gas, being warming up to 1200 degrees Celsius with the speed of 5 degrees/min, being incubated 1 hour, then being down to room temperature with the speed of 5 degrees/min, obtaining this routine porous ceramics.
The porous ceramics of this example preparation has been because added filler, and in the time of heating, silica gel has obtained inhibition to volumetric shrinkage in ceramic conversion process, so can preparation size be 10 centimetres of above bulk samples.The porous ceramics volume density of gained is 0.4-0.6 gram/cc, and porosity is 70-80%, is mainly open-celled structure, but includes a small amount of closed pore.This porous ceramics has good physical strength, and its tensile break strength is 5 MPa left and right after tested.
In addition, the consumption of this example to chemical foaming agent and the volume density of porous material are analyzed, result as shown in Figure 2, in figure, wherein a is porous silica gel data, b is porous ceramics data, loose point is actual measurement data, dashed curve is the variable density trend according to the mathematical model prediction of chemical foaming, when whipping agent is that weight percent in precursor mixture is below 3% time at ceramic size, the volume density of porous material follows the consumption of whipping agent to be inversely proportional to substantially, in the time that the weight percent of whipping agent exceedes 3%, because the gas producing is too much, cause bubble excessive and break, foam materials subsides, volume density increases on the contrary, corresponding porous ceramics is also like this, wherein porous silica gel is the porous material forming after organic polymer curing molding, and porous ceramics is to form after porous material thermal treatment.The analysis in the aperture of chemical foaming agent and porous material as shown in Figure 3, similar with the result trend of Fig. 2, in the time that the weight percent of whipping agent is below 3%, the mean pore size of porous material is along with the consumption of whipping agent increases and increases, in the time that the weight percent of whipping agent exceedes 3%, due to too large bubble stable breaking not, mean pore size trends towards a ultimate value, no longer continues to increase.
This example is also tested the consumption of filler, result shows, the consumption of filler is proper between volume percent 0%-30%, or not add filler, the amount of adding is no more than volume ratio 30%, because filler is too much, the viscosity that can make ceramic size is too high and cannot carry out mechanical stirring.Figure 4 shows that the scanning electron microscope shape appearance figure that does not add filler, adds the prepared porous ceramics of the silicon carbide filler of 18% and 30% volume ratio, wherein a, b is the porous ceramics containing filler not, c, d is the porous ceramics containing 18% silicon carbide filler, e, and f is the porous ceramics containing 30% silicon carbide filler; The uniform filling of visible interpolation is distributed in the skeleton of porous ceramics, meanwhile, has reduced the macroscopical volumetric shrinkage of pottery in the time transforming although add filler, has improved overall mechanical strength, still can not eliminate the tiny crack of skeleton inside on microcosmic.
In addition, this example has also adopted different fillers to test, result demonstration, and silicon carbide, silicon nitride, silicon oxide, aluminum oxide, zirconium white, titanium oxide, bio-vitric and hydroxylapatite all can be prepared the porous ceramics that meets service requirements.
The layering porous ceramics of embodiment tri-with connecting passage
This example prepared plus silicon carbide filler porous silicon glue-line, add the porous silicon glue-line of zirconia filler, the porous silicon glue-line of plus silicon carbide filler, three layers of compound layering porous ceramics.
Preparation method is as follows:
A. first, prepare the porous silica gel of one deck taking silicon carbide as filler, concrete grammar is with embodiment bis-;
B. after the first layer solidifies, prepare the porous silica gel of one deck taking zirconium white as filler on the first layer porous silica gel, preparation method is with the preparation method of the first layer, and just filler changes zirconium white into;
C. after the second layer solidifies, run through two-layer porous silica gel with punch tool.
D. on the second layer, pour into a mould the 3rd layer, the 3rd layer is the porous silica gel taking silicon carbide as filler, and due to the flowable of precursor mixture, bottom is connected by the porous silica gel in hole with top layer, the same the first layer of preparation method of the 3rd layer.
E. after the 3rd layer solidifies, the porous material of three layers is heat-treated and is converted into the porous ceramics with layered structure.
The layering porous ceramics of this example preparation can be used as a kind of high temperature insulating layer of improved properties, the first layer and the 3rd layer are because added silicon carbide filler, better mechanical property, play the effect of support structure, but heat-proof quality is bad, and the middle second layer is because added zirconia filler, so heat-proof quality is superior, play main heat-blocking action, although its mechanical property is poor, but just as interlayer, between the two-layer skin taking silicon carbide as filler that has connection, total just can reach good physical strength and heat-proof quality simultaneously like this.
It should be noted that, the present embodiment has just been described a kind of preparation method of multilayer porous structure, particularly, has embodied the handiness for porous ceramics by room temperature forming legal system, and the direct or indirect expansion of the method is not limited; Be appreciated that on the basis of this example, can also prepare the layering porous ceramics of some layers, and can adopt different combinations of materials to prepare the layering porous ceramics of various functions and purposes.
Embodiment tetra-has the preparation of the organic and inorganic mixing porous material of gradual change composition
The one end with the porous material of gradual change composition is the porous ceramics transforming completely, and the other end is the porous material that the organic polymer that do not transform is completely matrix, in the middle of two ends, is organic and inorganic narrow transitional zone.This example is tested with the porous silica gel of plus silicon carbide filler, and preparation method is as follows:
A. first, prepare porous silica gel according to the method for embodiment bis-, the porous material after solidifying, is cut into long strip shape;
B. the porous silica gel of long strip shape is put into silica tube, in pipe, be full of pure nitrogen;
C. by the hot-zone of silica tube one end inserting pipe-type stove, the other end remains on stove outside, carry out cooling to outer end with fan or current, the porous silica gel one end that ensures long strip type is positioned at stove hot-zone, the other end is positioned at the cold-zone of stove outside, and stove is heated to 1100 degrees Celsius, is incubated 1 hour, then cooling, obtain this routine gradual change porous material.
The gradual change porous material of this example preparation, its one end is the porous ceramics transforming completely, and the other end is the organic polymer-based porous body material not transforming completely, and centre is to the organic porous material zone of transition of transition gradually by inorganic porous ceramic; This gradual change porous material can be used as a kind of high temperature insulating material of superior performance.The thermal conductivity ratio stupalith of organic materials is much lower, but can not be used for high-temperature field.In this gradual change material, only experience organic and inorganic conversion in the organic materials of high-temperature zone, and organic materials in cold zone still keeps the character of its organic materials, this transformation from high temperature to low temperature gradually changes, so this thermofin also changes gradually to organic from inorganic from high-temperature zone to cold zone, has ensured that like this material in each temperature range can provide best heat-proof quality under safety temperature.
It should be noted that, the present embodiment has just been described a kind of preparation method of the vesicular structure with gradual change composition, has embodied the handiness for porous ceramics by room temperature forming legal system, and the direct or indirect expansion of the method is not limited.For example, utilize similar method to prepare to have organic-electrodeless mixing porous material of annular gradient gradual change composition, or to prepare certain local be basic gradual change porous material.
Above content is the further description of the application being done in conjunction with concrete embodiment, can not assert that the application's concrete enforcement is confined to these explanations.For the application person of an ordinary skill in the technical field, not departing under the prerequisite of the application's design, can also make some simple deduction or replace, all should be considered as belonging to the application's protection domain.
Claims (10)
1. a porous ceramics, is characterized in that: described porous ceramics, by the ceramic size certainly foaming, forms through room temperature foaming and high temperature sintering; The main component of the described ceramic size from foaming includes organic polymer, chemical foaming agent and catalyzer;
Described organic polymer is the not yet crosslinked organic polymer taking carbochain or siliceous main chain as skeleton, and organic polymer is in a liquid state when uncrosslinked, is solid-state after crosslinked;
Described chemical foaming agent is the chemical foaming agent that can produce in hydrogen or carbonic acid gas;
Described catalyzer is at least one in platinic compound or complex compound, titanium compound, tin compound, organo-peroxide.
2. porous ceramics according to claim 1, is characterized in that: described organic polymer is at least one in vinyl polysiloxane, vinyl silica gel resin, hydroxyl polysiloxane, hydroxyl silica gel resin, the poly-silicon-carbon alkane of allyl group, allyl group poly-silazane, allyl group polysiloxane and isocyanic ester.
3. porous ceramics according to claim 1, is characterized in that: described whipping agent is at least one in methyl alcohol, ethanol, ethylene glycol, propyl alcohol, glycerol, water or hydroxyl siloxanes.
4. porous ceramics according to claim 1, it is characterized in that: in the described ceramic size from foaming, also comprise linking agent, in described linking agent, contain can with the functional group of described organic polymer polymerization reaction take place, described functional group comprises at least one in silicon hydrogen base, hydroxyl or amino; Preferably, described linking agent is at least one in many hydrogen radical siloxane, polyhydroxy siloxane, polyvalent alcohol and polyamine.
5. porous ceramics according to claim 1, it is characterized in that: in the described ceramic size from foaming, also comprise filler, described filler is at least one in silicon carbide powder, alpha-silicon nitride powders, silicon oxide powder, alumina powder, Zirconium oxide powder, titanium dioxide powder, bio-vitric powder and hydroxyapatite powder.
6. porous ceramics according to claim 5, is characterized in that: the particle diameter of described filler is 1 nanometer to 1 millimeter.
7. porous ceramics according to claim 5, is characterized in that: described filler shared volume percent in described ceramic size is 0% to 30%.
8. according to the preparation method of the porous ceramics described in claim 1-7 any one, comprise, (a) preparation ceramic size, utilize the method for chemistry from foaming, at room temperature in liquid ceramic size, generate bubble, meanwhile, utilize chemical crosslink reaction, make liquid precursor solidifying and setting, form the porous material taking organic polymer as matrix; (b) curing porous material is carried out in controlled atmosphere to high-temperature heat treatment, be converted into porous ceramics.
9. preparation method according to claim 8, is characterized in that: described controlled atmosphere is the one in vacuum, air, nitrogen, argon gas or ammonia.
10. layering porous ceramics or the gradual change porous material that prepared by the preparation method described in employing claim 8 or 9; Described layering porous ceramics refers to the layering porous ceramics that the porous ceramics prepared by least two-layer different starting material is formed by stacking; Described gradual change porous material refers to that one end of the porous material to ceramic slurry curing moulding in described step (a) heats, and the other end does not heat, the one end forming is the porous ceramics transforming completely, the other end is the organic polymer porous material not transforming completely, and is the gradual change porous material of inorganic ceramic-organic porous material narrow transitional zone in the middle of two ends.
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| CN104497404A (en) * | 2014-12-31 | 2015-04-08 | 深圳市沃尔核材股份有限公司 | Porcelainized polyolefin composite material and preparation method thereof |
| CN108794042A (en) * | 2018-07-13 | 2018-11-13 | 航天材料及工艺研究所 | A kind of binder for porous ceramics and preparation method thereof and application method |
| WO2019184401A1 (en) * | 2018-03-29 | 2019-10-03 | 深圳大学 | Preparation method for porous carbon material and porous carbon material |
| CN110317067A (en) * | 2019-07-19 | 2019-10-11 | 广东金意陶陶瓷集团有限公司 | Foaming agent and its preparation method and application, foamed ceramic wallboard powder and preparation method thereof |
| CN110694462A (en) * | 2019-09-30 | 2020-01-17 | 北京工业大学 | PDMS and foamed ceramic composite filler and preparation method thereof |
| CN111004048A (en) * | 2019-11-26 | 2020-04-14 | 国装新材料技术(江苏)有限公司 | SiC foamed ceramic, heat exchange tube based on SiC foamed ceramic and engine cooling protection device |
| CN112043873A (en) * | 2020-09-16 | 2020-12-08 | 浙江甬誉生物科技有限公司 | Organic polymer bridging-containing bio-inorganic composite structure material and preparation method and application thereof |
| CN112481541A (en) * | 2020-10-27 | 2021-03-12 | 中南大学 | Preparation method of high-performance ceramic reinforced iron-based composite material |
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| CN104497404A (en) * | 2014-12-31 | 2015-04-08 | 深圳市沃尔核材股份有限公司 | Porcelainized polyolefin composite material and preparation method thereof |
| WO2019184401A1 (en) * | 2018-03-29 | 2019-10-03 | 深圳大学 | Preparation method for porous carbon material and porous carbon material |
| CN108794042A (en) * | 2018-07-13 | 2018-11-13 | 航天材料及工艺研究所 | A kind of binder for porous ceramics and preparation method thereof and application method |
| CN108794042B (en) * | 2018-07-13 | 2020-11-10 | 航天材料及工艺研究所 | Binder for porous ceramic and preparation method and use method thereof |
| CN110317067A (en) * | 2019-07-19 | 2019-10-11 | 广东金意陶陶瓷集团有限公司 | Foaming agent and its preparation method and application, foamed ceramic wallboard powder and preparation method thereof |
| CN110694462A (en) * | 2019-09-30 | 2020-01-17 | 北京工业大学 | PDMS and foamed ceramic composite filler and preparation method thereof |
| CN110694462B (en) * | 2019-09-30 | 2021-09-10 | 北京工业大学 | PDMS and foamed ceramic composite filler and preparation method thereof |
| CN111004048A (en) * | 2019-11-26 | 2020-04-14 | 国装新材料技术(江苏)有限公司 | SiC foamed ceramic, heat exchange tube based on SiC foamed ceramic and engine cooling protection device |
| CN112043873A (en) * | 2020-09-16 | 2020-12-08 | 浙江甬誉生物科技有限公司 | Organic polymer bridging-containing bio-inorganic composite structure material and preparation method and application thereof |
| CN112481541A (en) * | 2020-10-27 | 2021-03-12 | 中南大学 | Preparation method of high-performance ceramic reinforced iron-based composite material |
| CN113121258A (en) * | 2021-03-17 | 2021-07-16 | 宜兴摩根热陶瓷有限公司 | High-strength high-porosity porous ceramic and preparation method thereof |
| CN113121258B (en) * | 2021-03-17 | 2023-07-07 | 宜兴摩根热陶瓷有限公司 | High-strength high-porosity porous ceramic and preparation method thereof |
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