CN102643095B - SiC honeycomb ceramics material and preparation method thereof - Google Patents
SiC honeycomb ceramics material and preparation method thereof Download PDFInfo
- Publication number
- CN102643095B CN102643095B CN 201210109728 CN201210109728A CN102643095B CN 102643095 B CN102643095 B CN 102643095B CN 201210109728 CN201210109728 CN 201210109728 CN 201210109728 A CN201210109728 A CN 201210109728A CN 102643095 B CN102643095 B CN 102643095B
- Authority
- CN
- China
- Prior art keywords
- honeycomb
- powder
- honey comb
- ceramic honey
- sic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 238000005516 engineering process Methods 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 239000002356 single layer Substances 0.000 claims abstract description 4
- 241000264877 Hippospongia communis Species 0.000 claims description 86
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 60
- 238000000197 pyrolysis Methods 0.000 claims description 25
- 238000005245 sintering Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000010410 layer Substances 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 23
- 230000001413 cellular effect Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 230000008595 infiltration Effects 0.000 claims description 18
- 238000001764 infiltration Methods 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000013312 flour Nutrition 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 239000011812 mixed powder Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229960004106 citric acid Drugs 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 3
- 229920005546 furfural resin Polymers 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 3
- 229960004011 methenamine Drugs 0.000 claims description 3
- 229940116315 oxalic acid Drugs 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 230000035939 shock Effects 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 35
- 238000000034 method Methods 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004087 circulation Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000015895 biscuits Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Landscapes
- Ceramic Products (AREA)
Abstract
The invention belongs to the field of a porous ceramic material and a preparation technology thereof, particularly relates to a SiC honeycomb ceramics material which is thin in porous wall, high in strength, high in specific surface, low in expansion, high in heat conductivity, high in thermal shock resistance, and controllable in structure and a preparation method of the SiC honeycomb ceramics material. The SiC honeycomb ceramics material has a continuous and single integrated structure which is similar to the shape of a honeycomb, and is provided with a plurality of in-parallel passageways along the axial direction, wherein the shapes of the passageways can be triangular, wavelike and the like; the number of pores in each unit area, which form into a honeycomb structure, can be controlled in a range of 100/cm<2> to 5/cm<2>, and the thickness of the pore walls can be controlled in a range of 0.2mm to 2mm; the pore walls can be in an impact structure, and have a micro-pore structure as well; and the invention takes organic resin and SiC powder as main raw material, and the main raw material is prepared into a single-layer structure by a mould pressing technology and is assembled into the honeycomb structure, and is reacted, infiltrated and sintered into a final product after being pyrolyzed. The preparation technology provided by the invention is simple in technology, convenient to operate, free from complex equipment, and low in manufacture cost.
Description
Technical field
The invention belongs to porous ceramic film material and preparing technical field thereof, be specially controlled SiC ceramic honey comb material of a kind of stephanoporate thin wall, high strength, high-ratio surface, low bulk, high heat conduction, thermal shock resistance height, structure and preparation method thereof.
Background technology
Ceramic honey comb has single overall structure continuously, and many parallel passages are arranged vertically, and the shape of passage can be circle, square, triangle, hexagon, waveform etc., gains the name because being similar to favose structure.Therefore, with general block ceramic phase ratio, ceramic honey comb has characteristics such as porosity height, specific area is big, corrosion resistance is strong, weight is lighter; For general pelleted substrate, have that gas-flow resistance is little, the unit geometrical surface is big, bulk specific gravity is little, pressure fall little, diffusion length is little, be beneficial to entering and advantage such as leaving away of product of reactant, therefore be specially adapted to adsorb and the catalyst carrier of various uses; In addition, because fluid can utilize the partition of ceramic honey comb to carry out heat exchange and chemical reaction by the hole that runs through upper and lower surface on the ceramic honey comb partition.At present, ceramic honey comb has been applied to the aspects such as purification, purifying vehicle exhaust and noise elimination, sewage disposal, petrochemical refinery and molten metal filtration of industrial waste gas.
Ceramic honey comb can be made by various material, mainly contains cordierite, mullite, aluminium titanates, carborundum and silicon nitride etc.Wherein, the SiC ceramic honey comb has the thermal conductivity height, bulk density is little, specific area is high and high temperature resistant, characteristics such as chemical stability good, intensity height, therefore is suitable for the environment of high temperature, burn into oxidation, and application prospect is more extensive.
But existing problems were a lot of when extrusion forming process prepared the SiC ceramic honey comb at present, and the possibility of low precision, distortion, cracking is high during moulding; Mould is made difficulty, serious wear, and the life-span is low; The dry run organic principle must discharge totally fully, controls the bad biscuit that easily causes and damages, and yielding in the sintering, intensity is not high, and above reason causes the material preparation cost high, and performance is not high, has therefore limited applying of this kind ceramic honey comb.
Summary of the invention
The object of the present invention is to provide controlled SiC ceramic honey comb material of a kind of high-strength, high-ratio surface, structure and preparation method thereof, described ceramic honey comb material has the fundamental characteristics of SiC pottery,, resistance to chemical attack low as intensity height, thermal coefficient of expansion, anti-oxidant, high-temperature stable good, thermal shock resistance is strong etc.; The characteristics that have high-ratio surface, low bulk density, high porosity simultaneously; Described preparation method's technology is simple, and cost is low.
Technical scheme of the present invention is:
A kind of SiC ceramic honey comb material, described ceramic honey comb material is SiC, has single honeycombed overall structure continuously, and parallel passage is arranged vertically, the shape of passage is triangle or waveform; Form the unit are hole count control of honeycomb at 100～5/cm
2Between, pore wall thickness is controlled between 0.2～2mm.
Described SiC ceramic honey comb material, the hole wall structure of forming honeycomb is compact texture, perhaps adopts pore-creating technology to become a micron loose structure.
Described SiC ceramic honey comb preparation methods is raw material with powder of solid particles with the macromolecular material that has than high carbon output rate, adopts mold pressing to prepare individual layer cellular unit combination back pyrolysis, sintering, and concrete preparation process is as follows:
(1) raw material preparation
With powder of solid particles, macromolecular material, curing agent by mass percentage example be (70wt%～20wt%): (20wt%～70wt%): (1wt%～10wt%) be dissolved in the organic solvent altogether, ball milling after mechanical agitation, filter, get slip, described slurry solution solute is 5～80% of gross mass; By certain amount of organic solvent in the air-dry removal slip, making the organic solvent mass content after air-dry is between 10～15%;
Powder of solid particles is carborundum powder, silica flour or the two mixed-powder; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is: p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid;
(2) compression molding and assembling
Above-mentioned raw materials evenly is coated on the polyvinyl alcohol nonwoven, is layered on back matched moulds on the one side of splitting mould of heating then, become the individual layer cellular unit of mold shape; Perhaps, adopt the gear pair roller of heating, nonwoven after the coating is pushed curing molding between pair roller be the individual layer cellular unit with profile of tooth, then requisite number purpose individual layer cellular unit is got up with the bonding folded buttress of slip, solidify bonding slip and make it fixedly to become the honeycomb precast body, the preheat temperature of splitting mould or gear pair roller is 120-180 ℃;
(3) pyrolysis
With the pyrolysis under the protective atmosphere of argon gas, nitrogen or other inert gas of honeycomb precast body, perhaps pyrolysis under vacuum condition generates the carbonaceous honeycomb, and the polyvinyl alcohol nonwoven is burnt therebetween; Wherein, 1～10 ℃ of heating rate per minute is warming up to 800～1200 ℃, is incubated 0.5～2 hour;
(4) liquid phase reactor infiltration
The carbonaceous honeycomb that pyrolysis is obtained reacts melting infiltration sintering; the raw material of selecting for use in the reaction-sintered infiltration is silicon; sintering siliconising under the protective atmosphere of argon gas, nitrogen or other inert gas; perhaps under vacuum condition, carry out the sintering siliconising; heating rate is 5～15 ℃ of per minutes; melt temperature is: 1400～1900 ℃, be incubated 0.5～5 hour, and get SiC ceramic honey comb material.
Described organic solvent is ethanol or formaldehyde, and solvent quality concentration is between 50-90%.
Described silica flour and carborundum powder purity are more than 95%, and particle mean size is 10nm～25 μ m.
Described curing agent content is 1～10% of high molecular material resin quality; Under 100～250 ℃ of temperature, solidify 1～10 minute time.
Described compression molding mould is split cavity or gear mesh roller die tool, and mould molding is shaped as the individual layer of required honeycomb, and the single layer structure of compression moulding is triangle or waveform; Wall thickness control is between 0.2～2mm, and the unit are hole count that is assembled into honeycomb can be controlled in 100～5/cm
2Between.
Described SiC ceramic honey comb preparation methods adopts carborundum powder or carborundum powder and silica flour mixed-powder, and when wherein adopting mixed-powder, the two mass ratio is (20～90%): (80～10%).
The present invention mixes the air-dry slip made from powder of solid particles (carborundum powder, silica flour or the two mixed-powder) with the macromolecule of high carbon output rate; Slip is evenly applied the polyvinyl alcohol nonwoven, then it is layered on matched moulds pressurization in back on the one side of splitting mould of heating, make the slip compact curing, become the individual layer cellular unit with mold shape, perhaps adopt the profile of tooth pair roller extrusion modling of heating, after with the individual layer cellular unit that the obtains bonding folded buttress of slip with dilution, solidify the back and fixedly become the honeycomb precast body.
Honeycomb precast body after solidifying is carried out pyrolysis in vacuum or inert atmosphere furnace, obtain and the equiform carbon honeycomb of being formed by solid powder particle and RESEARCH OF PYROCARBON of honeycomb precast body.
In the reaction-sintered infiltration; it is overheated that silicon melt is melted under vacuum or protective atmosphere; and then the carbon of carbon honeycomb and gas phase or liquid-phase silicone reaction generate carborundum, and combine and obtain high-strength, high-ratio surface, the controlled SiC ceramic honey comb of structure material with original silicon-carbide particle in the carbon honeycomb.
The present invention is avoiding traditional preparation process SiC ceramic honey comb extrusion process poor controllability, on the high basis of cost, has developed a kind of high-strength, high-ratio surface, structure controlled SiC ceramic honey comb material and technology of preparing thereof, has following advantage:
1, the honeycomb pass is controlled.The compression molding mould is split cavity in the SiC ceramic honey comb preparation methods of the present invention, mould molding is shaped as the individual layer shape of required honeycomb, when making, mould can be shaped as triangle, waveform etc. by the designing mould fluting, as shown in Figure 1, mould fluting spacing and fluting size can be regulated, and then can be controlled to be corresponding shape at the single layer structure of slip compression moulding; Control just can be adjusted pore wall thickness in the die clearance up and down again, perhaps adopt profile of tooth pair roller extrusion process to prepare cellular unit, the pair roller profile of tooth can be triangle, it also can be waveform, roller adjustable gaps joint, cellular unit shape, controllable thickness, the unit are hole count that is assembled into honeycomb can be controlled in 100～5/cm
2Between, hole wall can be controlled between 0.2～2mm.
2, the SiC ceramic honey comb strength of materials is good.The present invention adopts the organic polymer pyrolysis to obtain carbon matrix precursor and liquid phase reactor melting infiltration sintering technology, the silicon carbide powder particle strong bonded of adding in the carborundum that the carbon that the resin pyrolysis obtains generates in the infiltration reaction and the slip, thereby silicon carbide ceramics phase particle bond strength height, there is strong interaction, even tissue is fine and closely woven, guaranteed that material has high mechanical property, avoided traditional pressureless sintering method to prepare SiC ceramic material SiC particle in conjunction with not firm, the shortcoming that intensity is not high.
3, the hole wall structure of SiC ceramic honey comb material can be controlled, and both can obtain fine and close hole wall, also can obtain a micron porous hole wall.Can add the pore-creating raw material in the raw material preparation of the present invention, the control temperature retention time obtains the hole wall structure of micron porous in sintering, also can not add the pore-creating raw material, directly obtains the ceramic honey comb material of fine and close hole wall behind the sintering.
4, technology is simple, and cost is low.Preparation technology is loaded down with trivial details in legacy cellular pottery extruding, the old-extrusion modling-drying-firing process that comprises that main material synthesize-mixes, and every step process requirement is all very strict, and raw material should be beneficial to extrusion modling and be beneficial to sintering again, and component is very complicated; Extrusion process requires very high to mould, the Mould Machining difficulty, the life-span is low, cost is high; Drying process complexity, cracking easily; Sintering process control difficulty, the risk height of distortion, yield rate is low thus, material preparation cost height.And the present invention prepares the SiC ceramic honey comb, and raw material is prepared easily; No extrusion process, Mould Machining is simple, the life-span is high; After the moulding in pyrolysis and the sintering process pottery not fragile, the yield rate height, technology is simple, and is with low cost.
In sum, the invention provides a kind of high-strength, high-ratio surface, structure controlled SiC ceramic honey comb material and technology of preparing thereof.This kind ceramic honey comb has been realized high-performance and has organically combined cheaply that preparation process is simple, controllability height, yield rate height.
Description of drawings
Fig. 1 is that the present invention splits the mould schematic diagram.
Fig. 2 is profile of tooth pair roller schematic diagram of the present invention.
Among the figure, 1 patrix; 2 counterdies; Nest unit, 3 individual layer peak; Serrated roller on 4; 5 lower toothed rollers.
The specific embodiment
The material of ceramic honey comb material of the present invention is SiC, and the ceramic honey comb material has continuously the single favose overall structure that is similar to, and many parallel passages are arranged vertically, and the shape of passage can be triangle, waveform etc.; The unit are hole count of forming honeycomb can be controlled in 100～5/cm
2Between, pore wall thickness can be controlled between 0.2～2mm.Honeycomb porous structure is controlled, and the hole wall structure of forming honeycomb can be compact texture, also can adopt pore-creating technology to become a micron loose structure.
Ceramic honey comb preparation methods technology of the present invention is simple, mainly comprises feedstock production, mold pressing unit formation, assembling and pyrolysis and firing process.
This preparation method is raw material with powder of solid particles with the macromolecular material that has than high carbon output rate, and mold pressing prepares individual layer cellular unit combination back pyrolysis, sintering, and concrete preparation process is as follows:
(1) powder of solid particles (carborundum powder, silica flour or the two mixed powder), macromolecular material, curing agent and organic solvent in certain ratio are mixed, ball milling after mechanical agitation filters, and gets slip, and described slurry solution solute is 5～80% of gross mass; By certain amount of organic solvent in the air-dry removal slip, making the organic solvent mass content after air-dry is between 10～15%.
The macromolecular material that adopts is selected from one or more of epoxy resin, phenolic resins and furfural resin, powder of solid particles can be carborundum powder, silica flour or the two mixed-powder, silica flour and carborundum powder purity are more than the 95wt%, and particle mean size is 10nm～25 μ m; Organic solvent can be ethanol, formaldehyde etc., between the solvent quality concentration 50-90%; Curing agent is: p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid etc., content is 1～10% of high molecular material resin quality, under 100～250 ℃ of temperature, solidify, 1～10 minute time, the mass percent example is (70wt%～20wt%): (20wt%～70wt%): (1wt%～10wt%) between powder of solid particles, macromolecular material and the curing agent.As adopting carborundum powder and silica flour mixed-powder, the two mass ratio is (20～90%): (80～10%).
(2) compression molding and assembling
Step (1) is obtained raw material evenly to be coated on the polyvinyl alcohol nonwoven, be layered on back matched moulds on the one side of splitting mould (seeing accompanying drawing 1) of heating then, in addition certain pressure is depressed into the spacing place that mould is subscribed then, making macromolecular material is that the slip of adhesive can compact curing under pressure, become the individual layer cellular unit of mold shape, perhaps adopt the gear pair roller (seeing accompanying drawing 2) of heating, nonwoven after the coating is pushed curing molding between pair roller be the individual layer cellular unit with profile of tooth, then the slip bonding folded buttress of requisite number purpose individual layer cellular unit with dilution got up, solidify bonding slip and make it fixedly to become the honeycomb precast body.The preheat temperature of splitting mould or gear pair roller here is 120-180 ℃.
As shown in Figure 1, the compression molding mould is the mould of splitting of patrix 1 and counterdie 2, and mould molding is shaped as the nest unit, individual layer peak 3 of required honeycomb, and nest unit, individual layer peak 3 structures of compression moulding can be triangle, waveform etc.As shown in Figure 2, the profile of tooth pair roller is that last serrated roller 4, lower toothed roller 5 are oppositely arranged structure, and the individual layer cellular unit 3 that the profile of tooth pair roller is produced is profile of tooth.
(3) pyrolysis
With the pyrolysis under protective atmosphere (argon gas, nitrogen or other inert gas) or vacuum condition of honeycomb precast body, generate the carbonaceous honeycomb, the polyvinyl alcohol nonwoven is burnt removal therebetween.Wherein, 1～10 ℃ of heating rate per minute is warming up to 800～1200 ℃, is incubated 0.5～2 hour.
(4) liquid phase reactor infiltration
The carbonaceous honeycomb that pyrolysis is obtained reacts the melting infiltration sintering siliconising; sintering carries out under protective atmosphere (argon gas, nitrogen or other inert gas) or vacuum condition; heating rate is 5～15 ℃ of per minutes; melt temperature is: 1400～1900 ℃; be incubated 0.5～5 hour, get SiC ceramic honey comb material.By controlling the hole wall structure that sintering time can access densification or micron porous, the raw material of selecting for use in the reaction-sintered infiltration is silicon.Be that sintering obtains fine and close hole wall structure below 2 hours as temperature retention time, remove as temperature retention time pore-creating raw material such as remaining Si in then can be with hole wall more than 2 hours, form micrometer level porous hole wall structure.
Experiment shows, in above-mentioned embodiment and parameter area, all can realize the object of the invention.Below by embodiment in detail the present invention is described in detail.
The particle mean size 5 μ m carborundum powders, ammonia phenolic resins, the p-methyl benzenesulfonic acid that mass ratio are respectively 60%: 35%: 5% are dissolved in the absolute ethyl alcohol altogether, and ball milling after mechanical agitation filters, and gets slip, and described slurry solution solute is 80% of gross mass; Certain ethanol in the air-dry removal slip, making the organic solvent mass content after air-dry is 10%.This raw material evenly is coated on the polyvinyl alcohol nonwoven, be layered on then on the one side of splitting mould with triangle fluting that is heated to 120 ℃, matched moulds is forced into spacing place, the spacing gap that guarantees is 0.3mm between the mould, be incubated after 1 minute and solidify, die sinking can obtain having the corrugated plate individual layer cellular unit of triangular slot, after mode prepares some blade units according to this, these unit are bonding with the folded buttress of slip, can obtain the ceramic honey comb precast body after solidifying firmly, its perforate be shaped as triangle, after with the pyrolysis under argon shield of this precast body, generate the carbonaceous ceramic honey comb; Wherein the heating rate per minute is 2 ℃, is warming up to 1200 ℃, is incubated 0.5 hour.After the pyrolysis, carry out the siliconising of vacuum reaction melting infiltration sintering, 1650 ℃ of reaction temperatures, heating rate is 10 ℃/minute, is incubated 1 hour, the infiltration raw material is Si, gets fine and close SiC ceramic honey comb material.
The technical indicator of present embodiment gained SiC ceramic honey comb material is as follows:
Unit are hole count: 100 holes/cm
2Surface volume ratio: 4800m
-1Density: 0.4g/cm
3Porosity: 85%; Compressive strength (being parallel to the hole): 70MPa; Thermal coefficient of expansion: 4.7 * 10
-6/ ℃; The strong acid-base resistance corrosion; 1000 ℃ of following shrend experiments can stand 10 circulations and not damage not oxidation.
Mass ratio was respectively 50%: 10%: 35%: 5% particle mean size 5 μ m carborundum powders and particle mean size are that 3 μ m silica flours, ammonia phenolic resins, p-methyl benzenesulfonic acid are dissolved in the absolute ethyl alcohol altogether, ball milling after mechanical agitation, filter, get slip, described slurry solution solute is gross mass 75%, certain ethanol in the air-dry removal slip, making the organic solvent mass content after air-dry is 15%.This raw material evenly is coated in the polyvinyl alcohol nonwoven, the back is pushed in being heated to the wavy profile of tooth pair roller of 150 ℃ have and is passed by, guarantee between the up-down rollers that the gap is 0.3mm, roll-in speed is 1m/1min, obtain having the corrugated plate individual layer cellular unit of wavy groove, after mode prepares some blade units according to this, these unit are bonding with the folded buttress of slip, can obtain the ceramic honey comb precast body after solidifying firmly, its perforate be shaped as waveform, after with the pyrolysis under argon shield of this precast body, generate the carbonaceous ceramic honey comb; Wherein the heating rate per minute is 2 ℃, is warming up to 900 ℃, is incubated 0.5 hour.After the pyrolysis, carry out the siliconising of vacuum reaction melting infiltration sintering, 1750 ℃ of reaction temperatures, heating rate is 10 ℃/minute, be incubated 2.5 hours, in this sintering process, the carbon reaction generates SiC in infiltration raw material Si and the carbonaceous ceramic honey comb, and SiC in the raw material is combined, continue in the vacuum heat-preserving in the back, remaining Si can be removed in the Si that adds in the slip raw material and the reaction, makes hole wall become porous, must have the SiC ceramic honey comb material of porous hole wall.
The technical indicator of present embodiment gained SiC ceramic honey comb material is as follows:
Unit are hole count: 75 holes/cm
2Surface volume ratio: 3600m
-1Density: 0.5g/cm
3Porosity: 85%; Hole wall is loose structure, and porosity is about 40%; Compressive strength (being parallel to the hole): 86MPa; Thermal coefficient of expansion: 4.7 * 10
-6/ ℃; The strong acid-base resistance corrosion; 1000 ℃ of following shrend experiments can stand 10 circulations and not damage not oxidation.
Mass ratio was respectively 60%: 20%: 15%: 5% particle mean size 1.5 μ m carborundum powders, ammonia phenolic resins, epoxy resin, p-methyl benzenesulfonic acid are dissolved in the absolute ethyl alcohol altogether, ball milling after mechanical agitation, filter, get slip, described slurry solution solute is 60% of gross mass; Certain ethanol in the air-dry removal slip, making the organic solvent mass content after air-dry is 12%.This raw material evenly is coated on the polyvinyl alcohol nonwoven, be layered on then on the one side of splitting mould with triangle fluting that is heated to 180 ℃, matched moulds is forced into spacing place, the spacing gap that guarantees is 0.8mm between the mould, be incubated after 1 minute and solidify, die sinking can obtain having the corrugated plate individual layer cellular unit of triangular slot, after mode prepares some blade units according to this, these unit are bonding with the folded buttress of slip, can obtain the ceramic honey comb precast body after solidifying firmly, its perforate be shaped as triangle, after with the pyrolysis under argon shield of this precast body, generate the carbonaceous ceramic honey comb; Wherein the heating rate per minute is 5 ℃, is warming up to 800 ℃, is incubated 2 hours.After the pyrolysis, carry out the siliconising of vacuum reaction melting infiltration sintering, 1850 ℃ of reaction temperatures, heating rate is 15 ℃/minute, is incubated 1.5 hours, the infiltration raw material is Si, gets fine and close SiC ceramic honey comb material.
The technical indicator of present embodiment gained SiC ceramic honey comb material is as follows:
Unit are hole count: 50 holes/cm
2Surface volume ratio: 2000m
-1Density: 0.8g/cm
3Porosity: 75%; Compressive strength (being parallel to the hole): 85MPa; Thermal coefficient of expansion: 4.7 * 10
-6/ ℃; The strong acid-base resistance corrosion; 1000 ℃ of following shrend experiments can stand 10 circulations and not damage not oxidation.
Claims (5)
1. SiC ceramic honey comb material, it is characterized in that: described ceramic honey comb material is SiC, has single honeycombed overall structure continuously, and parallel passage is arranged vertically, the shape of passage is triangle or waveform; Form the unit are hole count control of honeycomb at 100-5/cm
2Between, pore wall thickness is controlled between 0.2-2mm;
Be raw material with powder of solid particles and the macromolecular material that has than high carbon output rate, adopt mold pressing to prepare individual layer cellular unit combination back pyrolysis, sintering, concrete preparation process is as follows:
(1) raw material preparation
With powder of solid particles, macromolecular material, curing agent by mass percentage example for (70wt%-20wt%): (20wt%-70wt%): (1wt%-10wt%) be dissolved in the organic solvent altogether, ball milling after mechanical agitation, filter, get slip, described slurry solution solute is the 5-80% of gross mass; By certain amount of organic solvent in the air-dry removal slip, making the organic solvent mass content after air-dry is between the 10-15%;
Powder of solid particles is carborundum powder, silica flour or the two mixed-powder; Macromolecular material is selected from one or more of epoxy resin, phenolic resins and furfural resin; Curing agent is: p-methyl benzenesulfonic acid, methenamine, oxalic acid or citric acid;
(2) compression molding and assembling
Above-mentioned raw materials evenly is coated on the polyvinyl alcohol nonwoven, is layered on back matched moulds on the one side of splitting mould of heating then, become the individual layer cellular unit of mold shape; Perhaps, adopt the gear pair roller of heating, nonwoven after the coating is pushed curing molding between pair roller be the individual layer cellular unit with profile of tooth, then requisite number purpose individual layer cellular unit is got up with the bonding folded buttress of slip, solidify bonding slip and make it fixedly to become the honeycomb precast body, the preheat temperature of splitting mould or gear pair roller is 120-180 ℃;
The compression molding mould is split cavity or gear mesh roller die tool, and mould molding is shaped as the individual layer of required honeycomb, and the single layer structure of compression moulding is triangle or waveform; Wall thickness control is assembled into the unit are hole count control of honeycomb at 100-5/cm between 0.2-2mm
2Between;
(3) pyrolysis
With the pyrolysis under the protective atmosphere of argon gas, nitrogen or other inert gas of honeycomb precast body, perhaps pyrolysis under vacuum condition generates the carbonaceous honeycomb, and the polyvinyl alcohol nonwoven is burnt therebetween; Wherein, 1-10 ℃ of heating rate per minute is warming up to 800-1200 ℃, is incubated 0.5-2 hour;
(4) liquid phase reactor infiltration
The carbonaceous honeycomb that pyrolysis is obtained reacts melting infiltration sintering; the raw material of selecting for use in the reaction melting infiltration sintering is silicon; sintering siliconising under the protective atmosphere of argon gas, nitrogen or other inert gas; perhaps under vacuum condition, carry out the sintering siliconising; heating rate is per minute 5-15 ℃; melt temperature is: 1400-1900 ℃, be incubated 0.5-5 hour, and get SiC ceramic honey comb material.
2. by the described SiC ceramic honey comb of claim 1 material, be characterised in that: the hole wall structure of forming honeycomb is compact texture, perhaps adopts pore-creating technology to become a micron loose structure.
3. according to the described SiC ceramic honey comb of claim 1 material, it is characterized in that: described organic solvent is ethanol or formaldehyde, and solvent quality concentration is between 50-90%.
4. according to the described SiC ceramic honey comb of claim 1 material, it is characterized in that: described silica flour and carborundum powder purity are more than 95%, and particle mean size is 10nm-25 μ m.
5. according to the described SiC ceramic honey comb of claim 1 material, it is characterized in that: adopt carborundum powder or carborundum powder and silica flour mixed-powder, when wherein adopting mixed-powder, the two mass ratio is (20-90%): (80-10%).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210109728 CN102643095B (en) | 2012-04-16 | 2012-04-16 | SiC honeycomb ceramics material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210109728 CN102643095B (en) | 2012-04-16 | 2012-04-16 | SiC honeycomb ceramics material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102643095A CN102643095A (en) | 2012-08-22 |
| CN102643095B true CN102643095B (en) | 2013-10-09 |
Family
ID=46656215
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210109728 Expired - Fee Related CN102643095B (en) | 2012-04-16 | 2012-04-16 | SiC honeycomb ceramics material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102643095B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104876624A (en) * | 2015-05-22 | 2015-09-02 | 宁夏机械研究院股份有限公司 | Silicon carbide honeycomb ceramic pug and pugging method |
| CN109476560A (en) * | 2016-07-29 | 2019-03-15 | 日本碍子株式会社 | Porous ceramic particle and porous ceramic structure |
| CN108129162A (en) * | 2017-12-18 | 2018-06-08 | 蚌埠市宝运商品混凝土有限公司 | A kind of light-weight environment-friendly concrete material |
| CN108215339B (en) * | 2017-12-30 | 2020-04-21 | 嘉兴雅港复合材料有限公司 | High-strength aramid fiber paper honeycomb core and manufacturing method thereof |
| CN108975941A (en) * | 2018-09-17 | 2018-12-11 | 淄博正邦知识产权企划有限公司 | A kind of alumina ceramic material and preparation method thereof with biocompatibility |
| CN113277871A (en) * | 2020-02-19 | 2021-08-20 | 中国科学院金属研究所 | Porous silicon carbide honeycomb ceramic and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830901A (en) * | 2006-03-30 | 2006-09-13 | 中国科学院山西煤炭化学研究所 | Method for preparing ball shaped, porous ceramic material contg. silicon carbide with biological structure |
| CN1915520A (en) * | 2005-08-17 | 2007-02-21 | 陈庆华 | Carrier of ceramics catalyst, and microparticles collection device of constituting the carrier and their preparation method |
| EP2014630A2 (en) * | 2007-06-06 | 2009-01-14 | Ibiden Co., Ltd. | Firing jig and method for manufacturing honeycomb structured body |
| CN101555138A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院金属研究所 | Silicon carbide foamed ceramic corrugated plate and preparation method thereof |
| CN101580390A (en) * | 2008-05-15 | 2009-11-18 | 中国科学院金属研究所 | Silicon carbide ceramic tubular product and preparation method thereof |
-
2012
- 2012-04-16 CN CN 201210109728 patent/CN102643095B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915520A (en) * | 2005-08-17 | 2007-02-21 | 陈庆华 | Carrier of ceramics catalyst, and microparticles collection device of constituting the carrier and their preparation method |
| CN1830901A (en) * | 2006-03-30 | 2006-09-13 | 中国科学院山西煤炭化学研究所 | Method for preparing ball shaped, porous ceramic material contg. silicon carbide with biological structure |
| EP2014630A2 (en) * | 2007-06-06 | 2009-01-14 | Ibiden Co., Ltd. | Firing jig and method for manufacturing honeycomb structured body |
| CN101555138A (en) * | 2008-04-09 | 2009-10-14 | 中国科学院金属研究所 | Silicon carbide foamed ceramic corrugated plate and preparation method thereof |
| CN101580390A (en) * | 2008-05-15 | 2009-11-18 | 中国科学院金属研究所 | Silicon carbide ceramic tubular product and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102643095A (en) | 2012-08-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102643095B (en) | SiC honeycomb ceramics material and preparation method thereof | |
| CN101555138B (en) | Silicon carbide foamed ceramic corrugated plate and preparation method thereof | |
| KR100842595B1 (en) | Continuous firing kiln and process for producing porous ceramic member therewith | |
| US10350532B2 (en) | Porous alpha-SiC-containing shaped body having a contiguous open pore structure | |
| WO2007015550A1 (en) | Jig for silicon carbide firing and method for producing porous silicon carbide body | |
| US6699429B2 (en) | Method of making silicon nitride-bonded silicon carbide honeycomb filters | |
| US20090011208A1 (en) | Ceramics Made of Preceramic Paper or Board Structures, Method of Producing the Same and Use Thereof | |
| WO2006016430A1 (en) | Firing kiln and process for producing ceramic member therewith | |
| WO2006057344A1 (en) | Honeycomb structure | |
| CN102807384B (en) | Preparation method of high-porosity silicon-carbide porous ceramics | |
| JPWO2003081001A1 (en) | Honeycomb filter for exhaust gas purification | |
| JPWO2003067042A1 (en) | Honeycomb filter for exhaust gas purification | |
| WO2006003736A1 (en) | Jig for baking ceramic and method of manufacturing porous ceramic body | |
| JP5831453B2 (en) | Method for manufacturing ceramic honeycomb structure | |
| WO2008032391A1 (en) | Process for producing honeycomb structure and raw-material composition for burnt honeycomb | |
| JP2009515808A5 (en) | ||
| EP2105424A1 (en) | Method for manufacturing honeycomb structured body | |
| CN105688684B (en) | With three gradient pore structured pure matter foam silicon carbon supporter membrane tubes and preparation method | |
| WO2016052461A1 (en) | Method for producing honeycomb filter | |
| TW200844048A (en) | An extruded fibrous silicon carbide substrate and methods for producing the same | |
| WO2009095982A1 (en) | Honeycomb structure | |
| JP3998910B2 (en) | Method for firing silicon carbide molded body, method for producing porous silicon carbide member, and method for producing ceramic filter | |
| JP2002219317A (en) | Method for manufacturing ceramic structure | |
| CN115894060A (en) | Preparation method of carbon fiber brake disc | |
| JP4537669B2 (en) | Silicon carbide-based bonded component and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 |