CN102320856B - Method for preparing porous silicon-nitride ceramic material - Google Patents
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- CN102320856B CN102320856B CN 201110247169 CN201110247169A CN102320856B CN 102320856 B CN102320856 B CN 102320856B CN 201110247169 CN201110247169 CN 201110247169 CN 201110247169 A CN201110247169 A CN 201110247169A CN 102320856 B CN102320856 B CN 102320856B
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 62
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229920002472 Starch Polymers 0.000 claims abstract description 31
- 239000008107 starch Substances 0.000 claims abstract description 31
- 235000019698 starch Nutrition 0.000 claims abstract description 31
- 238000005245 sintering Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 21
- 239000011268 mixed slurry Substances 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 20
- 229910021426 porous silicon Inorganic materials 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 16
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 14
- 239000013530 defoamer Substances 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000007582 slurry-cast process Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 238000005452 bending Methods 0.000 abstract description 12
- 238000007710 freezing Methods 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 6
- 238000003756 stirring Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000001914 filtration Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000004108 freeze drying Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229920000881 Modified starch Polymers 0.000 abstract 2
- 201000005569 Gout Diseases 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 239000007767 bonding agent Substances 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 238000005266 casting Methods 0.000 abstract 1
- 238000007872 degassing Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000008014 freezing Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000011800 void material Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 230000008961 swelling Effects 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000003039 volatile agent Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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Abstract
The invention discloses a method for preparing a porous silicon-nitride ceramic material, which comprises the following steps of: stirring starch and water at the temperature of 40-90 DEG C to prepare pre-gelatinized starch; adding silicon nitride, a sintering aid, a bonding agent and a defoaming agent to the pre-gelatinized starch, and uniformly mixing through ball milling to prepare a mixed slurry; molding the mixed slurry through casting, and carrying gout degassing, curing, complete sample-freezing and freeze-drying processing to prepare a porous silicon-nitride ceramic blank body; removing organic volatile substances in the porous silicon-nitride ceramic blank body through heating; and sintering, and cooling a sample along with a furnace after sintering. The silicon-nitride ceramic material prepared by utilizing the preparation method disclosed by the invention has high open porosity (which can reach 60-90 percent) and low density (0.32-1.28g/<cm>3), the bending strength can be regulated within the range of 5-140MPa, and the application-performance requirements of materials in the fields of high-temperature gas and liquid filtration, purification and separation, chemical catalytic carriers and the like can be met.
Description
Technical field
The present invention relates to a kind of preparation method of porous silicon-nitride ceramic material, specifically, relate to a kind of curing in conjunction with Freeze Drying Technique with starch and prepare high open porosity, low density and have the method for the silicon nitride ceramic material of better intensity, belong to ceramic materials preparation technology field.
Background technology
Porous silicon-nitride ceramic material is owing to having lightweight, the characteristics such as high temperature resistant, corrosion-resistant, have wide practical use in fields such as high temperature air filtration, sensor, support of the catalyst, separatory membranes, therefore the preparation method about porous silicon nitride ceramic becomes one of focus of present research.For example: Chinese patent literature CN1473140A discloses a kind of take metal Si powder as raw material, Sm
2O
3, Er
2O
3, Yb
2O
3Deng being sintering aid, prepare high porosity (＞78%) under the microwave heating of frequency 28GHz, high strength (method of＞200MPa) porous silicon nitride ceramic, but its pore mostly is the hole of holding one's breath, and can't be applied to the fields such as filtration.The people such as Yu (J Sol-Gel Sci Technol (2010) 53:515～523) disclose a kind of method with the standby porous silicon nitride ceramic of gel injection legal system, by regulating content and the ratio of organic monomer, control the void content of base substrate, thereby obtain void content greater than 50%, intensity is greater than the sample of 130MPa.The people such as Yang (Acta Materialia (2002) 50:4831～4840) disclose a kind of take silicon nitride and carbon dust as raw material, prepare silicon carbide in conjunction with the method for porous SiN ceramic by the reaction in－situ sintering, the void content of prepared material is 50～70%, and bending strength is 100～20MPa.The people such as Shan (Scripta Materialia (2007) 56:193～196) disclose a kind of take silicon-dioxide and carbon dust as raw material, hot carbon reduction nitridation reaction prepares the method for porous silicon nitride ceramic, the sample gas porosity that obtains is 68.8%, and bending strength is 19.6MPa.
But how to prepare high open porosity, low density and have the silicon nitride ceramic material of better intensity, relevant report that so far there are no.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing high open porosity, low density and have the silicon nitride ceramic material of better intensity, to fill up the technological gap of this area.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of method for preparing porous silicon-nitride ceramic material comprises the steps:
A) starch and water are stirred under 40～90 ℃, make starch,pregelatinized;
B) add silicon nitride, sintering aid, binding agent and defoamer in starch,pregelatinized, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, carry out degassed, solidify, make sample fully charge and lyophilize to process, make the porous silicon nitride ceramic base substrate;
D) heat up remove step c) organic volatile in the porous silicon nitride ceramic base substrate that makes;
E) carry out sintering, sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
Starch and the mass ratio of water of step in a) be recommended as 0.01: 1～and 0.2: 1, be preferably 0.04: 1～0.12: 1.
The churning time of step in a) is recommended as 5～30 minutes.
The mass ratio of the silicon nitride step b), sintering aid, binding agent and defoamer and water is recommended as successively: (0.5～1): (0.01～0.1): (0～0.1): (0.001～0.02): 1.
Described sintering aid is recommended as Y
2O
3, Y (NO
3)
3, Yb
2O
3, Lu
2O
3, Nd
2O
3, Er
2O
3, Al
2O
3, SiO
2, Li
2Any one in O or the mixture that forms with arbitrary proportion more than two kinds.
Described binding agent is recommended as polyvinyl alcohol or methylcellulose gum.
Described defoamer is recommended as n-Octanol.
Step c) the degassed processing in is recommended as: in vacuum drying oven, in normal temperature, the following vacuum outgas of 100Pa more than 10 minutes.
Step c) solidification treatment in is recommended as: solidified 30～90 minutes in the airtight baking oven of 50～90 ℃.
Step c) the sample fully charge processing that makes in is recommended as: sample was placed in lower than the low temperature environment of-10 ℃ 4～48 hours.
Step c) lyophilize in is processed and is recommended as: lyophilize is 6～48 hours under the environment of 0～80 ℃ and 5～100Pa.
Steps d) operation that the intensification in removes organic volatile is recommended as: be raised to 600 ℃ with the temperature rise rate lower than 2 ℃/min in air, then be incubated 1～12 hour.
Step e) sintering condition in is recommended as: under nitrogen atmosphere, be raised to 1300～1950 ℃ with 5～10 ℃/min, then sintered heat insulating is 1～12 hour.
Compared with prior art, utilize the silicon nitride ceramic material that preparation method of the present invention makes open porosity high (can reach 60～90%), density is low (is 0.32～1.28g/cm
3), bending strength can be adjustable in 5～140MPa scope, can satisfy the application performance requirement of the field materials such as gas and liquid filtering, purification separation, chemical industry catalytic carrier.
Description of drawings
Fig. 1 is the XRD contrast figure of embodiment 1 silicon nitride raw material used (a) and the porous silicon-nitride ceramic material (b) that makes;
Fig. 2 is intensity, the void content curve contrast figure of embodiment 3,4,5 prepared porous silicon-nitride ceramic materials;
Fig. 3 is the pore size distribution contrast figure of embodiment 3,4,5 prepared porous silicon-nitride ceramic materials;
Fig. 4 is the scanning electron microscope contrast figure of the prepared porous silicon-nitride ceramic material of embodiment 5 under low multiple (a) and high multiple (b).
Embodiment
The present invention is described in further detail and completely below in conjunction with embodiment and accompanying drawing, but the present invention is not limited in the content in following embodiment.
Embodiment 1
A) with 8g starch and 75g deionized water 70 ℃ of lower violent stirring 10 minutes, make its water absorption and swelling, make starch,pregelatinized;
B) starch,pregelatinized that makes is transferred in ball grinder, then 50g silicon nitride, 2.5g sintering aid yttrium oxide, 2g binding agent polyvinyl alcohol and 1g defoamer n-Octanol are joined in ball grinder, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, then put into vacuum drying oven in the following vacuum outgas of normal temperature 100Pa 15 minutes, to eliminate the bubble in slurry; The baking oven of again sample sealing being put into 85 ℃ solidified 30 minutes, and the cryogenic refrigerator that sample is placed in after the room temperature-30 ℃ to be cooled kept 24 hours, made the sample fully charge; Sample fast transfer after freezing is in freeze drier, and under the environment of 5 ℃ and 10Pa, lyophilize is 24 hours, makes the ice crystal distillation in freezing base substrate, thereby forms porous body, makes the porous silicon nitride ceramic base substrate;
D) with step c) porous silicon nitride ceramic base substrate temperature rise rate with 1 ℃/min in air of making is raised to 600 ℃, then is incubated 2 hours, to remove the organic volatiles such as starch, binding agent;
E) sample is put into the pyrocarbon pipe furnace, the temperature rise rate with 10 ℃/min under nitrogen atmosphere is raised to 1680 ℃, and then sintered heat insulating is 2 hours, and sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
Adopt open porosity and the volume density (GB/T3810.3-2006) of Archimedes's drainage specimen; Bending strength test carries out on American I nstron company 5566 material universal testing machines, and loading rate is 0.5mm/min, and span is 30mm, and sample size is 3mm * 4mm * 36mm.
Learn after testing: the open porosity of the porous silicon-nitride ceramic material that the present embodiment makes is 82%, and density is 0.576g/cm
3, bending strength is 8MPa.
Fig. 1 is the XRD contrast figure of the present embodiment silicon nitride raw material used (a) and the porous silicon-nitride ceramic material (b) that makes, as seen from Figure 1: through high temperature sintering, silicon nitride changes the β phase into mutually by α almost completely, and the column beta phase silicon nitride is conducive to improve the mechanical property of material.
Embodiment 2
A) with 8g starch and 70g deionized water 90 ℃ of lower violent stirring 5 minutes, make its water absorption and swelling, make starch,pregelatinized;
B) starch,pregelatinized that makes is transferred in ball grinder, then 50g silicon nitride, 2g sintering aid yttrium oxide, 2g binding agent polyvinyl alcohol and 1.2g defoamer n-Octanol are joined in ball grinder, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, then put into vacuum drying oven in the following vacuum outgas of normal temperature 100Pa 20 minutes, to eliminate the bubble in slurry; The baking oven of again sample sealing being put into 70 ℃ solidified 60 minutes, and the cryogenic refrigerator that sample is placed in after the room temperature-30 ℃ to be cooled kept 24 hours, made the sample fully charge; Sample fast transfer after freezing is in freeze drier, and lyophilize is 24 hours under the environment of 7 ℃ and 20Pa, makes the ice crystal distillation in freezing base substrate, thereby forms porous body, makes the porous silicon nitride ceramic base substrate;
D) with step c) porous silicon nitride ceramic base substrate temperature rise rate with 1.5 ℃/min in air of making is raised to 600 ℃, then is incubated 2 hours, to remove the organic volatiles such as starch, binding agent;
E) sample is put into the pyrocarbon pipe furnace, the temperature rise rate with 10 ℃/min under nitrogen atmosphere is raised to 1680 ℃, and then sintered heat insulating is 2 hours, and sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
Learn after testing: the open porosity of the porous silicon-nitride ceramic material that the present embodiment makes is 78%, and density is 0.704g/cm
3, bending strength is 17MPa.
Embodiment 3
A) with 5g starch and 60g deionized water 70 ℃ of lower violent stirring 10 minutes, make its water absorption and swelling, make starch,pregelatinized;
B) starch,pregelatinized that makes is transferred in ball grinder, then 50g silicon nitride, 2.5g sintering aid yttrium oxide, 0g binding agent polyvinyl alcohol and 0.8g defoamer n-Octanol are joined in ball grinder, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, then put into vacuum drying oven in the following vacuum outgas of normal temperature 100Pa 20 minutes, to eliminate the bubble in slurry; The baking oven of again sample sealing being put into 70 ℃ solidified 60 minutes, and the cryogenic refrigerator that sample is placed in after the room temperature-30 ℃ to be cooled kept 24 hours, made the sample fully charge; Sample fast transfer after freezing is in freeze drier, and lyophilize is 24 hours under the environment of 4 ℃ and 10Pa, makes the ice crystal distillation in freezing base substrate, thereby forms porous body, makes the porous silicon nitride ceramic base substrate;
D) with step c) porous silicon nitride ceramic base substrate temperature rise rate with 1.5 ℃/min in air of making is raised to 600 ℃, then is incubated 2 hours, to remove the organic volatiles such as starch, binding agent;
E) sample is put into the pyrocarbon pipe furnace, the temperature rise rate with 10 ℃/min under nitrogen atmosphere is raised to 1680 ℃, and then sintered heat insulating is 2 hours, and sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
Learn after testing: the open porosity of the porous silicon-nitride ceramic material that the present embodiment makes is 72%, and density is 0.896g/cm
3, bending strength is 6MPa.
Embodiment 4
A) with 3.75g starch and 60g deionized water 60 ℃ of lower violent stirring 20 minutes, make its water absorption and swelling, make starch,pregelatinized;
B) starch,pregelatinized that makes is transferred in ball grinder, then 50g silicon nitride, 2.5g sintering aid yttrium oxide, 1.25g binding agent polyvinyl alcohol and 0.8g defoamer n-Octanol are joined in ball grinder, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, then put into vacuum drying oven in the following vacuum outgas of normal temperature 100Pa 20 minutes, to eliminate the bubble in slurry; The baking oven of again sample sealing being put into 90 ℃ solidified 30 minutes, and the cryogenic refrigerator that sample is placed in after the room temperature-30 ℃ to be cooled kept 24 hours, made the sample fully charge; Sample fast transfer after freezing is in freeze drier, and lyophilize is 24 hours under the environment of 7 ℃ and 5Pa, makes the ice crystal distillation in freezing base substrate, thereby forms porous body, makes the porous silicon nitride ceramic base substrate;
D) with step c) porous silicon nitride ceramic base substrate temperature rise rate with 1.5 ℃/min in air of making is raised to 600 ℃, then is incubated 2 hours, to remove the organic volatiles such as starch, binding agent;
E) sample is put into the pyrocarbon pipe furnace, the temperature rise rate with 10 ℃/min under nitrogen atmosphere is raised to 1680 ℃, and then sintered heat insulating is 2 hours, and sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
Learn after testing: the open porosity of the porous silicon-nitride ceramic material that the present embodiment makes is 74%, and relative density is 0.832g/cm
3, bending strength is 23MPa.
A) with 2.5g starch and 60g deionized water 90 ℃ of lower violent stirring 5 minutes, make its water absorption and swelling, make starch,pregelatinized;
B) starch,pregelatinized that makes is transferred in ball grinder, then 50g silicon nitride, 2.5g sintering aid yttrium oxide, 2.5g binding agent polyvinyl alcohol and 0.8g defoamer n-Octanol are joined in ball grinder, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, then put into vacuum drying oven in the following vacuum outgas of normal temperature 100Pa 20 minutes, to eliminate the bubble in slurry; The baking oven of again sample sealing being put into 80 ℃ solidified 40 minutes, and the cryogenic refrigerator that sample is placed in after the room temperature-30 ℃ to be cooled kept 24 hours, made the sample fully charge; Sample fast transfer after freezing is in freeze drier, and lyophilize is 24 hours under the environment of 10 ℃ and 10Pa, makes the ice crystal distillation in freezing base substrate, thereby forms porous body, makes the porous silicon nitride ceramic base substrate;
D) with step c) porous silicon nitride ceramic base substrate temperature rise rate with 1.5 ℃/min in air of making is raised to 600 ℃, then is incubated 2 hours, to remove the organic volatiles such as starch, binding agent;
E) sample is put into the pyrocarbon pipe furnace, the temperature rise rate with 10 ℃/min under nitrogen atmosphere is raised to 1680 ℃, and then sintered heat insulating is 2 hours, and sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
Learn after testing: the open porosity of the porous silicon-nitride ceramic material that the present embodiment makes is 73%, and relative density is 0.864g/cm
3, bending strength is 42MPa.
Fig. 2 is intensity, the void content curve contrast figure of embodiment 3,4,5 prepared porous silicon-nitride ceramic materials, as seen from Figure 2: the void content of sample mainly is subjected to the control of solid content, the proportioning of starch and polyvinyl alcohol changes the void content impact very little, but bending strength progressively improves along with the increase of polyvinyl alcohol content.
Fig. 3 is the pore size distribution contrast figure of embodiment 3,4,5 prepared porous silicon-nitride ceramic materials, as seen from Figure 3: embodiment 3,4 pore size distribution are that three peaks distribute, the pore size distribution of embodiment 5 is bimodal distribution, increase along with polyvinyl alcohol content, ice-crystal growth is suppressed, and the macropore about 30 μ m changes the aperture of 1 μ m and 0.3 μ m gradually into.
Fig. 4 is the scanning electron microscope contrast figure of the prepared porous silicon-nitride ceramic material of embodiment 5 under low multiple (a) and high multiple (b), as seen from Figure 4: column beta phase silicon nitride length-to-diameter ratio is higher, crystal grain is staggered in hole grows, be conducive to fill up hole, reduce pore size, improve the bending strength of material.
Claims (13)
1. a method for preparing porous silicon-nitride ceramic material, is characterized in that, comprises the steps:
A) starch and water are stirred under 40～90 ℃, make starch,pregelatinized;
B) add silicon nitride, sintering aid, binding agent and defoamer in starch,pregelatinized, ball milling makes and mixes, and makes mixed slurry;
C) with step b) the mixed slurry casting that makes, carry out degassed, solidify, make sample fully charge and lyophilize to process, make the porous silicon nitride ceramic base substrate;
D) heat up remove step c) organic volatile in the porous silicon nitride ceramic base substrate that makes;
E) carry out sintering, sample furnace cooling after sintering namely gets described porous silicon-nitride ceramic material.
2. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that, step in a) starch and the mass ratio of water be 0.01: 1～0.2: 1.
3. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that, the churning time of step in a) is 5～30 minutes.
4. the method for preparing porous silicon-nitride ceramic material according to claim 1, it is characterized in that step b) in silicon nitride, sintering aid, binding agent and defoamer and the mass ratio of water be followed successively by: (0.5～1): (0.01～0.1): (0～0.1): (0.001～0.02): 1.
5. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that, described sintering aid is Y
2O
3, Y (NO
3)
3, Yb
2O
3, Lu
2O
3, Nd
2O
3, Ee
2O
3, Al
2O
3, SiO
2, Li
2Any one in O or the mixture that forms with arbitrary proportion more than two kinds.
6. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that, described binding agent is polyvinyl alcohol or methylcellulose gum.
7. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that, described defoamer is n-Octanol.
8. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that step c) in degassed being treated to: in vacuum drying oven, in normal temperature, the following vacuum outgas of 100Pa more than 10 minutes.
9. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that step c) in solidification treatment be: solidified 30～90 minutes in the airtight baking oven of 50～90 ℃.
10. the method for preparing porous silicon-nitride ceramic material according to claim 1, is characterized in that step c) in the sample fully charge that makes be treated to: sample was placed in lower than the low temperature environment of-10 ℃ 4～48 hours.
11. the method for preparing porous silicon-nitride ceramic material according to claim 1 is characterized in that step c) in lyophilize be treated to: lyophilize is 6～48 hours under the environment of 0～80 ℃ and 5～100Pa.
12. the method for preparing porous silicon-nitride ceramic material according to claim 1, it is characterized in that, steps d) intensification in removes being operating as of organic volatile: be raised to 600 ℃ with the temperature rise rate lower than 2 ℃/min in air, then be incubated 1～12 hour.
13. the method for preparing porous silicon-nitride ceramic material according to claim 1 is characterized in that step e) in sintering condition be: under nitrogen atmosphere, be raised to 1300～1950 ℃ with 5～10 ℃/min, then sintered heat insulating is 1～12 hour.
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| CN104072148B (en) * | 2013-03-29 | 2016-06-15 | 北京市理化分析测试中心 | A kind of preparation method of low cost silicon nitride honeycomb pottery |
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| CN104311114B (en) * | 2014-10-16 | 2017-01-18 | 中国科学院上海硅酸盐研究所 | Method of preparing gradient porous silicon nitride ceramic material |
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