CN109503172A - A kind of preparation method of the porous silicon carbide ceramic with vermiform crystal grain - Google Patents
A kind of preparation method of the porous silicon carbide ceramic with vermiform crystal grain Download PDFInfo
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- CN109503172A CN109503172A CN201811456691.0A CN201811456691A CN109503172A CN 109503172 A CN109503172 A CN 109503172A CN 201811456691 A CN201811456691 A CN 201811456691A CN 109503172 A CN109503172 A CN 109503172A
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- silicon carbide
- crystal grain
- porous silicon
- vermiform
- carbide ceramic
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000919 ceramic Substances 0.000 title claims abstract description 43
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 31
- 239000013078 crystal Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 43
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 20
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 19
- 239000007791 liquid phase Substances 0.000 claims abstract description 16
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 6
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021431 alpha silicon carbide Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- 238000009702 powder compression Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000012071 phase Substances 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000012300 argon atmosphere Substances 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 14
- 230000006872 improvement Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910003978 SiClx Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
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Abstract
The invention discloses a kind of preparation methods of porous silicon carbide ceramic with vermiform crystal grain, this method is using the SiC of carbon nanotube and micro-meter scale as raw material, rare earth oxide is sintering aid, under the conditions of argon atmosphere, the gas-solid reaction in situ of the gas phase and carbon nanotube evaporated first by SiO powder obtains the equally distributed block of nano SiC, it is sintered using high-temperature liquid-phase, can get has vermiform crystal grain porous SiC ceramics.The size heredity initial configuration of carbon nanotube of SiC crystal grain, therefore porous material intensity with higher.Preparation process of the invention is simple, easily operated, by being deployed to raw material proportioning, sintering temperature and soaking time change can effectively control pore-size and porosity.The porous silicon carbide ceramic that the present invention obtains can be widely applied to the fields such as high-temperature filter or catalyst carrier.
Description
Technical field
The present invention relates to a kind of preparation method of porous silicon carbide ceramic with vermiform crystal grain, be suitable for adsorbent,
Vehicle purifier, catalyst carrier, heat-barrier material, self-lubricating material, temperature and moisture sensors and electromagnetic shielding material etc..
Background technique
Porous silicon carbide ceramic material have low thermal coefficient of expansion, good thermal-shock resistance, excellent mechanical performance and
The excellent properties such as chemical stability are now widely used in the filter for molten metal of purifying molten metal, the catalyst of deodorization device
Carrier, absorption column of gas, the filler of destilling tower and fluidized bed filter, cultivate the Biomedia of microorganism, battery isolator,
Clarifier, sewage treatment air diffusion apparatus and the sound-absorbing material for controlling noise of high-temp waste gas.
At present prepare porous SiC ceramics method can be divided into granulation mass area method, template duplicating method, sacrifice template and directly
Foaming, wherein granulation mass area method is direct method the simplest, but utilizes the hole wall of the porous ceramics of this method preparation
Often not fine and close, the porosity is lower.It is raw material and burning that particle packing method, which prepares the key factor in porous silicon carbide ceramic,
Therefore knot technique selects that there is the raw material of specific form and unique sintering process can greatly improve porous SiC ceramics material
Various performances improve the porosity.Multi-walled carbon nanotube has unique structure, and diameter is long between a few nanometers to tens of nanometers
Degree is at tens microns, the spacing being kept fixed between layers, with high mechanical strength and ideal elasticity, facilitates sintering
The interconnection of process is the high-quality carbon source in granulation mass area method.Currently used sintering method mainly has reaction-sintered, solid phase
Sintering, liquid-phase sintering and recrystallization sintering etc., single sintering method is difficult to obtain the porous SiC ceramics material of high quality；Make
It is carbon source with multi-walled carbon nanotube, in conjunction with the advantages of both gas phase reaction the preparation method and lqiuid phase sintering method, in lower sintering temperature
Degree can realize the close connection between crystal grain, and high-purity porous silicon carbide ceramic material with vermiform crystal grain is prepared
Material.By being deployed to raw material proportioning, sintering temperature and soaking time change can effectively control pore-size and porosity
(67.1%-89.6%) can be prepared with the high nanometer worms shape crystal grain of draw ratio, high performance porous SiC ceramics.
Summary of the invention
The object of the present invention is to provide a kind of preparation methods of porous silicon carbide ceramic with vermiform crystal grain.Material
The porosity can regulate and control on a large scale, and β-SiC is vermiform nanocrystal, and possess high draw ratio, thus with high tough
Property.
The present invention adopts the following technical scheme that realize:
A kind of preparation method of the porous silicon carbide ceramic with vermiform crystal grain, the porous silicon carbide ceramic is by by carbon
The mixing material of nanotube, silicon-carbide particle and rare earth oxide is pressed and molded, and is placed in graphite crucible, and high temperature sintering system is carried out
It is standby to obtain, specifically include the following steps:
1) prepared by porous silicon carbide pre-sintered body: according to mass percent by the carbon nanotube of 26.89~90.00wt%,
Life is formed after the rare earth oxide mixed-powder compression molding of the α-SiC and 5.00~16.17wt% of 0.00~67.22wt%
SiO powder is placed in crucible bottom by base, and green compact are placed on the graphite holders in the middle part of crucible, then crucible is placed on multi-functional burning
In freezing of a furnace, it is passed through argon gas, keeps the temperature 0.5~8 hour at 1400 DEG C~1700 DEG C, carbothermic reduction reaction is carried out and generates silicon carbide base
Body, wherein SiO and the mass ratio of carbon nanotube are (8~12): 1；
2) prepared by porous silicon carbide ceramic: 1700 DEG C~1800 DEG C progress liquid-phase sintering 0.5~2 hour are continuously heating to,
Silicon carbide sintering neck be combined with each other during this, obtains the porous silicon carbide ceramic with vermiform crystal grain.
A further improvement of the present invention lies in that selecting the average grain diameter of silicon carbide is 0.2~4 μm in step 1).
A further improvement of the present invention lies in that the rare earth oxide of selection is Y in step 1)2O3, Yb2O3, La2O3Or
Eu2O3。
A further improvement of the present invention lies in that the pressure of the compression molding is 10~80MPa, pressure maintaining in step 1)
Time is 1~3min.
A further improvement of the present invention lies in that the argon atmospheric pressure is 1~7atm in step 1).
1100 DEG C of heating is risen to from room temperature a further improvement of the present invention lies in that in step 1), in multifunctional sintering furnace
Speed is 500~700 DEG C/h, and the heating rate that sintering temperature is warming up to from 1100 DEG C is 100~300 DEG C/h.
A further improvement of the present invention lies in that carbon thermal reduction temperature rises to the heating speed of liquid phase sintering conditions in step 1)
Degree is 50~100 DEG C/h.
The present invention has following beneficial technical effect:
A kind of preparation method of porous silicon carbide ceramic with vermiform crystal grain provided by the invention, this method make first
Carbon nanotube (CNTs) pass through gas-solid reaction in-situ preparation nanometer silicon carbide, after carry out liquid-phase sintering at high temperature, had
There is the porous SiC material of vermiform nanocrystal.It is sintered first with carbon nanotube and the gas-solid reaction combination high-temperature liquid-phase of SiO
Preparation has nanometer worms shape porous nano carbofrax material, by adjusting α-SiC content and briquetting pressure in starting material
The porosity (67.1%-89.6%) of controllable producing porous ceramic.The microstructure of finally obtained porous SiC ceramics material is main
It is made of the silicon carbide vermiform crystal grain that diameter is 100~800nm, draw ratio is 10~50, while there is high porosity, high-purity
And obdurability, and show certain compression reaction performance.In addition, preparation process of the invention is simple, and it is easily operated, by right
Raw material proportioning allotment, sintering temperature and soaking time change can effectively control pore-size and porosity.What the present invention obtained
Porous silicon carbide ceramic can be widely applied to the fields such as high-temperature filter or catalyst carrier.
Detailed description of the invention
Fig. 1 is the SEM figure of sample after the first gas-solid reaction of embodiment 3, liquid-phase sintering.
Fig. 2 is the XRD diagram of sample after the first gas-solid reaction of embodiment 4, liquid-phase sintering.
Fig. 3 is gas-solid reaction schematic diagram.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.
Porous silicon carbide ceramic prepared by the present invention, embodiment composition is as shown in table 1, and the embodiment 1 shown in table 1~
In 8, a certain proportion of micron or nano silicon carbide granulate are added in carbon nanotube, while a small amount of sintering aid is added, and are passed through
After certain briquetting pressure is pressed into green compact, green compact carry out high temperature sintering, carbon nanotube and silicon monoxide steam generation in-situ carbon
Thermal reduction reaction is changed into silicon carbide.
The raw material of the carborundum porous ceramics of the present invention of table 1. forms
The sintering process parameter of the porous silicon carbide ceramic of the present invention of table 2.
1 embodiment of table is the preparation method of carborundum porous ceramics, first presses carbon nanotube and carborundum powder described in table 1 not
It is weighed respectively with composition, uses dehydrated alcohol to be prepared into uniform mixed-powder as solvent wet mixing, then rotate mixed-powder
It is dry, it places into 70 DEG C of baking oven and thoroughly dries, cross 200 meshes after dry, be put into metal die compression moulding and implemented
The green compact sample of example 1~8, in 10~80MPa, the dwell time is 1~3min, the matter of SiO and carbon nanotube for briquetting pressure control
Amount is than control in (8~12): 1.SiO powder is placed in crucible bottom, green compact are placed in the middle part of crucible, then crucible is placed on more function
In energy sintering furnace, 1100 DEG C first are risen to the heating rate of 500~700 DEG C/h under an argon atmosphere, then with 100~300 DEG C/h
Heating rate be warming up to 1400 DEG C~1700 DEG C heat preservations, 2~5 hours progress gas-solid carbothermic reduction reactions, obtain silicon carbide base
Body；Then it is warming up to 1700-1800 DEG C with the speed of 50~100 DEG C/h, under an argon atmosphere liquid-phase sintering, obtains porous silicon carbide
Silicon ceramics.
The formulation of technique is for consideration: the volume by changing micron or nanometer silicon carbide, thus it is possible to vary crystal grain
Size adjusts the ratio of thickness vermiform crystalline substance, obtains the sample of the rodlike brilliant ratio of different thicknesses, and then realize the tune of crystal grain distribution
Control, the molding pressure of green compact should be controlled in 10~80MPa, and in the case where food ingredient determines, the green body porosity is by precast body
Briquetting pressure determines that it directly affects the porosity of final ceramics.The carborundum porous ceramics obtained by the above method, with 3 points
The bending strength of bending method measurement at room temperature；Open porosity is measured with Archimedes's drainage；It is being tried with scanning electron microscope
Microscopic structure is observed on sample section；With the object phase composition of X-ray diffractometer analysis sintered body.These porositys and bending strength
Results of property is as shown in table 3.
The performance of the carborundum porous ceramics sintered body of the present invention of table 3.
Embodiment 1 is using the carbon nanotube of 90.0wt% as raw material, 5.0wt% rare earth oxide as can be seen from Table 3
Y2O3、Al2O3、Yb2O3、La2O3And Eu2O3For sintering aid, silicon carbide, briquetting pressure 10MPa, by 1400 is not added
DEG C heat preservation 5h gas-solid reaction, then keep the temperature 2h at 1700 DEG C and carry out liquid-phase sintering, the porosity of gained porous SiC ceramics material is
89.1%, due to the nanometer worms shape crystal grain only generated, the porosity is higher.
Embodiment 4 is made using the carbon nanotube of 54.36wt% and 2 μm of carborundum powders of 38.83wt% as can be seen from Table 3
For raw material, 6.81wt% rare earth oxide Y2O3、Al2O3、Yb2O3、La2O3And Eu2O3For sintering aid, briquetting pressure is
60MPa by 1500 DEG C of heat preservation 4h gas-solid reactions, then keeps the temperature 2h at 1750 DEG C and carries out liquid-phase sintering, gained porous SiC ceramics
The porosity of material is 74.3%.From attached drawing 1 as can be seen that by the diameter dimension of the ratio of height to diameter obtained after carbon nanotube reaction
It is sintered for nanoscale vermiform crystal and micro-scale crystal grain, forms porous ceramics.
Embodiment 6 is using the carbon nanotube of 35.19wt% and (0.5 μm) nano-sized carbon of 49.22wt% as can be seen from Table 3
SiClx is as raw material, briquetting pressure 40MPa, by 1600 DEG C of heat preservation 2h gas-solid reactions, then keep the temperature at 1750 DEG C 0.5h into
Row liquid-phase sintering, the porosity of gained porous SiC ceramics material are 70.8%.
Embodiment 8 is using the carbon nanotube of 26.89wt% and the carborundum powder conduct of 67.22wt% as can be seen from Table 3
Raw material, the rare earth oxide Y of 5.89wt%2O3、Al2O3、Yb2O3、La2O3And Eu2O3For sintering aid, briquetting pressure is
20MPa by 1700 DEG C of heat preservation 0.5h gas-solid reactions, then keeps the temperature 0.5h at 1800 DEG C and carries out liquid-phase sintering, gained porous SiC
The porosity of ceramic material is 67.1%.
From attached drawing 1 as can be seen that the diameter dimension of high length-diameter ratio is nanoscale vermiform crystal grain and micrometer silicon carbide silicon knot
It closes, forms porous ceramics.
Fig. 2 is the XRD diagram of the porous silicon carbide ceramic material obtained of embodiment 2.As shown, by liquid-phase sintering
Afterwards, phase obtained is the compound phase of β-SiC and α-SiC.
Fig. 3 is gas-solid reaction schematic device, wherein serial number 1 is sintering furnace, and serial number 2 is the graphite crucible lid for being coated with BN,
Serial number 3 is the green compact containing CNT, and serial number 4 is the graphite inner cover for being coated with BN, and serial number 5 is the graphite holders for being coated with BN, and serial number 6 is
SiO powder, serial number 7 are graphite base.
Claims (7)
1. a kind of preparation method of the porous silicon carbide ceramic with vermiform crystal grain, which is characterized in that porous silicon carbide pottery
Porcelain is placed in graphite crucible, carries out by the way that the mixing material of carbon nanotube, silicon-carbide particle and rare earth oxide to be pressed and molded
High temperature sintering is prepared, specifically include the following steps:
1) prepared by porous silicon carbide pre-sintered body: according to mass percent by the carbon nanotube of 26.89~90.00wt%, 0.00
Green compact are formed after the rare earth oxide mixed-powder compression molding of the α-SiC and 5.00~16.17wt% of~67.22wt%, it will
SiO powder is placed in crucible bottom, green compact is placed on the graphite holders in the middle part of crucible, then crucible is placed on multifunctional sintering furnace
In, it is passed through argon gas, keeps the temperature 0.5~8 hour at 1400 DEG C~1700 DEG C, carbothermic reduction reaction is carried out and generates silicon carbide green body,
Middle SiO and the mass ratio of carbon nanotube are (8~12): 1；
2) prepared by porous silicon carbide ceramic: being continuously heating to 1700 DEG C~1800 DEG C progress liquid-phase sintering 0.5~2 hour, this mistake
Silicon carbide sintering neck be combined with each other in journey, obtains the porous silicon carbide ceramic with vermiform crystal grain.
2. the preparation method of the porous silicon carbide ceramic according to claim 1 with vermiform crystal grain, which is characterized in that
In step 1), selecting the average grain diameter of silicon carbide is 0.2~4 μm.
3. the preparation method of the porous silicon carbide ceramic according to claim 1 with vermiform crystal grain, which is characterized in that
In step 1), the rare earth oxide of selection is Y2O3, Yb2O3, La2O3Or Eu2O3。
4. the preparation method of the porous silicon carbide ceramic according to claim 1 with vermiform crystal grain, which is characterized in that
In step 1), the pressure of the compression molding is 10~80MPa, and the dwell time is 1~3min.
5. the preparation method of the porous silicon carbide ceramic according to claim 1 with vermiform crystal grain, which is characterized in that
In step 1), the argon atmospheric pressure is 1~7atm.
6. the preparation method of the porous silicon carbide ceramic according to claim 1 with vermiform crystal grain, which is characterized in that
In step 1), 1100 DEG C of heating rate is risen to as 500~700 DEG C/h from room temperature in multifunctional sintering furnace, is heated up from 1100 DEG C
Heating rate to sintering temperature is 100~300 DEG C/h.
7. the preparation method of the porous silicon carbide ceramic according to claim 1 with vermiform crystal grain, which is characterized in that
In step 1), the heating rate that carbon thermal reduction temperature rises to liquid phase sintering conditions is 50~100 DEG C/h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979319A (en) * | 2021-02-05 | 2021-06-18 | 奉化市飞固凯恒密封工程有限公司 | Toughened silicon carbide ceramic and preparation method thereof |
| WO2023134781A1 (en) * | 2022-01-11 | 2023-07-20 | 南京工业大学 | Method for one-step regulation of pore structure and surface properties of silicon carbide film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293772A (en) * | 2008-05-30 | 2008-10-29 | 上海工程技术大学 | Preparation technique for SiC/CNTs composite ceramic |
| US20110111205A1 (en) * | 2009-11-09 | 2011-05-12 | Korea Institute Of Machinery & Materials | METHOD OF MANUFACTURING POROUS SINTERED REACTION-BONDED SILICON NITRIDE CERAMICS FROM GRANULAR Si MIXTURE POWDER AND POROUS SINTERED REACTION-BONDED SILICON NITRIDE CERAMICS MANUFACTURED THEREBY |
| CN104387102A (en) * | 2014-10-30 | 2015-03-04 | 苏州莱特复合材料有限公司 | Carbon nano-tube ceramic composite material and preparation method thereof |
| CN104987125A (en) * | 2015-07-10 | 2015-10-21 | 国家电网公司 | Preparation method of carbon nanotube modified foamed ceramics |
| CN105541370A (en) * | 2015-12-21 | 2016-05-04 | 哈尔滨工业大学 | Preparation method for porous silicon carbide ceramic material |
-
2018
- 2018-11-30 CN CN201811456691.0A patent/CN109503172B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293772A (en) * | 2008-05-30 | 2008-10-29 | 上海工程技术大学 | Preparation technique for SiC/CNTs composite ceramic |
| US20110111205A1 (en) * | 2009-11-09 | 2011-05-12 | Korea Institute Of Machinery & Materials | METHOD OF MANUFACTURING POROUS SINTERED REACTION-BONDED SILICON NITRIDE CERAMICS FROM GRANULAR Si MIXTURE POWDER AND POROUS SINTERED REACTION-BONDED SILICON NITRIDE CERAMICS MANUFACTURED THEREBY |
| CN104387102A (en) * | 2014-10-30 | 2015-03-04 | 苏州莱特复合材料有限公司 | Carbon nano-tube ceramic composite material and preparation method thereof |
| CN104987125A (en) * | 2015-07-10 | 2015-10-21 | 国家电网公司 | Preparation method of carbon nanotube modified foamed ceramics |
| CN105541370A (en) * | 2015-12-21 | 2016-05-04 | 哈尔滨工业大学 | Preparation method for porous silicon carbide ceramic material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979319A (en) * | 2021-02-05 | 2021-06-18 | 奉化市飞固凯恒密封工程有限公司 | Toughened silicon carbide ceramic and preparation method thereof |
| WO2023134781A1 (en) * | 2022-01-11 | 2023-07-20 | 南京工业大学 | Method for one-step regulation of pore structure and surface properties of silicon carbide film |
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