CN105502403A - Preparation method of ordered mesoporous silicon carbide - Google Patents
Preparation method of ordered mesoporous silicon carbide Download PDFInfo
- Publication number
- CN105502403A CN105502403A CN201610022824.8A CN201610022824A CN105502403A CN 105502403 A CN105502403 A CN 105502403A CN 201610022824 A CN201610022824 A CN 201610022824A CN 105502403 A CN105502403 A CN 105502403A
- Authority
- CN
- China
- Prior art keywords
- silicon carbide
- order mesoporous
- mesoporous silicon
- preparation
- microwave
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention relates to a method for preparing ordered mesoporous silicon carbide through microwave roasting. The method comprises the steps that 1, an ordered mesoporous SiO2-C composite is prepared; 2, the ordered mesoporous silicon carbide is prepared through microwave reduction. The ordered mesoporous SiO2-C composite is firstly prepared, a microwave radiation carbothermal reduction reaction is performed in an inert atmosphere through the good microwave absorbing property of carbon, and then impurity removing and drying are performed to obtain the ordered mesoporous silicon carbide. The preparation method is short in preparation time, and the product has the advantages of being relatively uniform in pore diameter and larger in specific surface area.
Description
Technical field
The present invention relates to a kind of method that microwave calcining prepares order mesoporous silicon carbide, belong to ordered mesoporous material synthesis technique field.
Background technology
Silicon carbide has the good characteristics such as good chemical stability, high-temperature stability, high thermal conductivity, antioxidant anticorrosive, make silicon carbide can as the substrate of high-temperature structural components, large-scale integrated circuit, also can be used as the excellent carrier of high temperature reaction catalyst, be widely used in the industrial circles such as chemical, machinery, metallurgy.Silicon carbide preparation utilizes carbothermic reduction reaction usually, needs to be heated on 2000 DEG C, and the little and atresia of obtained silicon carbide specific surface area, improvement is badly in need of in the time-consuming power consumption of the method.
The preparation of current mesoporous silicon carbide is divided into hard template and soft template two kinds of methods; if patent CN201510269148 is that hard template method prepares mesoporous silicon carbide; Polycarbosilane is dissolved in organic solvent; Polycarbosilane is made to be filled in ordered mesoporous silica dioxide; high-temperature roasting under protection of inert gas again; obtain the mixture of silicon carbide and silicon-dioxide, hydrofluoric acid removing template, namely obtains ordered nano mesoporous silicon carbide material.For another example patent CN201010152336 is water-soluble by sucrose, makes it enter in the mesopore orbit of SBA-15 or KIT-6, sucrose carbonization, and be filled with the mixture of carbon in obtained mesoporous silicon oxide, under the effect of magnesium powder, low-temperature bake obtains mesoporous silicon carbide.Hard template method cost is higher and add and remove the step of template.Soft template as patent CN201210146069 with Resorcinol, formaldehyde, tetraethyl orthosilicate for raw material, obtain silicon carbide precursor by sol-gel method, through carbothermic reduction generate mesoporous silicon carbide.Two kinds of methods all need high-temperature roasting, and energy consumption is high.
Summary of the invention
The present invention prepares mesoporous silicon carbide tediously long, the problem such as energy consumption is high consuming time to solve in prior art, provides a kind of preparation method of order mesoporous silicon carbide.
The present invention is achieved by the following technical solutions: a kind of preparation method of order mesoporous silicon carbide, the steps include:
(i) order mesoporous SiO is prepared
2/ C composite
(ii) microwave reduction prepares order mesoporous silicon carbide
Order mesoporous SiO
2/ C composite is placed in microwave oven region intermediate, and adjustment position, until infrared temperature probe records the maximum temperature point of matrix material; Being evacuated to vacuum tightness is 0.09MPa, and passing into nitrogen to vacuum tightness is 0.03MPa, vacuumizes, logical nitrogen steps carries out twice repeatedly, after to be again evacuated to vacuum tightness be 0.09MPa, passing into nitrogen to vacuum tightness is 0.07MPa; Open microwave oven cooling water circulating device, open microwave control switch, regulate microwave power to make to be warming up to 1300 DEG C ± 10 DEG C in stove, isothermal reaction 20min; Close microwave control switch, stop heating, being evacuated to vacuum tightness is 0.09MPa, after naturally cooling to room temperature, closes recirculated water in stove; Open blow-off valve, when microwave oven internal pressure reaches atmospheric pressure, fire door is opened automatically, takes out, obtains pulverous order mesoporous silicon carbide.
The microwave oven adopted during actually operating of the present invention is that Nanjing Jie Quan microwave equipment company limited produces, and its model is NJZ4-3.
The present invention is by the preparation of microwave technique application in silicon carbide, rapid temperature increases in short period of time, remarkable shortening preparation time, reduce energy consumption, greatly reduce traditional preparation methods and prepare long shortcoming consuming time, preparing shorter, reasonable raw material proportioning, product stable consuming time, is prepare a kind of very good method of order mesoporous silicon carbide.
In addition, the order mesoporous silicon carbide powder that (ii) step of the present invention obtains has carried out removal of impurities process subsequently, and this removal of impurities process comprises high temperature carbon removal treatment and the process of pickling silica removal.
During concrete enforcement, the step of described high temperature carbon removal treatment is: be placed in retort furnace by order mesoporous silicon carbide powder, and 700 DEG C of roasting 2h, remove unreacted carbon.The step of described pickling silica removal process is: the hydrofluoric acid solution order mesoporous silicon carbide powder being placed in 50% volume fraction, leaves standstill 24h; Centrifugally afterwards outwell supernatant liquor, cleaning, dry, remove unreacted silicon.
Further, the present invention does template with triblock copolymer body structure directed agents F127, does silicon source, do carbon source with phenol resin oligomer with tetraethoxy; And prepare order mesoporous SiO
2the step of/C composite is:
1. be dissolved in dehydrated alcohol by F127, add hydrochloric acid soln, 40 DEG C of constant temperature stir 1h; After add the ethanolic soln of tetraethoxy and phenol resin oligomer successively, 40 DEG C of constant temperature stir 2h, obtain mixing solutions;
2. mixing solutions is placed in container, and ambient temperatare puts 5 ~ 8h, is then placed in 24h in 100 DEG C of constant temperature ovens, and form yellow film in container, scraping wears into fine powder;
3. this fine powder is placed in tube furnace, is warming up to 350 DEG C with 1 DEG C/min and insulation 3h, then is warming up to 600 DEG C with 1 DEG C/min, be warming up to 900 DEG C with 5 DEG C/min subsequently and insulation 2h, obtain the order mesoporous SiO of black
2/ C composite.
Aforesaid method utilizes soft template method first obtained order mesoporous SiO
2the matrix material of/C, then adopt microwave calcining carbothermic reduction obtained order mesoporous silicon carbide fast, obtained silicon carbide aperture is concentrated, and specific surface area is large.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope enlarged view of order mesoporous silicon carbide of the present invention.In figure: orderly regular mesoporous existence can be found out.
Fig. 2 is the X-ray small-angle diffraction intensity collection of illustrative plates of order mesoporous silicon carbide of the present invention.In figure, ordinate zou is diffracted intensity, and X-coordinate is diffraction angle 2 θ, and little angle XRD occurs peak 0.8 ° time, and explanation is ordered mesopore structure.
Fig. 3 is the X-ray full-shape diffracted intensity collection of illustrative plates of order mesoporous silicon carbide of the present invention.In figure, 35.579o, 41.383o, 59.977o, 71.777o, 75.492o are silicon carbide standard diffraction peak, fit like a glove with standard card PDF#29-1129, illustrate that the product of synthesis is silicon carbide.
Fig. 4 is the suction-desorption isothermal curve figure of order mesoporous silicon carbide of the present invention.The curve at figure orbicular spot place represents adsorption curve figure, and the curve at some place, side represents desorption curve figure.As seen from the figure, suction-desorption isotherm meets H1 type and returns stagnant ring, and what H1 type returned the reflection of stagnant ring is the cylindrical hole of even aperture distribution, and specific surface area is 446.55m
2/ g.
Fig. 5 is the pore size distribution curve figure of order mesoporous silicon carbide of the present invention.Known in figure, pore size distribution curve can find out that aperture concentrates on about 6.3nm.
Embodiment
The chemical substance material that the present invention uses is: structure directing agent F127, phenol, formaldehyde, tetraethoxy, dehydrated alcohol, sodium hydroxide, hydrochloric acid, hydrofluoric acid, deionized water, nitrogen, and it prepares consumption with gram, milliliter, centimetre
3for measure unit
F127: polyoxyethylene-poly-oxypropylene polyoxyethylene 16.00g ± 0.01g
Phenol: C
6h
5oH18.30g ± 0.01g
Formaldehyde: HCHO28.50ml ± 0.01ml
Tetraethoxy: Si (OC
2h
5)
44.40ml ± 0.01ml
Dehydrated alcohol: C
2h
5oH180.00mL ± 0.01mL
Sodium hydroxide: NaOH25.065g ± 0.001g
Hydrochloric acid: HCl10.00mL ± 0.01mL
Hydrofluoric acid: HF15.00mL ± 0.01mL
Deionized water: H
2o3000ml ± 50ml
Nitrogen: N
210000cm
3± 100cm
3
Preparation method is as follows:
(1) obtain solution
1. 20wt.% sodium hydroxide solution is configured
Weighing sodium hydroxide 25.065g ± 0.001g, is dissolved in beaker, pours the volumetric flask of 100mL into, repeatedly washs beaker and pours water into volumetric flask, being titrated to 100ml, teetertottering and fully dissolve formation: 20wt.% sodium hydroxide solution.
2. 2mol/L, 0.2mol/L hydrochloric acid soln is configured
Graduated cylinder measures 8.33ml ± 0.01ml concentrated hydrochloric acid, pours the volumetric flask of 50ml into, repeatedly washs graduated cylinder and pours water into volumetric flask, being titrated to 50ml, teetertottering and be thoroughly mixed to form: 2mol/L hydrochloric acid soln.
Graduated cylinder measures 1.66ml ± 0.01ml concentrated hydrochloric acid, pours the volumetric flask of 50ml into, repeatedly washs graduated cylinder and pours water into volumetric flask, being titrated to 50ml, teetertottering and be thoroughly mixed to form: 0.2mol/L hydrochloric acid soln.
(2) formulated phenolic resin oligomer solution
1. take phenol 18.30g ± 0.01g to place in beaker, beaker is in constant temperature 40 DEG C of heating in water bath states, and phenol is melted completely.
2. add the 20wt.% sodium hydroxide solution of pre-configured 3.20ml ± 0.01ml, stir 10min.
3., under 40 DEG C of temperature constant states, the formaldehyde solution of 28.50ml ± 0.01ml is dropwise added.
4. be warming up to 72 DEG C, constant temperature stirs 1h, and mixture solution is cooled to room temperature 20 DEG C.
5. with 2mol/L hydrochloric acid soln, the pH of mixture solution is adjusted to 7.
6. the solution rotary vacuum evaporator obtained rotary evaporation 2h under vacuum tightness is 0.09MPa temperature 50 C, obtains phenol resin oligomer, airtight preservation.
7. measure phenol resin oligomer 29.625g ± 0.001g, then measure 150ml dehydrated alcohol, fully mix, be made into 20wt% phenol resin oligomer solution.
(3) prepare order mesoporous SiO
2/ C composite
Triblock copolymer body structure directed agents F127 does template, and tetraethoxy does silicon source, and phenol resin solution does carbon source.
1. the F127 weighing 3.2g ± 0.01g is dissolved in 20.50ml ± 0.01ml dehydrated alcohol, adds the hydrochloric acid soln of the 0.2mol/L of 2.20ml ± 0.01ml, stirs 1h at constant temperature 40 DEG C.
2. add the tetraethoxy of 4.40ml ± 0.01ml and the 20wt% phenol resin solution of 12.80ml ± 0.01ml successively, constant temperature stirs 2h.
3. the solution obtained is poured in furnace pot, and room temperature keeps 5-8h, then puts into baking oven, 100 DEG C of constant temperature 24h, furnace pot leaves the yellow film of one deck, is scraped and wear into fine powder.
4. powder is put into quartz boat, be placed in tube furnace center, be warming up to 350 DEG C from room temperature 20 DEG C with 1 DEG C/min and keep 3h, then be warming up to 600 DEG C with 1 DEG C/min, be warming up to 900 DEG C with 5 DEG C/min, at 900 DEG C of constant temperature 2h, obtain the order mesoporous SiO of black
2/ C composite.
(4) order mesoporous silicon carbide is prepared in carbothermic reduction
1. the SiO of 3.00g ± 0.01g is weighed
2/ C composite puts into corundum crucible, corundum crucible is put into insulating brick center groove, is placed in the region intermediate of micro-wave oven furnace chamber, adjusting position, until infrared temperature probe records sample maximum temperature point.
2. being evacuated to vacuum tightness is 0.09MPa, and passing into nitrogen to vacuum tightness is 0.03MPa, vacuumizes, logical nitrogen steps carries out twice repeatedly, after to be again evacuated to vacuum tightness be 0.09MPa, passing into nitrogen to vacuum tightness is 0.07MPa.
3. open microwave oven circulating water cooling device, then open microwave, regulate microwave power to make in-furnace temperature rise to 1300 DEG C ± 10 DEG C gradually by 25 DEG C, constant temperature 20min, solid-phase mixture is fully reacted;
SiO
2＋3C=2CO↑＋SiC
In formula: SiO
2: silicon-dioxide, C: carbon, CO: carbon monoxide, SiC: silicon carbide.
4. react rear closedown microwave, be evacuated to 0.09MPa, until cavity temperature along with after water coolant slowly cools to 25 DEG C, close recirculated water.
5. product is taken out
Open blow-off valve, when microwave oven internal pressure reaches normal atmosphere, fire door is opened automatically, and the powder in corundum crucible is the order mesoporous silicon carbide of non-removal of impurities.
(5) dedoping step
1. high temperature de-carbon
Upper step is obtained powder and puts into quartz boat, be placed in retort furnace, the lower 700 DEG C of roasting 2h of air atmosphere, remove unreacted carbon.
2. pickling silica removal
Measure hydrofluoric acid 15mL, be diluted to 30mL, by the sample dipping after de-carbon in a solution of hydrofluoric acid, leave standstill 24h.
3. centrifugation
Mixed solution is placed in centrifuge tube, with the centrifugal 6min of the rotating speed of 12000 turns/min, outwells supernatant liquid, clean to supernatant liquid pH close to 7, retain the solid sample in centrifuge tube.
4. kept dry
The sample obtained after dry 24h, is loaded in sample sack, posts label, be placed in moisture eliminator, airtight preservation in 80 DEG C of baking ovens.
(6) detect, analyze, characterize
Use transmission electron microscope observation sample topography;
Crystal phase analysis and order mesoporous qualification is carried out with X-ray powder diffractometer;
The mensuration of order mesoporous silicon carbide is carried out with specific surface and Porosimetry.
Claims (5)
1. a preparation method for order mesoporous silicon carbide, is characterized in that,
The steps include:
(i) order mesoporous SiO is prepared
2/ C composite
(ii) microwave reduction prepares order mesoporous silicon carbide
Order mesoporous SiO
2/ C composite is placed in microwave oven region intermediate, and adjustment position, until infrared temperature probe records the maximum temperature point of matrix material; Being evacuated to vacuum tightness is 0.09MPa, and passing into nitrogen to vacuum tightness is 0.03MPa, vacuumizes, logical nitrogen steps carries out twice repeatedly, after to be again evacuated to vacuum tightness be 0.09MPa, passing into nitrogen to vacuum tightness is 0.07MPa; Open microwave oven cooling water circulating device, open microwave control switch, regulate microwave power to make to be warming up to 1300 DEG C ± 10 DEG C in stove, isothermal reaction 20min; Close microwave control switch, stop heating, being evacuated to vacuum tightness is 0.09MPa, after naturally cooling to room temperature, closes recirculated water in stove; Open blow-off valve, when microwave oven internal pressure reaches atmospheric pressure, fire door is opened automatically, takes out, obtains pulverous order mesoporous silicon carbide.
2. the order mesoporous silicon carbide preparation method of one according to claim 1, is characterized in that: use Small angle X-ray powder diffraction to go out peak at 0.8o place, illustrate that synthetic product is regular orderly mesoporous material.
3. the order mesoporous silicon carbide preparation method of one according to claim 1, it is characterized in that: use suction-desorption isotherm that specific surface and Porosimetry obtain, suction-desorption isotherm meets H1 type and returns stagnant ring, what H1 type returned the reflection of stagnant ring is the cylindrical hole of even aperture distribution, pore size distribution curve can find out that aperture concentrates on 6.3nm, and the two illustrates that the silicon carbide of synthesis is ordered mesopore structure jointly.
4. the preparation method of a kind of order mesoporous silicon carbide according to claim 1, is characterized in that, the order mesoporous silicon carbide powder that (ii) step obtains has carried out removal of impurities process subsequently, and this removal of impurities process comprises high temperature carbon removal treatment and the process of pickling silica removal.
5. the preparation method of a kind of order mesoporous silicon carbide according to any claim of Claims 1-4, it is characterized in that, the method does template with triblock copolymer body structure directed agents F127, does silicon source, do carbon source with phenol resin oligomer with tetraethoxy;
The order mesoporous SiO of described preparation
2the step of/C composite is:
1. be dissolved in dehydrated alcohol by F127, add hydrochloric acid soln, 40 DEG C of constant temperature stir 1h; After add the ethanolic soln of tetraethoxy and phenol resin oligomer successively, 40 DEG C of constant temperature stir 2h, obtain mixing solutions;
2. mixing solutions is placed in container, and ambient temperatare puts 5 ~ 8h, is then placed in 24h in 100 DEG C of constant temperature ovens, and form yellow film in container, scraping wears into fine powder;
3. this fine powder is placed in tube furnace, is warming up to 350 DEG C with 1 DEG C/min and insulation 3h, then is warming up to 600 DEG C with 1 DEG C/min, be warming up to 900 DEG C with 5 DEG C/min subsequently and insulation 2h, obtain the order mesoporous SiO of black
2/ C composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610022824.8A CN105502403B (en) | 2016-01-14 | 2016-01-14 | Preparation method of ordered mesoporous silicon carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610022824.8A CN105502403B (en) | 2016-01-14 | 2016-01-14 | Preparation method of ordered mesoporous silicon carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105502403A true CN105502403A (en) | 2016-04-20 |
| CN105502403B CN105502403B (en) | 2017-05-10 |
Family
ID=55710790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610022824.8A Active CN105502403B (en) | 2016-01-14 | 2016-01-14 | Preparation method of ordered mesoporous silicon carbide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105502403B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106540733A (en) * | 2016-10-27 | 2017-03-29 | 太原理工大学 | A kind of method for preparing graphite phase carbon nitride material |
| CN107416837A (en) * | 2017-05-09 | 2017-12-01 | 武汉科技大学 | A kind of method that porous nano carborundum is prepared using silicate glass as raw material |
| CN111729678A (en) * | 2020-06-30 | 2020-10-02 | 同济大学 | Copper-palladium-loaded mesoporous silicon carbide-based catalyst and preparation method and application thereof |
| CN112093801A (en) * | 2020-05-11 | 2020-12-18 | 武汉科技大学 | Rice hull-based nano silicon carbide/carbon composite wave-absorbing material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
| WO2015015662A1 (en) * | 2013-07-31 | 2015-02-05 | 太平洋セメント株式会社 | Silicon carbide powder and method for producing silicon carbide single crystal |
-
2016
- 2016-01-14 CN CN201610022824.8A patent/CN105502403B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN102674354A (en) * | 2012-05-11 | 2012-09-19 | 南京工业大学 | Preparation method for mesoporous silicon carbide material |
| WO2015015662A1 (en) * | 2013-07-31 | 2015-02-05 | 太平洋セメント株式会社 | Silicon carbide powder and method for producing silicon carbide single crystal |
Non-Patent Citations (2)
| Title |
|---|
| YIFENG SHI ET AL.: ""Low-Temperature Pseudomorphic Transformation of Ordered Hierarchical Macro-mesoporous SiO2/C Nanocomposite to SiC via Magnesiothermic Reduction"", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 何晓燕 等: ""微波辅助碳热还原法制备碳化硅粉体"", 《伊犁师范学院学报（自然科学版）》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106540733A (en) * | 2016-10-27 | 2017-03-29 | 太原理工大学 | A kind of method for preparing graphite phase carbon nitride material |
| CN106540733B (en) * | 2016-10-27 | 2019-04-05 | 太原理工大学 | A method of preparing graphite phase carbon nitride material |
| CN107416837A (en) * | 2017-05-09 | 2017-12-01 | 武汉科技大学 | A kind of method that porous nano carborundum is prepared using silicate glass as raw material |
| CN112093801A (en) * | 2020-05-11 | 2020-12-18 | 武汉科技大学 | Rice hull-based nano silicon carbide/carbon composite wave-absorbing material and preparation method thereof |
| CN111729678A (en) * | 2020-06-30 | 2020-10-02 | 同济大学 | Copper-palladium-loaded mesoporous silicon carbide-based catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105502403B (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105502403A (en) | Preparation method of ordered mesoporous silicon carbide | |
| CN105609881B (en) | Inorganic solid electrolyte material and preparation method thereof | |
| CN109705808A (en) | A kind of cobalt-nickel alloy with MOF structure-porous carbon composite wave-suction material and preparation method thereof | |
| CN105418071B (en) | The synthetic method of high pure and ultra-fine ZrC SiC composite granules | |
| CN111004029B (en) | Far infrared energy-saving radiation coating for high-temperature furnace | |
| CN104923796A (en) | Method for industrially preparing graphene coated aluminum nanopowders | |
| CN108840683B (en) | Process for preparing zirconium nitride ceramic microspheres and zirconium nitride ceramic microspheres | |
| CN104004496B (en) | The preparation method of a kind of redox graphene/nickel oxide composite wave-suction material | |
| CN104130004B (en) | The preparation method of the block porous aluminum oxide nano pottery of high strength | |
| CN108183192A (en) | A kind of ceramic slurry and lithium ion battery separator | |
| CN110194441A (en) | The preparation method of hollow ball shape aluminium nitride powder material and aluminum nitride porous ceramic | |
| CN106542515B (en) | A kind of synthetic method of meso-porous carbon material | |
| CN108383128A (en) | A kind of preparation method of rice husk base micro-nano structure porous silica | |
| CN108640102B (en) | Preparation method and application of hollow carbon sphere micro-nano aggregate/sulfur composite material | |
| CN105489885B (en) | A kind of rodlike cobaltosic oxide of multi-pore micron and the preparation method and application thereof | |
| CN101844934A (en) | Preparation method of porous Al2O3 ceramic | |
| CN104591163B (en) | Graphene preparation method based on soft-hard plate | |
| CN101698487B (en) | Method for preparing mullite powder | |
| CN101805201B (en) | Preparation method of porous silicon carbide ceramics with high thermal shock resistance | |
| CN104129983B (en) | The preparation method of high strength block porous magnesium aluminate nano ceramics | |
| CN114835122B (en) | Method for preparing silicon carbide aerogel powder from coal gangue | |
| Jana et al. | Processing of low-density alumina foam | |
| CN101700980A (en) | Method for preparing nano-mullite powder by sol-gel-hydrothermal method | |
| CN104556210B (en) | A kind of employing hot two-step method of microwave-assisted solvent prepares Sm2sn2o7/ SnO2the method of nano-complex | |
| CN102674355A (en) | Alpha crystal phase mesoporous silicon carbide material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |