CN1569748A - Gelcasting method for producing refractory materials using millimeter-class large granule - Google Patents
Gelcasting method for producing refractory materials using millimeter-class large granule Download PDFInfo
- Publication number
- CN1569748A CN1569748A CN 200410020419 CN200410020419A CN1569748A CN 1569748 A CN1569748 A CN 1569748A CN 200410020419 CN200410020419 CN 200410020419 CN 200410020419 A CN200410020419 A CN 200410020419A CN 1569748 A CN1569748 A CN 1569748A
- Authority
- CN
- China
- Prior art keywords
- refractory materials
- add
- sialon
- gel
- macrobead
- 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
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Ceramic Products (AREA)
Abstract
The invention discloses a gelcasting method for producing refractory materials using millimeter-class large granule which comprises, subjecting the Si micropowder for preparing the Sialon raw material to organic modification, and subjecting the Al micropowder to chemical reaction coating, carrying out granulate batching to the near-spherical flame-proof coarse granule and micron level Sialon raw material fines and flame-proof fines, charging fire resistive material into water solution by the proportion of AM : MBAM = 100 : (1-7), charging dispersing agent and suspending agent, agitating, defoaming at room temperature and under normal atmosphere, charging catalyst and initiating agent into the slurry, mixing uniformly and charging the slurry into die arrangement, and carrying out heat preservation, demoulding and sintering.
Description
Technical field
According to International Patent Classification (IPC), the invention belongs to nitride, oxide compound is the preparation method of the fire resistive material product of base-material, what specially refer to complicated shape a kind ofly uses the gel-casting method that millimeter level macrobead is made refractory materials.
Background technology
Gel casting forming (gelcasting) is a kind of novel colloidal state consolidation in-situ forming methods with low-cost, quick production high reliability, complicated shape ceramic component.This method is to be invented by the engineers of Oak Ridge National Laboratoty (ORAL).It is based upon on the basis of traditional ceramics forming technique and polymer chemistry theory.Its core is to use organic monomer solution, and this solution can polymerization becomes the gel of the polymkeric substance-solvent of high-intensity, horizontal connection.Ceramic powder is dissolved in that formed slurry is cast in the mould in the solution of organic monomer, and the monomer mixture polymerization forms the agglomerative parts.Because the polymkeric substance of 10%~20% (massfraction) is laterally only arranged in the polymkeric substance-solvent that connects; Therefore, be easy to by the solvent in the drying step removal gel parts.Because the horizontal connection of polymkeric substance, in drying process, polymkeric substance can not move with solvent.The main component of this method is ceramic powder, organic monomer, polymeric initiator, dispersion agent and solvent.Gel casting forming comprises two kinds of forms of moisture and non-water.If solvent is a water, this method is called aqueous gel casting (aqueous gelcasting); If solvent is an organic solvent, this method is called non-aqueous solution gel casting forming (nonaqueous gelcasting).The green strength height of gel casting forming can be reprocessed, and can be used for making monophasic and the compound ceramic component, and the ceramic component of plastic manufacturing complicated shape, accurate size also has report to environment-friendly type macromolecule polymer application gel casting forming.
Patent of invention for example:
(1) Functionally Graded Materials gel injection moulding preparation in the static magnetic field of tight, clear, Yang Deren in the Lian, the number of applying for a patent: 03116449.8, this invention provides a kind of can utilize sophisticated ceramic gel injection method moulding process, prepare the gradient material of composition continually varying all thickness, formality simplification, cost reduction, the performance of production Functionally Graded Materials are improved.
(2) preparation method of a kind of lamination sheet type PTC themistor of Zhou Dongxiang, Hu Yunxiang, Zheng Zhiping, Gong Shuping, the number of applying for a patent: 03128235.0, this invention provides a kind of bar-shaped PTC ceramic body that adopts gel-casting method to prepare even compact, with the base substrate of moulding at high temperature sintering obtain bar-shaped PTC pottery, the lamination sheet type PTC themistor that makes has high PTC effect.
But the application of gel casting process at present concentrates on uses micron order and nano level fine powder to make on the stupalith as raw material, uses millimeter level large-size particle raw material to adopt the gel casting process moulding to make refractory materials and does not appear in the newspapers.
Summary of the invention
The present invention is directed to the lower problem of difficult forming, performance that present manufacturing refractory materials complicated shape product exists and the needs of special purpose, a kind of gel-casting method that millimeter level large-size particle is made refractory materials of using is provided, prepare complicated shape, excellent property, size accurately, homogeneous microstructure, the regular fire resistive material product of outward appearance.
The millimeter grade particle that is shaped to spheroidal that adopts median size 1.7mm is as meal, and micron order Si powder, Al powder after surface modification, coating are handled are by rational grain graininess batching; Nitride, oxide compound, the carbide of using gel injection technology manufacturing complicated shape are base-material, and the manufacturing fire resistive material product of the thing that mutually combines between them.This size accurately, homogeneous microstructure, the regular novel manufacturing fire resistive material product of outward appearance, can have wide practical use in industries such as ferrous metallurgy, nonferrous metallurgy, electronics, potteries.
Its process flow sheet as shown in drawings, technology is divided into:
(1) to preparing the pre-treatment step of Sialon activated feedstock
Sialon is to the abbreviation by the elementary composition a kind of synthetic mineral of Si, Al, O, N.
A, Industrial Metal Si powder is adopted the organism modification, be that the micron-sized metal industry Si of granularity 5~80 μ m powder is immersed in the polyacrylic resin aqueous solution, under normal temperature, normal pressure induction stirring, mix 1~4h, dry 24h down at 80 ℃ after filtering, make metal industry Si powder surface coat the last layer organic film.
B, adopt chemical reaction to coat to industrial Al powder, it is the pure stove of well heater that the micron-sized industrial Al powder of 5~80 μ m is placed molybdenum filament.Under the flowing nitrogen effect, heat 5h down at 300~900 ℃, nitrogen partial pressure is 0.01~0.08MPa in the stove, has generated the film of very thin aluminium nitride on Al powder surface.
Form Sialon activated feedstock micron order fine powder Si: the Al atomic ratio is 1: (0~3), and look the refractory materials of required production and adjust its value.Si sometimes for example: the Al atomic ratio is 1: 1, Si sometimes: the Al atomic ratio is 1: 0, does not promptly use the Al powder, preparation silicon nitride combined with silicon carbide refractory material goods.
(2) preparation premixed liquid step
With organic monomer acrylamide (AM) and linking agent N-N ' methylene-bisacrylamide (MBAM), by weight AM: MBAM=100: (1~7) is dissolved in the water, the concentration 3~12wt% of this AM+MBAM in the aqueous solution
(3) preparation slurry stage
Becoming the oarse-grained nitride of millimeter level, oxide compound, the carbide of spheroidal with integer is base-material, and the manufacturing refractory materials meal of the thing that mutually combines between them, median size d
50: the 1.7mm proportioning is weight ratio 15~55wt%, with first step pre-treatment granularity be active Si of Sialonl and the Al powder of 5~80 μ m, proportioning is weight ratio 10~20wt%, and granularity is the micron fine powder of the refractory materials of 5~80 μ m, and proportioning is that weight ratio 35~55wt% joins in the premixed liquid.Add as the weak caustic solution of ammoniacal liquor, the pH value of solution is adjusted to 7~10 from 4~5, and adding organic dispersing agent and suspension agent.Suspension agent is that calcium lignin sulphonate, polyvinyl alcohol etc. are multiple, its amount of allocating into is 1~7wt% of total solution weight, dispersion agent will be selected the dispersion agent of its specific adsorption for different refractory materialss, for example just use the citric acid diamines of 20% concentration to make dispersion agent for corundum, add-on is 0.5~3wt% of slurry gross weight ratio.
Above-mentioned slurries are stirred de-bubble under normal temperature, the condition of normal pressure in the speed governing stirrer.The rotating speed of stirrer is controlled at 12~80r/min, and de-bubble 2~8h in slowly stirring slowly eliminates the bubble in the slurries, make solid formation and premixed liquid uniform mixing, made viscosity<1000mPa.s, solid load 78~81vol%, the stable slurry that high stability does not promptly worsen in 48h.
(4) gel casting forming, baking step
Add catalyzer and initiator in slurry, make it evenly to stir 3-20min under 50~80r/min rotating speed in the speed governing stirrer, catalyzer is that concentration is 20% Tetramethyl Ethylene Diamine solution, and add-on is the 0.1~1wt ‰ of total solution weight ratio.Initiator is the ammonium persulfate solution of 5% concentration, and add-on is 0.01~0.1wt% of total solution weight ratio, afterwards slurry is injected mould and solidifies 12~24h down at 60~80 ℃; Curing and demolding obtains fine and close high strength base substrate uniformly, and base substrate is dried 24~48h down at 80~100 ℃.
(5) sintering step
With base substrate under nitrogen atmosphere, 1360~1520 ℃ of following sintering 12~72h, obtained size accurately, homogeneous microstructure, the regular refractory products of outward appearance.
It is the manufacturing fire resistive material product that material forming prepares different sorts, complicated shape that the present invention is suitable for adopting millimeter level large-size particle, be applicable to that with nitride, oxide compound, carbide be base, and the manufacturing refractory materials moulding of the thing that mutually combines between them; Be particularly suitable for silicon nitride combined silicon carbide, Sialon based on silicon carbide, Sialon combined corundum and the Sialon of the complicated shape moulding in conjunction with the zircon corundum refractory materials, constituting millimeter level refractory materials macrobead is the particle that is processed into spheroidal through shaping.Its product has physicochemical property and the weave construction close with mechanical-moulded product, can improve the performance that Idiotype is made refractory materials effectively, reduces manufacturing cost.
For example:
Refractory materials | Volume density g/cm 3 | Folding strength MPa | |||
Mechanical-moulded | Gel casting forming | Mechanical-moulded | Gel casting forming | ||
????1 | Silicon nitride combined silicon carbide | ????2.65 | ??2.65 | ??45 | ??52 |
????2 | The Sialon based on silicon carbide | ????2.67~2.7 | ??2.68 | ??48 | ??57 |
????3 | The Sialon combined corundum | ????3.10 | ??3.08 | ??27 | ??41 |
Description of drawings
The gel injection molding and forming technology schema.
Embodiment
(1) gel casting forming of Sialon carborundum refractory material and nitridation sintered
With median size 1.7mm through being shaped to spheroidal the silicon carbide macrobead and the carbide fine powder of granularities at different levels, the method narrated as the front after handling micron order modification Si powder and coat the Al powder and add acrylamide (AM).In the aqueous solution of the premix of N-N ' methylene-bisacrylamide (MBAM), AM: MBAM=100: 5, the concentration 10% of AM+MBAM in the aqueous solution.In the speed governing stirrer, stir while adding.Grade is prepared burden in weight ratio, median size d
50: 1.7mm level meal 45wt%, granularity is the carbide fine powder 40wt% of 5~50 μ m, 1 μ m α-Al
2O
3Powder 3wt%, modification Si powder, coat Al powder 12wt% (atomic ratio Si: Al=1: 0.98), slurry solid content 80vol%.
In the speed governing stirrer, stirred 6 hours with rotating speed 30r/min, the bubble of slurry is excluded, with weak ammonia pH value of slurry is adjusted to 9 from 4~5 simultaneously, and add organic suspending agent and dispersion agent, preparation viscosity is the stable slurry of 800mPa.s, solid load 80vol%.Suspension agent is a polyvinyl alcohol, and add-on is the 1wt% of slurry gross weight; Dispersion agent is the tetramethylammonium hydroxide aqueous solution of concentration 20%, and add-on is the 1wt% of slurry gross weight.
Add in slurry and after catalyzer and initiator stir slurry is injected mould, catalyzer is the Tetramethyl Ethylene Diamine class solution of 20% concentration, and add-on is the 0.05wt% of slurry gross weight.Initiator is the ammonium persulfate solution of 5% concentration, and add-on is 0.01% of a slurry weight, stirs 15min under 50~80r/min mixing speed.Into mould is poured slurries in the back, solidifies 16h at 60 ℃, and curing and demolding obtains fine and close high strength base substrate uniformly.Base substrate at 80 ℃ of following oven dry 24h, is sent in the sintering oven of nitrogen atmosphere, the most at last base substrate in 1465 ℃ of nitrogen atmosphere sintering ovens, sinter into obtain size accurately, homogeneous microstructure, the regular refractory materials of outward appearance, the volume density of product is 2.68g/cm
3, folding strength is 57MPa.
(2) gel casting forming of Sialon combined corundum refractory materials and nitridation sintered
With median size 1.7mm through being shaped to spheroidal brown corundum in granules and the corundum fine powder of granularities at different levels, micron order modification Si powder and coat the Al powder and add in the premix aqueous solution of acrylamide (AM), N-N ' methylene-bisacrylamide (MBAM), AM: MBAM=100: 5, the concentration of AM+MBAM in the aqueous solution is 10%.Stir while adding in the speed governing stirrer, grade is prepared burden in weight ratio, median size d
50: 1.7mm shaping palm fibre corundum in granules 43wt%, granularity is the brown corundum fine powder 40wt% of 5~20 μ m, 1 μ m α-Al
2O
3Powder 3wt%, modification Si powder, (atomic ratio Si: Al=1: 0.98), the slurry solid content is 81vol% to coat Al powder 12wt%.
In the speed governing stirrer, stirred 8 hours with rotating speed 30r/min, the bubble of slurry is excluded, with weak ammonia pH value of slurry is adjusted to 9 from 4~5 simultaneously, and add organic suspending agent and dispersion agent, preparation viscosity is the stable slurry of 800mPa.s, solid load 81vol%.Suspension agent is a polyvinyl alcohol, and add-on is the 5wt% of slurry gross weight.Dispersion agent is citric acid two amine aqueous solutions of 20% concentration, and add-on is the 1wt% of slurry gross weight.In slurry, add and after catalyzer and initiator stir slurry is injected mould.Catalyzer is 20% concentration Tetramethyl Ethylene Diamine class solution, and add-on is the 0.5wt% of slurry gross weight.Initiator is the ammonium persulfate solution of 5% concentration, and add-on is the 0.02wt% of slurry gross weight.Stir 15min under 50~80r/min mixing speed, into mould is poured slurries in the back.Solidify 24h at 60 ℃, curing and demolding, obtain fine and close high strength base substrate uniformly, base substrate is dried 24h down at 80 ℃, send into the sintering oven under the nitrogen atmosphere, with base substrate in 1500 ℃ of nitrogen atmosphere sintering ovens, sinter into obtain size accurately, homogeneous microstructure, the regular refractory materials of outward appearance, the volume density of product is 3.08g/cm
3, folding strength is 41MPa.
(3) gel casting forming of silicon nitride combined with silicon carbide refractory material and nitridation sintered
Carbide fine powder, the micron order modification Si powder of the silicon-carbide particle of median size 1.7mm through being shaped to spheroidal and each grade are added in the premix aqueous solution of acrylamide (AM), N-N ' methylene-bisacrylamide (MBAM), AM: MBAM=100: 7, the concentration 10% of AM+MBAM in the aqueous solution.In the speed governing stirrer, stir while adding.Grade is prepared burden in weight ratio, median size d
50: 1.7mm silicon carbide shaping particle 45wt%, the modification Si powder of 5~30 μ m carbide fine powder 40wt% and one-size is 15wt%, total solid load 78vol%.In the speed governing stirrer, stir 6h, the bubble of slurry is excluded, with weak ammonia pH value of slurry is adjusted to 9 from 4~5 simultaneously, and add organic suspending agent and dispersion agent, the stable slurry of preparation low viscosity, solid load 78vol% with rotating speed 30r/min.Suspension agent is a polyvinyl alcohol, and add-on is the 3wt% of total solution weight.Dispersion agent is the Tetramethylammonium hydroxide of 20% concentration, and this solution add-on is the 1wt% of total solution weight.The viscosity of slurries is 800mPa.s, adds catalyzer and initiator in slurry, and catalyzer is identical with embodiment 1 with initiator.Under 50~80r/min rotating speed, stir 15min and evenly the back slurry is poured into mould; at 80 ℃ of heat preservation solidification 24h; the demoulding obtains fine and close high strength base substrate uniformly; base substrate is dried 24h down at 80 ℃; send in the sintering oven under the nitrogen atmosphere; with base substrate in 1420 ℃ of nitrogen atmosphere sintering ovens, sinter into size accurately, homogeneous microstructure, the regular refractory materials of outward appearance, the volume density of product is 2.65g/cm
3, folding strength is 52MPa.
Claims (5)
1, a kind of gel-casting method of using millimeter level macrobead manufacturing refractory materials is characterized in that preparation method's composition step and each step technique condition are as follows:
(1) to constituting Sialon activated feedstock pre-treatment step
A, to carry out the organism modification to the Industrial Metal Si powder that constitutes the Sialon activated feedstock and handle, be that granularity 5~80 μ m metal industry Si powder are immersed in the polyacrylic resin aqueous solution, mix 1~4h, afterwards after filtration, dry 24h down at 80 ℃, coat the film of last layer resin on Industrial Metal Si powder surface;
B, carry out chemical reaction and coat constituting Sialon activated feedstock industry activated feedstock, be the industrial Al powder of particle diameter 5~80 μ m to be put into molybdenum filament heat pure stove, under flowing nitrogen atmosphere, nitrogen partial pressure 0.01~0.08MPa, heat 5~6h down at 300~900 ℃, generated the film of very thin aluminium nitride on Al powder surface;
(2) preparation premixed liquid step
With organic monomer acrylamide (AM) and exchanger N-N ' methylene-bisacrylamide (MBAM), by weight AM: MBAM=100: (1~7) is soluble in water, and this AM+MBAM concentration in the aqueous solution is 3~12wt%;
(3) preparation slurry stage
With d
50: 1.7mm millimeter level is shaped to the refractory materials meal of the macrobead manufacturing of spheroidal, by weight 15~55wt%, 5~80 μ m granularity micron order refractory materials fine powders, by weight 35~55wt%, and the Sialon1 activated feedstock Si after handling and Al micropowder join in the premixed liquid by weight 10~20wt%, add while stirring, make the slurry of solid formation content 78~81vol%, the dispersion agent of the specific adsorption that the adding suspension agent is matched with looking different material adds and as the ammoniacal liquor weak caustic solution pH value of slurries is adjusted to 7~10 from 4~5; Under normal temperature and normal pressure, stir 2~8h, remove the bubble in the slurries with 12~80r/min low-rotate speed; Make the slurries of its stability of viscosity<1000mPa.s for can in 48h, not worsening;
(4) gel casting forming, baking step
The initiator that catalyzer that the Tetramethyl Ethylene Diamine solution of adding regulation ratio constitutes in slurries and ammonium persulfate solution constitute, under 50~80r/min rotating speed, stir 3~20min and evenly inject mould in the back, solidify 12~24h down at 60~80 ℃, the demoulding is afterwards dried 24~48h down at 80~100 ℃ again, makes the base substrate of special refractories goods;
(5) sintering step
In the nitrogen atmosphere sintering oven, base substrate at 1360~1520 ℃ of following sintering 12~72h, has been made complex-shaped fire resistive material product.
2, a kind of gel-casting method that millimeter level macrobead is made refractory materials of using according to claim 1, in the 3rd step of its preparation method, to add suspension agent, suspension agent is characterised in that and is calcium lignin sulphonate or polyvinyl alcohol that add-on is 1~7wt% of total solution weight.
3, a kind of gel-casting method that millimeter level macrobead is made refractory materials of using according to claim 1, in the 4th step of its preparation method, to add catalyzer and initiator, these two kinds of additives are characterised in that, Tetramethyl Ethylene Diamine by 20% concentration constitutes catalyzer, add-on is 0.1~1wt% of total solution weight, by the initiator that 5% concentration ammonium persulphate constitutes, add-on is 0.01~0.1wt% of total solution weight.
4, a kind of gel-casting method that millimeter level macrobead is made refractory materials of using according to claim 1, prepare at the first step of its preparation method that used Si micro mist and Al micro mist are characterised in that its Si in the pre-treatment of Sialon activated feedstock: Al proportioning atomic ratio is 1: (0~3), and look the refractory materials of required production and adjust its value.
5, a kind of gel-casting method that millimeter level macrobead is made refractory materials of using according to claim 1, it is characterized in that this method is applicable to that by nitride, oxide compound, carbide be the moulding that complicated shape base-material and that mutually combine thing between them is made fire resistive material product, be particularly suitable for silicon nitride combined silicon carbide, Sialon based on silicon carbide, Sialon combined corundum, the Sialon of complicated shape make refractory materials in conjunction with zircon corundum moulding; Constituting millimeter level refractory materials macrobead is the particle that is processed into spheroidal through shaping.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB200410020419XA CN1296322C (en) | 2004-04-20 | 2004-04-20 | Gelcasting method for producing refractory materials using millimeter-class large granule |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB200410020419XA CN1296322C (en) | 2004-04-20 | 2004-04-20 | Gelcasting method for producing refractory materials using millimeter-class large granule |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1569748A true CN1569748A (en) | 2005-01-26 |
CN1296322C CN1296322C (en) | 2007-01-24 |
Family
ID=34479682
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB200410020419XA Expired - Fee Related CN1296322C (en) | 2004-04-20 | 2004-04-20 | Gelcasting method for producing refractory materials using millimeter-class large granule |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1296322C (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101693619B (en) * | 2009-10-16 | 2012-06-06 | 清华大学 | Method for preparing high-imitation stone sculpture by utilizing stone powder |
CN103613402A (en) * | 2013-12-04 | 2014-03-05 | 天津大学 | O-Sialon porous material prepared by gel-casting and preparation method thereof |
CN104002374A (en) * | 2014-05-19 | 2014-08-27 | 济南大学 | Plaster concrete building block forming machine |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05506066A (en) * | 1990-04-20 | 1993-09-02 | マーチン・マリエッタ・エナジー・システムズ・インク | Nitriding method for heat-resistant metal articles |
CN1092168C (en) * | 2000-09-29 | 2002-10-09 | 清华大学 | Non-oxygen polymerization-inhibiting gel injection process for preparing ceramic parts |
JP2003176183A (en) * | 2001-12-11 | 2003-06-24 | Taiheiyo Cement Corp | Inorganic joining member and production method therefor |
KR20030057134A (en) * | 2001-12-28 | 2003-07-04 | 한국기계연구원 | Slip for making ceramic core and its making method |
-
2004
- 2004-04-20 CN CNB200410020419XA patent/CN1296322C/en not_active Expired - Fee Related
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101693619B (en) * | 2009-10-16 | 2012-06-06 | 清华大学 | Method for preparing high-imitation stone sculpture by utilizing stone powder |
CN103613402A (en) * | 2013-12-04 | 2014-03-05 | 天津大学 | O-Sialon porous material prepared by gel-casting and preparation method thereof |
CN103613402B (en) * | 2013-12-04 | 2015-04-22 | 天津大学 | O-Sialon porous material prepared by gel-casting and preparation method thereof |
CN104002374A (en) * | 2014-05-19 | 2014-08-27 | 济南大学 | Plaster concrete building block forming machine |
Also Published As
Publication number | Publication date |
---|---|
CN1296322C (en) | 2007-01-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104446487A (en) | Slurry and method for gelcasting pressureless sintered silicon carbide ceramics | |
US20080292862A1 (en) | Method for producing anisoptropic bulk materials | |
JP2010132549A (en) | Ceramic component containing inclusion | |
CN101503299A (en) | Gel injection moulding preparation for gradient material in rotating magnetic field | |
CN110668813A (en) | Preparation method of nano zirconia granulated powder | |
CN101164987A (en) | Silicon carbide water-base casting slurry containing alpha-silicon nitride whisker and preparation method thereof | |
KR20170130778A (en) | The manufacturing method of ceramic molded object using gel casting | |
CN1686949A (en) | Method for preparing poruos material in micro-nano magnitude | |
EP0905107B1 (en) | Method for molding an article from a powder slurry | |
Wang et al. | Lattice-structured SiC ceramics obtained via 3D printing, gel casting, and gaseous silicon infiltration sintering | |
CN1915626A (en) | Method for preparing gradient material of strong magnetism and weak magnetism through flow casting molding in pulse magnetism | |
CN104959594A (en) | Method for preparing high-solid-phase low-adherence magnetic alloy powder used for 3D printing | |
CN1296322C (en) | Gelcasting method for producing refractory materials using millimeter-class large granule | |
CN1445196A (en) | Method for preparing gelatin mold made from functional gradient material in static magnetic field | |
CN103849790B (en) | A kind of in-situ preparation homogeneous nano level ceramic-metal composite material and preparation method thereof | |
CN112321297B (en) | Method for preparing porous oxide microspheres by using geopolymer as binder | |
CN111410533A (en) | Method for preparing large-size ceramic material by gel injection molding | |
CN1817511A (en) | Gel mould-injecting formation of porous titanium with various shape | |
CN1206069C (en) | Press filtering process to form functional gradient material in static magnetic field | |
CN108503360B (en) | Preparation method of LSM bulk material | |
CN1911619A (en) | Preparation method of strong magnetic-weak magnetic gradient material gel injection mould in pulse magnetic field | |
CN1065285A (en) | Vibratable resin-bonded fire proofing composition | |
JP4572290B2 (en) | Manufacturing method of conductive ceramic products | |
CN1438084A (en) | Functional gradient material slip-casting formation preparation method in maynetostatic field | |
CN1293021C (en) | Method for producing metal-ceramic gradient materials |
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 | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070124 |