CN100403588C - Method for producing solid oxide fuel cell anode substrate and die - Google Patents
Method for producing solid oxide fuel cell anode substrate and die Download PDFInfo
- Publication number
- CN100403588C CN100403588C CNB2005101027534A CN200510102753A CN100403588C CN 100403588 C CN100403588 C CN 100403588C CN B2005101027534 A CNB2005101027534 A CN B2005101027534A CN 200510102753 A CN200510102753 A CN 200510102753A CN 100403588 C CN100403588 C CN 100403588C
- Authority
- CN
- China
- Prior art keywords
- weight
- slip
- substrate
- ball
- plasticizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
This invention relates to a method for preparing porous anode base plates of solid oxide fuel batteries and moulds, in which, the process flow is as follows: preliminary batching, preliminary ball mill, secondary batch, secondary ball mill, injection mould, heating of gel, taking off the mould, drying, baking and sintering, which utilizes the self-initiation character of nickelous oxide and applies two steps of ball mill procedures without adding initiators or eliminating air bubbles so as to simplify the operation and reduce cost.
Description
Technical field
The invention belongs to field of solid oxide fuel, relate to a kind of method and mould for preparing the Solid Oxide Fuel Cell porous anode substrate.
Background technology
As a kind of energy conversion device of efficient, environmental protection, Solid Oxide Fuel Cell (SOFC) has two kinds of typical structural styles: board-like and tubular type.Wherein, board-like SOFC because simple in structure, preparation cost is low, power density advantages of higher and quite being paid attention to.The SOFC of this structure generally has electrolyte-supported and anode-supported dual mode, and wherein the anode-supported mode has been subjected to because of the internal resistance of cell is lower adopting more widely.When adopting the anode-supported mode, need prepare flawless porous anode supporting substrate, employed raw material is generally the mixed system of nickel protoxide and doped zirconia, and the method that is adopted mostly is the The tape casting of the invention forties in 20th century.The basic process steps of The tape casting comprises: batching, ball milling, moulding, drying, peel off, sintering etc.Its key technology is, adds organic bond in slip, and as polyvinyl butyral resin (PVB), by the volatilization of solvent in the dry run, organic bond is set up network configuration between solid phase particles, forms base substrate.Often need to use high-volatile poisonous organic solvents such as toluene, dimethylbenzene in this method, contaminated environment not only, health risk, and also cost is higher.In addition, content of organics is higher in the base substrate of being prepared by this method, and it is big, seriously polluted to remove organic energy consumption, and it is big to remove in the organic substance process base substrate change in volume, easily deformable and cracking.In addition, also there is the shortcoming of apparatus expensive in this method.In recent years, people begin to develop water base casting process, are solvent with water, to avoid with an organic solvent, reduce slip viscosity simultaneously, improve the solid concentration in slip and the base substrate, reduce content of organics.But the shortcoming that has apparatus expensive equally, and wayward (silicate circular, 2001,20 (5): 22-27) of green body quality.
U.S.'s Oak Ridge (Oak Ridge) National Laboratory in 1991 invented equipment simple, pollute the little water base notes type method (U.S.PatentNo.5028362) of congealing into, constantly be improved subsequently and use.This method generally comprises following processing step: batching, ball milling, degasification, adding initator, injection molding, gelling, the demoulding, drying, sintering etc.This method adopts water-soluble organic monomer and crosslinking agent, under catalysis or heating condition, by the initiation of initator, finishes polymerization reaction, sets up network configuration, forms base substrate.Organic monomer generally adopts acrylamide, Methacrylamide etc.; Crosslinking agent generally adopts N, N-methylene-bisacrylamide etc.; Initator is generally persulfate solution, or the mixed solution of persulfate and sulphite (CN 1370758A).But this method is used to prepare the DB of single constituent element more, and Shang Weiyou adopts the report of this method moulding SOFC nickel protoxide/doped zirconia complex phase porous anode substrate.Someone adopts water base notes to coagulate the NiO-SDC (Sm of method system SOFC
2O
3Doped Ce O
2) the anode powder, to improve the mixing uniformity of complex phase powder, (J.PowerSources 2004,132:36-41) but do not use this method moulding anode or anode support.And up to the present, this method needs in the slip that ball milling finishes to add separately initator in use all the time, and do not see as yet utilize nickel protoxide in the slip system from initiation characteristic, save the report of independent this step of adding initator.After adding initiator solution, general by the manual slip that stirs, so that initator is evenly distributed, this has not only increased the complexity of operation, and be easy to change the original rheological behavior of slip, destroy the uniformity of slip, and stir and be not easy to guarantee that initator is evenly distributed by hand, often cause the inhomogeneous of the inconsistent and gel structure that forms of the gelation rate at each position in the slip.In addition, this method is generally only carried out Ball milling one time to raw material, this is inappropriate often for preparation multicomponent mixed system, because the dispersing characteristic of different constituent elements is generally different, only adopts a kind of ball-milling technology often to be difficult to realize the fine dispersion of polynary mixed system.Even for single constituent element system, owing to disperse bad, usually contain bubble in the slip, thereby this method often will remove bubble to the slip behind the ball milling and handle, as vacuumizes stirring, machinery or sonic oscillation, add defoamer etc., this has not only increased operating procedure, has improved cost, and may destroy original rheological behavior of slip and uniformity.With regard to the mould that uses, the particular manufacturing craft of appear in the newspapers (CN 1370759A) only is applicable to that slip viscosity is lower, flowability system preferably, and higher for viscosity, the mobile relatively poor or tangible system of thixotropy then can produce more defective; And because mould is uprightly placed, slip is easy to cause gel structure inhomogeneous because of significantly uneven distribution takes place in the gravitational settling effect before gelling.
Summary of the invention
The objective of the invention is, prepare shortcomings such as the existing apparatus expensive of SOFC anode substrate, energy consumption are big, contaminated environment at present The tape casting, concentrate on and prepare single constituent element dense green with the water base notes type fado that congeals into, and there are drawbacks such as initator adds separately, single step ball milling slip, and existing annotate coagulate mould be not suitable for the higher slip of viscosity, gelling before slip be easy to produce shortcomings such as uneven distribution, a kind of water base notes that prepare Solid Oxide Fuel Cell porous composite anode substrate congeal into type method and particular manufacturing craft are proposed.
Technical scheme of the present invention is, a kind of method for preparing solid oxide fuel cell anode substrate is characterized in that, utilize nickel protoxide in the slip system from initiation characteristic, need not to add separately initator, may further comprise the steps:
1, first batching---take by weighing doped zirconia powder, organic monomer, crosslinking agent, water, dispersant, suspending agent and plasticizer; Doped zirconia is Y
2O
3, Sm
2O
3ZrO Deng doped with rare-earth oxide
2Its particle diameter is 0.1～10.0 μ m, organic monomer is acrylamide or Methacrylamide, crosslinking agent is N, N-methylene-bisacrylamide, water are running water, pure water, deionized water or distilled water, and dispersant is ammonium polyacrylate, ammonium polymethacrylate or ammonium citrate, suspending agent is a gum arabic, and plasticizer is a polyethylene glycol; The weight of doped zirconia should be determined according to the substrate size of required preparation, general every preparation 1cm
3The final anode substrate of volume, need to add 1.2～2.2g, the weight of organic monomer, water, dispersant, suspending agent and plasticizer is respectively 10.0～30.0%, 55.0～200.0%, 0.0～7.0%, 0.0～1.3% and 0.0～3.0% of doped zirconia weight, and the weight of crosslinking agent is 1/10～1/30 of organic monomer weight;
2, first ball milling---above-mentioned material is put into the ball grinder that has abrading-ball, and abrading-ball weight is 70～250% of above-mentioned material total weight, and with the rotating speed of 500～1100rpm, ball milling 8～48h forms first slip;
3, second batch---take by weighing nickel protoxide powder, dispersant and plasticizer; The particle diameter of nickel protoxide is 0.1～10.0 μ m, and dispersant is ammonium polyacrylate, ammonium polymethacrylate or ammonium citrate, and plasticizer is a polyethylene glycol; The weight of nickel protoxide is 100～160% of doped zirconia weight described in the step 1, and the weight of dispersant, plasticizer is respectively 0.0～7.0% and 0.0～3.0% of nickel protoxide weight;
4, secondary ball milling---with the material that 3 steps took by weighing, add in the first slip of step 2 acquisition, adopt the ball grinder and the abrading-ball of step 2, with the rotating speed of 400～850rpm, ball milling 0.5～6.0h forms the secondary slip;
5, injection molding and gelling---with above-mentioned secondary slip, inject particular manufacturing craft, seal the exhaust outlet of particular manufacturing craft then, perhaps particular manufacturing craft is placed inert gas atmospheres such as nitrogen or argon gas, heat 0.5～8h down at 40～80 ℃, make the abundant gelling of secondary slip in the particular manufacturing craft, form the substrate wet gel;
6, the demoulding---above-mentioned particular manufacturing craft is removed sealing, or from inert atmosphere, take out, take out the substrate wet gel in the mould then;
7, drying---the aforesaid substrate wet gel is placed between the plasterboard of two surfacings, in static or moving air, be no more than under 80 ℃ the temperature, carry out dried, form the substrate xerogel.
8, roasting and sintering---the aforesaid substrate xerogel is placed between the ceramic wafer such as aluminium oxide, zirconia of two surfacings, that carries out 300～450 ℃ * 0.5～10h removes the organic substance roasting, with the sintering processes of 1100～1350 ℃ * 0.5～10h, form final Solid Oxide Fuel Cell porous anode substrate.
The described mould for preparing the method for solid oxide fuel cell anode substrate is characterized in that, comprises that the backing plate (1) of a horizontal positioned, a special-shaped that is bonded on the backing plate (1) cut apart a circle (2) and a cover plate (3); The overall dimension of described backing plate (1) is slightly larger than the overall dimension of cutting apart circle (2), the inboard of cutting apart circle is shaped as square or rectangular, on its corner location, have exhaust passage (4), exhaust passage (4) has the part of exposing cover plate (3), be the exhaust outlet in the above-mentioned steps 5, behind the injection molding if need seal exhaust outlet, then adopt sealing strip (5), the profile of cover plate is a rectangle, be placed on and cut apart on the circle (2), size on Width should guarantee that part covers, part exposes the exhaust passage, and size in the longitudinal direction is slightly larger than cuts apart the size of circle on this direction; Backing plate (1) and cover plate (3) adopt any surface finish, smooth fine and close sheet material, and as making such as glass plate, metallic plate, plastic plates, thickness is generally 2～10mm; Cutting apart circle (2) is manufacturing materials with any surface finish, smooth rubber or plastics, and thickness is generally 0.5～3.0mm by the thickness decision of target base plate; The width of exhaust passage (4) is generally 2～8mm, and length is 5～50mm; Sealing strip (5) adopts material such as adhesive tape.
Compare with the The tape casting of existing preparation SOFC anode substrate, the present invention has advantages such as equipment is simple, energy consumption is little, environmental pollution is little.Compare with the existing water base notes type method of congealing into, at first, the present invention utilize nickel protoxide in the slip system from initiation, need not to add initators such as persulfate separately after ball milling finishes, this has not only simplified operation, also avoided adding initiator solution to the inhomogeneity destruction of the slip that finishes with Ball milling, with change to the slip rheological behavior, and the manual stirring initator skewness that may cause, these all help to improve the uniformity of gel; Secondly, the present invention adopts two step ball-milling technologies, successfully realized the fine dispersion of nickel protoxide and doped zirconia mixed powder, its dispersion effect is better than existing single step Ball milling, because good dispersion does not have bubble in the slip, thereby need not to remove bubble and handle, simplified technology, reduced cost, also avoided except that the slip contingent rheological behavior of institute in the bubble process and be evenly distributed sexually revising.The particular manufacturing craft of the present invention's design is because in use earlier with backing plate (1) horizontal positioned, in cutting apart circle (2), special-shaped pours slip into again, cover cover plate (3) then from top to bottom, when this congeals into the type particular manufacturing craft with the existing water base notes of use, fix mould earlier, in mold cavity, inject slip again and compare, can be fit to that viscosity is higher, flowability is poorer, just under same dispersing technology, the slip that solid concentration is higher more helps satisfying the requirement that people improve the solid concentration in the slip.And because die horizontal is placed, the sedimentation degree that because of action of gravity take place of the solid phase particles in the slip before gelling weakens, and the prepared gel uniformity that goes out improves.
Description of drawings
Fig. 1 is that the water base notes of the present invention type method of congealing into prepares the process chart of SOFC anode substrate.
Fig. 2 is water base notes that the present invention the designs type method particular manufacturing craft installation diagrams that congeal into.Drawing is described as follows: (1) backing plate, (2) cut apart circle, (3) cover plate, (4) exhaust passage, (5) sealing strip.
Embodiment
Embodiment 1: put into agate abrading-ball 170g in nylon ball grinder, average grain diameter is the 8YSZ (8mol.%Y of 5.0 μ m
2O
3The ZrO that mixes
2) 60.00g, Methacrylamide (MAM) 13.50g, N, N-methylene-bisacrylamide (MBAM) 0.67g, distilled water 36.00g, ammonium polyacrylate (PAA) 1.20g; With ball grinder with 750rpm ball milling 15h; Adding average grain diameter in above-mentioned ball grinder is nickel protoxide 88.80g, the PAA2.20g of 5.0 μ m; With 650rpm ball milling 1h; Be ready to each parts of particular manufacturing craft shown in Figure 2, to be stained with the rubber special-shaped and cut apart glass backing plate (1) horizontal positioned of circle (2), in cutting apart the zone that circle (2) limited, special-shaped pours above-mentioned slip into, cover glass cover-plate (3) from top to bottom, exhaust passage (4) are exposed the part (exhaust outlet) of cover plate (3), seal, then this is marked with the mold heated to 70 ℃ of slip with adhesive tape sealing strip (5), and maintenance 3h, the slip complete gelation in the mould; Remove sealing strip (5), open cover plate (3), take out the substrate wet gel of any surface finish; Be placed between two block gypsum plates of surfacing, air dry forms any surface finish, smooth substrate xerogel; This xerogel is placed between two surfacings, the bright and clean alumina plate, roasting through 400 ℃ * 10h removes organic substance, with the sintering of 1300 ℃ * 5h, it is all suitable promptly to obtain porosity, intensity, and internal structure is even, the SOFC anode substrate of surfacing.
Embodiment 2: put into agate abrading-ball 90g in nylon ball grinder, average grain diameter is 8YSZ 27.00g, acrylamide (AM) 6.10g, MBAM 0.34g, distilled water 16.50g, polyethylene glycol (PEG) 0.27g, ammonium polyacrylate (PAA) 0.27g of 5.0 μ m; With ball grinder with 500rpm ball milling 1h, again with 800rpm ball milling 13h; Adding average grain diameter in above-mentioned ball grinder is nickel protoxide 40.50g, PEG 0.40g, the PAA 0.40g of 2.0 μ m; With 420rpm ball milling 0.5h, again with 800rpm ball milling 1h; Be ready to each parts of particular manufacturing craft shown in Figure 2, to be stained with the plastics special-shaped and cut apart glass backing plate (1) horizontal positioned of circle (2), in cutting apart the zone that circle (2) limited, special-shaped pours above-mentioned slip into, cover glass cover-plate (3) from top to bottom, exhaust passage (4) are exposed the part (exhaust outlet) of cover plate (3), seal, then this is marked with the mold heated to 60 ℃ of slip with adhesive tape sealing strip (5), and maintenance 3.5h, the slip complete gelation in the mould; Remove sealing strip (5), open cover plate (3), take out the substrate wet gel of any surface finish; Be placed between two block gypsum plates of surfacing, air dry forms any surface finish, smooth substrate xerogel; This xerogel is placed between two surfacings, the bright and clean alumina plate, roasting through 310 ℃ * 10h removes organic substance, with the sintering of 1250 ℃ * 8h, it is all suitable promptly to obtain porosity, intensity, and internal structure is even, the SOFC anode substrate of surfacing.
Embodiment 3: put into agate abrading-ball 76g in nylon ball grinder, average grain diameter is 8YSZ 27.00g, AM 6.30g, MBAM0.23g, gum arabic 0.42g, the deionized water 50.60g of 8.0 μ m; With ball grinder with 1100rpm ball milling 12h; Adding average grain diameter in above-mentioned ball grinder is the nickel protoxide 40.50g of 3.0 μ m; With 650rpm ball milling 2h; Be ready to each parts of particular manufacturing craft shown in Figure 2, to be stained with the rubber special-shaped and cut apart glass backing plate (1) horizontal positioned of circle (2), in cutting apart the zone that circle (2) limited, special-shaped pours above-mentioned slip into, cover glass cover-plate (3) from top to bottom, the mould that then this is marked with slip is heated to 50 ℃ in nitrogen atmosphere, and maintenance 2h, the slip complete gelation in the mould; Open cover plate (3), take out the substrate wet gel of any surface finish; Be placed between two block gypsum plates of surfacing, air dry forms any surface finish, smooth substrate xerogel; This xerogel is placed between two surfacings, the bright and clean alumina plate, roasting through 430 ℃ * 10h removes organic substance, with the sintering of 1120 ℃ * 8h, it is all suitable promptly to obtain porosity, intensity, and internal structure is even, the SOFC anode substrate of surfacing.
Claims (2)
1. a method for preparing solid oxide fuel cell anode substrate is characterized in that, utilize nickel protoxide in the slip system from initiation characteristic, need not to add separately initator, may further comprise the steps:
Step 1, take by weighing doped zirconia powder, organic monomer, crosslinking agent, water, dispersant, suspending agent and plasticizer; Doped zirconia is the doped with rare-earth oxide zirconium dioxide, its particle diameter is 0.1～10.0 μ m, organic monomer is acrylamide or Methacrylamide, crosslinking agent is N, N-methylene-bisacrylamide, water are running water, pure water, deionized water or distilled water, and dispersant is ammonium polyacrylate, ammonium polymethacrylate or ammonium citrate, suspending agent is a gum arabic, and plasticizer is a polyethylene glycol; Every preparation 1cm
3The final anode substrate of volume, need to add 1.2～2.2g doped zirconia, the weight of organic monomer, water, dispersant, suspending agent and plasticizer is respectively 10.0～30.0%, 55.0～200.0%, 0.0～7.0%, 0.0～1.3% and 0.0～3.0% of doped zirconia weight, and the weight of crosslinking agent is 1/10～1/30 of organic monomer weight;
Step 2, the material that step 1 is taken by weighing are put into the ball grinder that has abrading-ball, and abrading-ball weight is 70～250% of above-mentioned material total weight, and with the rotating speed of 500～1100rpm, ball milling 8～48h forms first slip;
Step 3, take by weighing nickel protoxide powder, dispersant and plasticizer; The particle diameter of nickel protoxide is 0.1～10.0 μ m, and dispersant is ammonium polyacrylate, ammonium polymethacrylate or ammonium citrate, and plasticizer is a polyethylene glycol; The weight of nickel protoxide be in the above-mentioned steps one doped zirconia weight 100～160%, the weight of dispersant, plasticizer is respectively 0.0～7.0% and 0.0～3.0% of nickel protoxide weight;
Step 4, the material that step 3 is taken by weighing add in the first slip that step 2 obtains, and adopt the ball grinder and the abrading-ball of step 2, and with the rotating speed of 400～850rpm, ball milling 0.5～6.0h forms the secondary slip;
Step 5, with above-mentioned secondary slip, inject particular manufacturing craft, seal the exhaust outlet of particular manufacturing craft then, perhaps particular manufacturing craft is placed nitrogen or inert gas atmosphere, heat 0.5～8h down at 40～80 ℃, make the abundant gelling of secondary slip in the mould, form the substrate wet gel;
Step 6, above-mentioned particular manufacturing craft is removed sealing, or from nitrogen, inert atmosphere, take out, take out the substrate wet gel in the mould then;
Step 7, the aforesaid substrate wet gel is placed between the plasterboard of two surfacings, in static or moving air, be no more than under 80 ℃ the temperature, carry out dried, form the substrate xerogel;
Step 8, the aforesaid substrate xerogel is placed between the ceramic wafer of two surfacings, that carries out 300～450 ℃ * 0.5～10h removes the organic substance roasting, with the sintering of 1100～1350 ℃ * 0.5～10h, form the Solid Oxide Fuel Cell porous anode substrate.
2. one kind is used for the mould for preparing the method for solid oxide fuel cell anode substrate as claimed in claim 1, it is characterized in that, comprise as lower member: the backing plate of a horizontal positioned (1), a special-shaped that is bonded on the backing plate (1) are cut apart a circle (2) and a cover plate (3); The overall dimension of described backing plate (1) is slightly larger than the overall dimension of cutting apart circle (2), the inboard of cutting apart circle is shaped as square or rectangular, on its corner location, have exhaust passage (4), exhaust passage (4) has the part of exposing cover plate (3), be the exhaust outlet in the above-mentioned steps five, behind the injection molding if need seal exhaust outlet, then adopt sealing strip (5), the profile of cover plate is a rectangle, be placed on and cut apart on the circle (2), size on Width should guarantee that part covers, part exposes the exhaust passage, and size in the longitudinal direction is slightly larger than cuts apart the size of circle on this direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101027534A CN100403588C (en) | 2005-09-14 | 2005-09-14 | Method for producing solid oxide fuel cell anode substrate and die |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101027534A CN100403588C (en) | 2005-09-14 | 2005-09-14 | Method for producing solid oxide fuel cell anode substrate and die |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1933223A CN1933223A (en) | 2007-03-21 |
| CN100403588C true CN100403588C (en) | 2008-07-16 |
Family
ID=37878926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101027534A Expired - Fee Related CN100403588C (en) | 2005-09-14 | 2005-09-14 | Method for producing solid oxide fuel cell anode substrate and die |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100403588C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101525248B (en) * | 2009-04-22 | 2012-07-04 | 哈尔滨工业大学 | Ceramic aerogel and method for preparing the ceramic aerogel by gel injection moulding |
| CN102060514A (en) * | 2010-11-29 | 2011-05-18 | 沈阳临德陶瓷研发有限公司 | Method for preparing high-density magnesia ceramic |
| CN115818585A (en) * | 2023-01-06 | 2023-03-21 | 刘长英 | Process for smelting and extracting selenium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028362A (en) * | 1988-06-17 | 1991-07-02 | Martin Marietta Energy Systems, Inc. | Method for molding ceramic powders using a water-based gel casting |
| CN1370758A (en) * | 2001-02-22 | 2002-09-25 | 北京航空材料研究院 | Molding process of water-thinned ceramic slurry gel |
| CN1370759A (en) * | 2001-02-22 | 2002-09-25 | 北京航空材料研究院 | Method and special mold for preparing unfired ceramic element sheet |
| CN1464577A (en) * | 2002-06-20 | 2003-12-31 | 中国科学院大连化学物理研究所 | Moderate temperature solid oxide fuel battery composite double layer anode and process for preparing |
-
2005
- 2005-09-14 CN CNB2005101027534A patent/CN100403588C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5028362A (en) * | 1988-06-17 | 1991-07-02 | Martin Marietta Energy Systems, Inc. | Method for molding ceramic powders using a water-based gel casting |
| CN1370758A (en) * | 2001-02-22 | 2002-09-25 | 北京航空材料研究院 | Molding process of water-thinned ceramic slurry gel |
| CN1370759A (en) * | 2001-02-22 | 2002-09-25 | 北京航空材料研究院 | Method and special mold for preparing unfired ceramic element sheet |
| CN1464577A (en) * | 2002-06-20 | 2003-12-31 | 中国科学院大连化学物理研究所 | Moderate temperature solid oxide fuel battery composite double layer anode and process for preparing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1933223A (en) | 2007-03-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105777133B (en) | The preparation method and particular manufacturing craft of the whole shellproof plate of the more curved surfaces of disposal molding | |
| CN101322919B (en) | Method for preparing micropore ceramic separation film | |
| CN100403588C (en) | Method for producing solid oxide fuel cell anode substrate and die | |
| US20090159853A1 (en) | Colloidal templating process for manufacture of highly porous ceramics | |
| CN105236986A (en) | Preparation method and application of multi-channel silicon carbide plate ceramic membrane support | |
| CN105552212B (en) | A kind of 33 type piezoelectric ceramics/cement piezoelectric composite material and preparation method thereof | |
| CN107914333A (en) | The method that zirconia ceramics cell phone rear cover is made using gel injection molding and forming technology | |
| CN1151094C (en) | Method and special mold for preparing unfired ceramic element sheet | |
| CN109176828B (en) | Gel injection molding method for large-size planar ceramic blank capable of preventing warping deformation | |
| CN105084874A (en) | Gelcasting method of alumina or ZTA ceramic | |
| CN108249952A (en) | A kind of preparation method of porous ceramics load bearing board | |
| CN104058729A (en) | Method for preparing large-specification ITO (indium tin oxide) target material | |
| CN114538899A (en) | Preparation method of 996 aluminum oxide ceramic substrate | |
| CN104402522B (en) | The direct foaming of a kind of heavy gas shield prepares method and the device of porous ceramics | |
| CN108000684A (en) | A kind of adhesive for powder injection forming preparation method and applications | |
| CN105128128A (en) | Mold-free material forming method and device | |
| CN112265118A (en) | Annealing device for processing honeycomb ceramics for diesel engine and honeycomb ceramics | |
| CN219054792U (en) | Concrete experimental device | |
| CN105237027A (en) | Preparation method and application of multi-channel cordierite plate ceramic membrane support | |
| CN101857443A (en) | Method for preparing large-sized ceramic grinding balls | |
| CN211977437U (en) | Energy-efficient soft stone heating and drying device | |
| CN110357589A (en) | A kind of Aqueous injection moulding process of structural ceramics | |
| CN115368116A (en) | Method for rapidly preparing aluminum oxide ceramic wafer and prepared aluminum oxide ceramic wafer | |
| CN115626818A (en) | Ceramic slurry preparation method and precision direct-writing 3D printing method | |
| CN108274610B (en) | Mould suitable for water-based slurry gel injection molding process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080716 Termination date: 20140914 |
|
| EXPY | Termination of patent right or utility model |