CN100349828C - Process for preparing oxide compacting ceramic film on porous substrate - Google Patents
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- CN100349828C CN100349828C CNB2005100226668A CN200510022666A CN100349828C CN 100349828 C CN100349828 C CN 100349828C CN B2005100226668 A CNB2005100226668 A CN B2005100226668A CN 200510022666 A CN200510022666 A CN 200510022666A CN 100349828 C CN100349828 C CN 100349828C
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- 239000000758 substrate Substances 0.000 title claims abstract description 46
- 239000000919 ceramic Substances 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 20
- 238000005516 engineering process Methods 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 15
- 239000010419 fine particle Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 239000011362 coarse particle Substances 0.000 claims description 26
- 238000005507 spraying Methods 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000007590 electrostatic spraying Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 15
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000001035 drying Methods 0.000 abstract description 4
- 239000011195 cermet Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 31
- 239000000463 material Substances 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 13
- 101150058765 BACE1 gene Proteins 0.000 description 11
- 238000000498 ball milling Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- 238000010671 solid-state reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052574 oxide ceramic Inorganic materials 0.000 description 3
- 239000011224 oxide ceramic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000015895 biscuits Nutrition 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 239000002131 composite material Substances 0.000 description 2
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- 238000000151 deposition Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007750 plasma spraying Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
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- 239000010416 ion conductor Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910002119 nickel–yttria stabilized zirconia Inorganic materials 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
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- -1 under 1450 °C Substances 0.000 description 1
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Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Fuel Cell (AREA)
Abstract
本发明涉及致密陶瓷薄膜制备技术。该方法包括利用现有技术制备金属陶瓷或陶瓷多孔衬底，并在多孔衬底表面施加涂层，所述在多孔衬底表面施加涂层的步骤是：首先采用喷涂或悬浮颗粒浆料浸渍涂膜技术在多孔衬底表面形成由团聚粉体疏松堆积成的粗颗粒骨架膜层；干燥后用细小颗粒粉体浆料对粗颗粒骨架膜层进行覆涂，使相对密度达到60%以上；最后在1200-1450℃、空气条件下烧结后冷却得成品；粗颗粒骨架膜层中粉体粒径d50为0.2-2.0微米；覆涂用浆料中颗粒的粒度与骨架膜层中粉体的粒度比为1∶5-50，其浆料中固含质量为1-10%。本方法制备膜层的厚度能较方便地控制在5-100微米范围内，具有质量稳定、制备周期短和成本低等优点。The invention relates to the preparation technology of dense ceramic film. The method comprises the steps of preparing a cermet or ceramic porous substrate by using the prior art, and applying a coating on the surface of the porous substrate. Membrane technology forms a coarse-grained skeleton film layer composed of agglomerated powder loosely accumulated on the surface of the porous substrate; after drying, coat the coarse-grained skeleton film layer with fine particle powder slurry to make the relative density reach more than 60%; finally After sintering at 1200-1450°C under air conditions, the finished product is obtained after cooling; the particle size d 50 of the powder in the coarse-grained skeleton film layer is 0.2-2.0 microns; The particle size ratio is 1:5-50, and the solid content in the slurry is 1-10%. The thickness of the film layer prepared by the method can be conveniently controlled within the range of 5-100 microns, and has the advantages of stable quality, short preparation period, low cost and the like.
Description
Technical field
The present invention relates to the compacting ceramic film technology of preparing.
Background technology
Prepare oxide compacting ceramic film on the porous ceramics substrate, especially function ceramic membrane has the utmost point in many technical fields and uses widely.For example, in the Solid Oxide Fuel Cell technology, fine and close stable zirconium white (YSZ) electrolytic thin-membrane of Yttrium oxide doping of preparation on porous supporting body male or female substrate, be the core of intermediate temperature solid oxide fuel cell (IT-SOFC) technology, the thickness of dielectric film and compactness directly influence the performance and the output rating of battery.According to Holland " solid state ionics " (Solid State Ionics) magazine, the 176th volume (2005) 451-456 page or leaf, the 175th volume (2004) 171-176 page or leaf and 152-453 volume (2002) 373-381 page or leaf report, the technology for preparing film-type fuel cell or thin-film material parts at present mainly comprises: casting method (Tape casting), slurry cladding process (Slurrycoating), roll method (Tape calendering), electrophoretic deposition (Electrophoretic depositionmethod), sputter (Sputtering), electrochemical deposition (Electrochemical vapor deposition), CVD (Chemical Vapor Deposition) method (Chemical Vapor deposition) or the like.These preparation methods have some shortcomings, for example casting method and slurry cladding process are difficult to the dense film of preparation thin thickness, the roll method requires high to powder, electrophoretic deposition and CVD (Chemical Vapor Deposition) method etc. require harsh to substrate surface smooth finish, poor repeatability, manufacturing cost height, what have also can discharge toxic byproduct.
The plasma spraying technology that developed recently gets up is by solid ceramic particle melted by heat or partial melting in ceramic membrane preparation, flies to solidify on the cold substrate and form film.With traditional method relatively, plasma spraying have energy density height, microreaction temperature height (10000K) but, fast, the substrate arbitrary shape of deposition speed, pollute advantages such as few.But this technology is except that shortcomings such as equipment cost height, generally can not be used to prepare thickness less than 50 microns dense film, and the preparation dense film is then more difficult on the porous substrate.
Summary of the invention
The objective of the invention is to, on the porous substrate, prepare the problem that oxide ceramic film exists at prior art, proposed a kind of on the porous substrate comparatively convenient, the low-cost method for preparing the oxide compacting ceramic membrane.
The object of the invention realizes in the following manner.
The method that on the porous substrate, prepares oxide compacting ceramic film of the present invention, comprise and utilize prior art for preparing sintering metal or ceramic porous substrate, and apply coating at the porous substrate surface, it is characterized in that the described step that applies coating at the porous substrate surface is: at first adopt spraying or suspended particle slurry dipping to be coated with membrane technique and form the coarse particles skeleton rete that becomes by reunion powder fluff packing at the porous substrate surface; Dry back is covered coarse particles skeleton rete with the fine particle powdery pulp and is coated with, promptly established membrane bone frame is carried out calking, relative density is reached more than 60%, perhaps a presintering is handled to the advanced row of dried coarse particles skeleton rete, and then cover and be coated with, its pre-sintering temperature is 800-1100 ℃, and sintering time is 1-2 hour; The sintering postcooling gets finished product under 1200-1450 ℃, air conditions at last; Diameter of particle d in the described coarse particles skeleton rete
50Be the 0.2-2.0 micron; Described to cover the size ratio that is coated with used powder in particulate granularity in the fine particle powdery pulp and the coarse particles skeleton rete be 1: 5-50, containing quality in its fine particle powdery pulp admittedly is 1-10%.
Among the above-mentioned preparation method, described spraying is meant electrostatic spraying powder technology commonly used in the prior art, or suspended particle slurry spraying technology.When using spraying of suspended particle slurry or dipping to film, solid content is 5-25% (quality) in its slurry.
Be to guarantee the compactness requirement of product, common whole film layer thickness should be in coarse particles skeleton rete more than 5 times of powder granularity.
When preparing suspended particle slurry or dipping with powdery pulp or preparation fine particle powdery pulp, usually be solvent with water or ethanol, and add an amount of dispersion agent, for example PAA dispersion agent, PEG (M200-20000) dispersion agent, PVP (M3000) dispersion agent etc. are even, stable to guarantee slurry.
Among the present invention, the material of described substrate can be multiple materials such as sintering metal or oxide ceramics, if with the thin-film material of subsequent preparation chemically compatible, chemical reaction or diffusion mutually physically promptly do not take place, and can tolerate follow-up thermal treatment, can select for use.As porous or fine and close perovskite Composite Oxides Materials, Ni-YSZ, Cu-SDC, two-phase composite cermet materials such as Ni-SDC etc.
The present invention prepares the method for dense oxide ceramic membrane on the porous substrate, at first adopt spraying or suspended particle slurry dipping to be coated with membrane technique and become coarse particles skeleton rete at the fluff packing that the porous substrate surface forms by the reunion powder, formation is by the skeleton structure of the fluff packing one-tenth of reunion powder, then by in covering the pasting process, being coated with the more slurry of fine particle, since the ratio of the size of the fine particle in the coacervate that forms skeleton and the slurry be 5-50 doubly, therefore the fine particle in the slurry is under the effect of capillary force, can be filled into the skeleton gap fully, formation has high relative density powder biscuit layer, the relative density of biscuit layer is brought up to more than 60%, its density also is improved largely behind the sintering, thereby has eliminated the disadvantageous effect of substrate surface defective to preparation dense film process.
The present invention prepares the method for oxide compacting ceramic film on the porous substrate, the thickness of its preparation rete can be controlled in the 5-100 micrometer range more conveniently; Its relative density can reach more than 95%, and evenly, free of pinholes.Whole process of preparation also has the control of being easy to, steady quality, and the short and low cost and other advantages of preparation cycle is suitable for industrial applications.
Use the inventive method to prepare oxide compacting ceramic film, owing to be the gastight material membrane, thereby can be used as the high quality supercoat, and gas delivery layer of different nature.Under the situation of oxygen ion conductor material, can be used as the solid electrolyte layer of electrochemistry of solids device, particularly can be used as dielectric substrate of the Solid Oxide Fuel Cell that porous anode (or negative electrode) supports or the like.
Be further described below by embodiment.
Embodiment
Embodiment 1: preparation compact YSZ film on porous NiO-YSZ substrate.
(1) (YSZ represents 8% mole of Y to preparation porous NiO-YSZ substrate
2O
3Stable ZrO
2): YSZ powder and NiO powder are pressed 4: 6 (mass ratio), add a certain amount of ethanol and make solvent, ball milling mixed in 4 hours, and heating evaporation removes and desolvates and drying then.
(2) add an amount of pore-forming material (as carbon black) in the powder mix of YSZ and NiO, and then mixing (air-flow mixing)
(3) the dry-pressing formed diameter of the powder mix that utilizes step 2 to obtain is 50 millimeters, and thickness is 1.5 millimeters disk, 900 ℃ of following pre-burnings 2 hours, makes porous NiO-YSZ porous substrate.
(4) with granularity d
50The YSZ powder of (diameter of particle is in the 0.5-2 micrometer range usually) mixed than ball milling by 1: 20 quality with ethanol in 8 hours, then slurry was poured in high about 1 meter column precipitator (about 0.9 meter of slurry post height).Behind the standing sedimentation 4 hours, open a spout, take out the screened stock material of the first half about 1/3rd places of slurry post height; And then the coarse particles slurry of taking-up Lower Half.
(5) the screened stock material that takes out from the slurry settling leg first half also adds the PAA dispersion agent of about 1-5 ‰, and ball milling is 12 hours again, as the fine particle powdery pulp, and its diameter of particle d
500.2 micron of ≈, the quality of solid content is 1% in its slurry; To remove from the coarse particles slurry that slurry settling leg Lower Half is taken out and desolvate, and oven dry, be used as the coarse particles powder that electrostatic dusting prepares YSZ membrane bone frame, its diameter of particle d
501 micron of ≈.
(6) the coarse particles powder that will utilize step 5 to obtain adopts the electrostatic dusting technology to spray coarse particles skeleton rete on the porous NiO-YSZ substrate that has prepared, preparation YSZ membrane bone frame.Voltage during electrostatic dusting is 100KV, and the distance of shower nozzle and substrate is 150 millimeters, and coarse particles framework film layer thickness is controlled at the 20-30 micron 1.2-1.5 of product thicknesses of layers (be generally doubly).
(7) the screened stock material that step 5 is obtained adopts the mechanically spraying technology, and spray to above-mentioned coarse particles powder and be coated with on the rete, and about 2 hours of oven dry under 80 ℃, the condition of control gas velocity; And then spraying screened stock material, oven dry so repeats 10-20 time again, obtains the rete relative density and reaches green compact film more than 60%.
(8) sintering: with above-mentioned green compact film, under 1450 ℃, air conditions, sintering 4-5 hour, naturally cooling obtained the compact YSZ film that thickness is the 15-20 micron.
Embodiment 2: at NiO-BaCe
0.8Gd
0.2O
3Prepare BaCe on the porous substrate
0.8Gd
0.2O
3Dense ceramic membrane.
(1) BaCe that citric acid method is prepared
0.8Gd
0.2O
3Powder and NiO powder are solvent by 4: 6 mass ratioes with ethanol, and ball milling mixed in 24 hours; Evaporation remove desolvate and drying after, with NiO and BaCe
0.8Gd
0.2O
3It is 15 millimeters that mixed powder is pressed into diameter, and thickness is the disk of 1-2 millimeter, and 900 ℃ of sintering 2 hours obtain NiO-BaCe
0.8Gd
0.2O
3The porous substrate.
(2) BaCe that adopts citric acid method to prepare
0.8Gd
0.2O
3Powder (aggregated particle size of powder is the 1-2 micron) is a solvent with ethanol, and PEG (M4000) is a dispersion agent, is prepared into stable BaCe
0.8Gd
0.2O
3Slurry, wherein, the dispersion agent add-on is the 2-5% of powder quality, the slurry solid content is 10% (quality); Then porous substrate dipping is filmed 30 seconds in slurry, promptly on the porous substrate, prepare BaCe
0.8Gd
0.2O
3Coarse particles skeleton rete, wherein thicknesses of layers is controlled at the 20-30 micron, and with the presintering 2 hours in 900 ℃, air ambient of this rete, the cooling back is stand-by again.
(3) BaCe that adopts glycine to prepare
0.8Gd
0.2O
3Powder (diameter of particle is the 0.1-0.3 micron) is a solvent with ethanol, preparation BaCe
0.8Gd
0.2O
3Slurry is as the short grained screened stock material of calking, and the solid content in the screened stock material is 8%.
(4) adopt the mechanically spraying technology, at the BaCe of (2) preparation
0.8Gd
0.2O
3Spraying screened stock material on the coarse particles framework film laminar surface, under 80 ℃ of conditions dry 2 hours then, film again thereafter, dry again, so repeat 10-20 time, obtain relative density and reach green compact film more than 60%.
(5) sintering: under 1250 ℃, air conditions, sintering 8-10 hour, obtaining thickness was the fine and close BaCe of 20-30 micron with above-mentioned green compact film
0.8Gd
0.2O
3Film.
Adopt method for preparing BaCe
0.8Gd
0.2O
3Film, its densification sintering temperature reduces about 200-300 degree than the temperature (nearly 1600 ℃) of the densification sintering of general briquetting.
Embodiment 3: preparation SDC dense film on SDC-NiO porous substrate
(1) SDC (Ce that glycine method is prepared
0.8Sm
0.2O
2) powder mixes with the NiO powder, the mass ratio of SDC and NiO is 4: 6, and being pressed into diameter then is 20 millimeters, and thickness is the disk of 1-2 millimeter, and 950 ℃ of following pre-burnings 2 hours obtain SDC-NiO porous substrate.
(2) adopt solid reaction process to prepare the SDC powder, that is: be raw material with cerous nitrate and Samarium trioxide, mix for the solvent ball milling with water, oven dry then is again at the High Temperature Furnaces Heating Apparatus internal heating, along with the rising of temperature, nitrate decomposes, continue to be heated to certain temperature, solid state reaction fast takes place, obtain the SDC powder at last.The solid state reaction temperature that present embodiment adopts is 600 ℃ and 1000 ℃, and the time is 2 hours.(diameter of particle is the 0.1-0.5 micron to the small-particle powder that 600 ℃ of solid state reactions obtain, note is done: SDC-600) be used to prepare calking fine particle powdery pulp, (diameter of particle is the 1-3 micron to the coarse particles powder that 1000 ℃ of solid state reactions obtain, and note is done: the slurry that SDC-1000) is used to prepare the skeleton rete.
(3) preparation coarse particles skeleton rete slurry: earlier SDC-1000 is mixed 3 hours (mass content of solid powder is 20%) with water for ball milling, PVP (M3000) dispersion agent that adds water solvent quality 7.5 ‰ then, ball milling is 3 hours again, regulate pH value of slurry to 10 and continued ball milling 8 hours, form stable SDC-1000 slurry thereafter.
(4) adopt the mechanically spraying technology, above-mentioned SDC-1000 slurry is sprayed on the porous substrate of step 1 preparation, form coarse particles skeleton rete, its thickness 20-30 micron was handled 2 hours 1000 ℃ of presintering then, and the cooling back is stand-by.
(5) preparation screened stock material: with ethanol is solvent, and ball milling mixes 24 hours preparation SDC-600 powdery pulps, and the solid powder mass content is 6% in the slurry.
(6) adopt the mechanically spraying technology with step 5 preparation fine particle powdery pulp (SDC-600) be sprayed on the coarse particles skeleton rete, then 80 ℃ of dryings 2 hours, be cooled to room temperature, film once more, dry again, so repeat 15-20 time, make that the relative density of film reaches more than 60% on the substrate.
(7) sintering: 1400 ℃ of sintering 5 hours, obtaining thickness at last was the fine and close SDC film of 20-25 micron with the film of above-mentioned preparation.
More than the ceramic membrane of three embodiment preparation, relative density all reaches more than 95%, and evenly, free of pinholes.
Claims (5)
1. method that on the porous substrate, prepares oxide compacting ceramic film, comprise preparation sintering metal or ceramic porous substrate, and apply coating at the porous substrate surface, it is characterized in that the described step that applies coating at the porous substrate surface is: at first adopt spraying or suspended particle slurry dipping to be coated with membrane technique and form the coarse particles skeleton rete that becomes by reunion powder fluff packing at the porous substrate surface; Dry back is covered coarse particles skeleton rete with the fine particle powdery pulp and is coated with, and relative density is reached more than 60%; The sintering postcooling gets finished product under 1200-1450 ℃, air conditions at last; Diameter of particle d in the described coarse particles skeleton rete
50Be the 0.2-2.0 micron; Described to cover the size ratio that is coated with used powder in particulate granularity in the fine particle powdery pulp and the coarse particles skeleton rete be 1: 5-50, containing quality in its fine particle powdery pulp admittedly is 1-10%.
2. the method for preparing oxide compacting ceramic film on the porous substrate as claimed in claim 1 is characterized in that described spraying is meant the electrostatic spraying powder technology, or suspended particle slurry spraying technology.
3. the method for preparing oxide compacting ceramic film on the porous substrate as claimed in claim 1 or 2 is characterized in that, when using spraying of suspended particle slurry or dipping to film, containing quality in its slurry admittedly is 5-25%.
4. the method that on the porous substrate, prepares oxide compacting ceramic film as claimed in claim 1, it is characterized in that a presintering of the advanced row of described dried coarse particles skeleton rete is handled, and then cover and be coated with, its pre-sintering temperature is 800-1100 ℃, and sintering time is 1-2 hour.
5. the method for preparing oxide compacting ceramic film on the porous substrate as claimed in claim 1 is characterized in that, described film layer thickness is more than 5 times of powder granularity in coarse particles skeleton rete.
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| CN113948704A (en) * | 2021-10-15 | 2022-01-18 | 中汽创智科技有限公司 | Solid electrolyte composite layer, preparation method and application thereof |
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| JP2002128582A (en) * | 2000-10-18 | 2002-05-09 | Mitsui Mining & Smelting Co Ltd | Tool for calcinating electronic part |
| US6534211B1 (en) * | 1999-11-01 | 2003-03-18 | Mitsubishi Heavy Industries, Ltd. | Fuel cell having an air electrode with decreased shrinkage and increased conductivity |
| CN1409427A (en) * | 2001-09-18 | 2003-04-09 | 中国科学技术大学 | PEN multilayer film of middle temperature solid oxide fuel cell and its producing method |
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2005
- 2005-12-24 CN CNB2005100226668A patent/CN100349828C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11343185A (en) * | 1998-05-28 | 1999-12-14 | Toto Ltd | Production of dense sintered film |
| US6534211B1 (en) * | 1999-11-01 | 2003-03-18 | Mitsubishi Heavy Industries, Ltd. | Fuel cell having an air electrode with decreased shrinkage and increased conductivity |
| JP2002128582A (en) * | 2000-10-18 | 2002-05-09 | Mitsui Mining & Smelting Co Ltd | Tool for calcinating electronic part |
| CN1409427A (en) * | 2001-09-18 | 2003-04-09 | 中国科学技术大学 | PEN multilayer film of middle temperature solid oxide fuel cell and its producing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446893A (en) * | 2013-09-06 | 2013-12-18 | 南京工业大学 | Method for preparing metal organic framework membrane on inner wall of tubular ceramic support |
| CN103446893B (en) * | 2013-09-06 | 2015-09-02 | 南京工业大学 | Method for preparing metal organic framework membrane on inner wall of tubular ceramic support |
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| CN1793056A (en) | 2006-06-28 |
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