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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- porous substrate
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Abstract
The present invention relates to technology fro preparing compact ceramic films. In the method, the prior art is utilized to prepare metal ceramic or porous ceramic substrates, and coatings are applied on the surfaces of the porous substrates in the way that firstly, spraying or suspended particle slurry dip film coating technology is adopted to make agglomerate powders stacked loosely on the surface of a porous substrate to form a coarse particle frame film layer; after dried, the coarse particle frame film layer is coated with fine particle powder slurry to make the relative density reach more than 60%; finally, the coarse particle frame film layer is sintered in the air of 1200 to 1450 DEG C and then is cooled to obtain a finished product. The particle sizes d50 of powders in the coarse particle frame film layer are from 0.2 to 2.0 micrometers, the radio of the granularity of particles in the slurry to the granularity of the powders in the frame film layer is 1: 5 to 50, and the quality of solids in the slurry is from 1% to 10%. The thickness of a film layer prepared by using the method can be conveniently controlled within the range of 5 to 100 micrometers, and the present invention has the advantages of stable quality, short preparing circle, low cost, etc.
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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| 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 |
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| CN102503578A (en) * | 2011-11-25 | 2012-06-20 | 西安交通大学 | Method for preparing ceramic coating on surface of porous ceramic substrate |
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| JPH11343185A (en) * | 1998-05-28 | 1999-12-14 | Toto Ltd | Production of dense sintered film |
| 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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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 |
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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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