CN100563799C - A kind of preparation technology of porous stainless steel-ceramic compound film - Google Patents
A kind of preparation technology of porous stainless steel-ceramic compound film Download PDFInfo
- Publication number
- CN100563799C CN100563799C CNB2008100203180A CN200810020318A CN100563799C CN 100563799 C CN100563799 C CN 100563799C CN B2008100203180 A CNB2008100203180 A CN B2008100203180A CN 200810020318 A CN200810020318 A CN 200810020318A CN 100563799 C CN100563799 C CN 100563799C
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- powder
- ceramic
- preparation technology
- technology according
- 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.)
- Active
Links
Images
Abstract
The present invention relates to the preparation technology of porous stainless steel-ceramic compound film.Add layer of metal powder (2) between ceramic layer (1) and stainless steel base (3), with ceramic layer (1) high temperature co-firing, it both can play the effect of adhesive, can repair the defective of matrix surface again, did not influence the membrane filtration precision simultaneously.The present invention at matrix material (3) also can be molded but without the base substrate of sintering, can directly ceramic layer (1) be coated in billet surface like this and one step of two parts sintering is formed; Metal dust (2) as adhesive both can be that monometallic can also be a stainless steel alloy.Powder of stainless steel and ceramic powders are made suspension with the additive mixing respectively, after matrix surface successively prepares metal dust coating and ceramic coating, removes organic matter, 600～1400 ℃ of sintering in vacuum or protective atmosphere.
Description
Technical field:
The present invention relates to a kind of preparation technology of composite film material; Relate in particular to a kind of preparation technology of porous stainless steel-ceramic compound film material.
Background technology:
The continuous expansion in application of membrane separation technology field has proposed requirements at the higher level to the production of membrane material.Difference according to membrane material, film can be divided into polymeric membrane and inoranic membrane two big classes, wherein polymeric membrane is most widely used, but distinct issues are arranged also,, poor chemical stability big, be difficult to clean and sterilization and easily cause secondary pollution etc. as the restriction ratio that is subjected to operating pressure and serviceability temperature in the use, these are the advantage of inoranic membrane just, and its market share increases fast.Inoranic membrane mainly is ceramic membrane and stainless steel membrane two big classes.Comparatively speaking, ceramic membrane has more excellent chemical stability, the aperture in addition can be little to nanoscale, all be applied in micro-filtration, ultrafiltration, nanofiltration field.But pottery belongs to fragile material, and bad sealing when working under hot conditions.Porous stainless steel then has outstanding advantage in this respect.
The porous stainless steel membrane generally is made up of two parts at least, and the one, have high porosity, wide-aperture supporter; The 2nd, the pore layer that approaches claims the aperture key-course again, also needs transition zone between the two sometimes.Its preparation process generally is: stainless steel powder that will be thinner mixes formation suspension and is coated on the supporter with suitable medium, degreasing at a certain temperature after the drying, after high temperature sintering form.Particle is in contact with one another part and is sintered together intergranular hole formation duct in the sintering process.The factor that influences the membrane aperture distribution has powder granule size, grain shape, particle diameter distribution, additive, sintering temperature, heating schedule, temperature retention time etc.For making desirable aperture key-course, the particle diameter of stainless steel powder should be even, is preferably regular spherical.Different with ceramic membrane, the aperture of porous stainless steel membrane is difficult to narrow down to below 1 micron as ceramic membrane, because:
1. be difficult to the uniform nanoscale stainless steel of prepared sizes powder.Stainless steel is because its special composition and crystal structure make it have the incomparable advantage of any monometallic, and also just because of this reason, its particle diameter is difficult to thin again, otherwise stainless composition will be offset, and performance also will change;
2. the surface of fine powder can be very big, and convergent force is big during sintering, and the easy peeling of rete, cracking cause yield rate low.
3. the stainless steel powder that is used to fire the aperture key-course is thin more, and then price is high more, corrosion resistance is poor more, also high more to the requirement of environment for use.
Have the stainless production technology in ultra-fine hole though many companies and research institution all claim, because the finished product rate is low, cost is high, and this series products in world markets is very limited, and is mainly used in scientific research.In order to have stainless steel membrane high mechanical properties and the ceramic membrane high score advantage from precision concurrently, people have proposed porous stainless steel---the product concept of ceramic composite membrane, and obtained progress.It is to be that matrix, porous ceramics are the composite of rete with the porous stainless steel, and wherein the most key sport technique segment is at porous stainless steel surface preparation ceramic coating.Desirable coating should satisfy following requirement:
1. ceramic coating is complete, does not have defectives such as crack;
2. has high porosity to realize high membrane flux.
3. good physical strength is arranged.This both had been meant between ceramic coating and the porous stainless steel collective enough adhesive force, and coating material itself can not be too loose simultaneously, otherwise ceramic layer is in use fragile.
4. can prepare the larger area coating, so that commercial the application.
In above requirement, the requirement of ceramic layer intensity generally is difficult to most realize.On the one hand, pottery and porous stainless steel are complete materials with different properties, and particularly the two has significantly different thermal coefficient of expansion.
Ceramic layer material commonly used is Al
2O
3, TiO
2, SiO
2, ZrO
2, YSZ (Zr
0.92Y
0.08O
x) etc., the preparation method of ceramic layer is a lot, as sol-gel process, hot spray process (thermal spray), magnetron sputtering method (magnetron sputtering), wet-milling spraying process (wet powder spray), spread coating (brush coating) etc.Sol-gel process [Spencer H G.US 5130166,1992; John J P, Regina S P.J.Membr.Sci., 1995,101:67-81; Mchenry J A, Deckman H W, Lai W Y F, et al.US 5186833,1991; Lee D W, Yu Y G, et al.J.Membr.Sci., 2004,236:53-63] generally be raw material with the metal alkoxide, it is hydrolyzed into stable sols and is coated on porous stainless steel, drying and high-temperature roasting and form.By hydrolysis (medium, temperature), the drying (temperature, humidity) of colloidal sol and the roasting condition of gel of strictness control alkoxide, can obtain that porosity is big, the ceramic layer of even aperture distribution.In addition, [MchenryJ A such as Mchenry, Deckman H W, Lai F W, et al.US 5186833,1992] adopted a kind of pH value of uniqueness to induce the boehmite gel method: to make the methanol solution of 25% benzyltrimethylammonium hydroxide flow through porous stainless steel base,, methyl alcohol is volatilized naturally to be full of its duct and to form one deck liquid film on its surface.Boehmite sol is covered stainless steel surfaces fast produce one deck colloidal sol, the alkalescence of benzyltrimethylammonium hydroxide can make it form gel after about 20 seconds.[Newman P executes the special S of Tag that, Lee Z etc. to the wet-milling spraying process, hierarchy type filter and preparation method thereof, CN 1487850A, 2002] be that oxide particle is mixed with into suspension with organic solvent, additive etc., suspension is sprayed at porous stainless steel surface, carries out sintering again.The thin layers of ceramic aperture of sol-gel process and wet-milling spraying process preparation is even, and defective is less, but often poor adhesive force, [Huang Y.Dittmeyer R.J.Membr.Sci., 2006,282 (1-2): 296-310] easily come off.Hot spray process [Yilmaz S, Ipek M, Celebi G F, et al.Vacuum, 2005,779 (3): 315-321; Sarikaya O.Surf.Coat.Tech., 2005, (3): 388-393] and be ceramic powder to be heated to fusion or semi-molten state by thermal source, be sprayed into and form coating on the matrix.Plasma spray technology commonly used has HVOF (claiming the spraying of Supersonic velocity oxygen fuel again, highvelocity oxygen fuel spray), pinking spraying (detonation spray), electric arc spraying (electrical arcspray), plasma spraying (plasma spray) etc.Hot spray process is easy and simple to handle, is suitable for preparing the large tracts of land coating most, and coating adhesion is strong, but shortcoming is that coating is often too fine and close, flux is on the low side.Gaddis and Jernigan[Gaddis J L., Jernigan D A, Sintered coating for porous metallic filter surfaces USPatent:4888114,1989] etc. invented a kind of filling perforation method, not to carry out ceramic coating at matrix surface, but oxide powder is infiltrated in the hole of matrix surface certain depth, still, such composite membrane flux can descend unavoidably.In a word, existing all multi-methods or properties of product are difficult to reach requirement, or complex operation, cost too high, be difficult to industrialization.
Summary of the invention:
Technical problem to be solved by this invention is: to have now in problems such as porous stainless steel-ceramic compound film material preparation process ceramic layer poor adhesive force and proposed the technology that the powder sintered adhesion technique of a kind of interface metal prepares the stainless steel-ceramic compound film material in order to improve.
Technical scheme of the present invention is: stainless steel base and ceramic layer are because material character is far different, and the two lacks affinity.Solution thinking of the present invention is to add layer of adhesive between the two, makes it adhesion preferably all be arranged to ceramic layer and porous stainless steel base.Conventional organic and inorganic bond be difficult to accomplish not only satisfy composite membrane preparation condition (as high temperature), but also do not influence the strainability of composite membrane.Therefore the present invention was coated with the layer of metal powder earlier as adhesive, as shown in Figure 1 before preparation ceramic layer on the porous stainless steel base.Metal powder layer and porous stainless steel base are all metal material, no doubt can by the phase counterdiffusion securely sintering together, metal powder also can produce good binding with the ceramic powder high temperature co-firing time.This is because metal-powder has higher specific surface than stainless steel base, improve greatly with the contact area of ceramic powder, under suitable sintering temperature, the initial liquid phase that the metal-powder surface produces can and ceramic layer between produce effect of impregnation may.The metal powder layer that is adopted in this patent can also play the effect of transition zone, can repair the porous stainless steel base surface, improve its surface smoothness, helps preparing flawless ceramic layer.The performance of matrix particularly surface parameter is most important to the preparation of ceramic layer.Generally speaking, " aperture " of porous material be the size at thin place in the finger-hole road often, and promptly the duct allows the size that sees through.But ceramic layer is the surface that is coated in matrix, and just the aperture is located, and port size may be far above in this.In addition, the porous stainless steel surface has defectives such as crackle, super big hole unavoidably.When selecting the stainless steel base of larger aperture (this means that also its surface apertures is bigger) for use, be directly at the flawless ceramic membrane of its surface preparation, difficulty is too big when particularly preparing the pore ceramic membrane.General porous stainless steel surface appearance is difficult to meet the requirement of system film, and ultra-fine hole stainless steel cost is high, this series products is very limited on the market, develops the composite membrane product with this again and loses practical value unavoidably.
Concrete technical scheme of the present invention is:
A kind of preparation technology of porous stainless steel-ceramic compound film material, its concrete steps are: the preparation of A. metal dust tack coat: metal-powder is mixed forming suspension with additive, be coated on the porous stainless steel base surface, drying for standby gets the metal dust adhesive linkage; B. the preparation of porous ceramic layer: ceramic powder and additive are mixed and made into suspension, and the suspension that will contain ceramic powder is coated on the above-mentioned metal dust adhesive linkage, gets the composite membrane base substrate; C. with behind the prepared composite membrane blank sintering of step B, metal powder layer combines matrix and ceramic layer, forms composite membrane.
The metal-powder that can be used as adhesive both can be a monometallic, preferred nickel, iron, copper powder; Also can be alloy, preferred stainless steel, the kind of stainless steel powder is a lot, as 316,304,310 or the like; The metal powder particle diameter is 1～50 μ m, and metal dust bonding bed thickness is 20～500 μ m.The raw material ceramic powder is of a great variety, preferred TiO
2, Al
2O
3, ZrO
2, SiO
2, among the YSZ any one; The granularity of ceramic powder is 0.01～5 μ m, and preferred 0.1～5 μ m, ceramic layer thickness are 5～200 μ m.The preparation method of suspension is with reference to prior art; Wherein organic matter contains a kind of in dispersant, thickener and the defoamer at least in the additive, and organic quality percentage composition is 1～5% in the additive solution; Wherein dispersant can be polyethylene glycol (PEG), polymine (PEI), polymethylacrylic acid or ammonium citrate, the optional carboxymethyl cellulose of thickener (CMC), methylcellulose (MC) or polyvinyl alcohol (PVA); Defoamer is a silicone defoaming agent.The metal dust suspension solid content is 10～75%; The ceramic powder suspension fluid solid content is 1～20%.
Sintering process was divided into for two steps: the first step is to remove the organic matter that is added in the preparation process, and second step was the particle sintering.The former adopts the heating rate of 0.5～2 ℃/min to be heated to 350～500 ℃ gradually usually, is incubated 0.5～2 hour, selects suitable temperature and temperature retention time according to organic addition; The latter generally is heated to 600～1400 ℃ gradually with the heating rate of 0.5～5 ℃/min, is incubated 0.5～5 hour, and temperature and temperature retention time are according to material and granule size and decide.Sintering process at vacuum or protective atmosphere (as H
2, N
2, Ar etc. or its gaseous mixture) in carry out.
In this patent at matrix be not limited only to have the porous stainless steel material of metal strength, also can be compression moulding but still unsintered porous stainless steel base substrate.Like this, can omit the metal dust coating, directly ceramic layer is coated in billet surface, and the sintering between sintering, base substrate and the ceramic layer of the sintering of base substrate, ceramic layer was finished through one step of high-temperature process.The method of powder of stainless steel moulding has die pressing, isostatic pressing method, and injection moulding etc., its shape mostly is flat or tubular type.When adopting the stainless steel base substrate, as long as the heat treatment temperature of base substrate and ceramic layer coupling as matrix.
Beneficial effect:
The present invention is by adding the layer of metal powder adhesives between matrix and ceramic layer, solve ceramic layer and adhered to hypodynamic key issue, not only do not influence simultaneously the strainability of composite membrane, also can repair the porous stainless steel base surface, improve its surface smoothness, help preparing flawless ceramic layer.
Description of drawings:
Fig. 1 is the porous stainless steel-ceramic compound film structural representation, wherein the 1-porous ceramic layer; The 2-metal powder layer; The 3-porous stainless steel base.
Fig. 2 is the prepared composite film material surface SEM photo of embodiment 1, and wherein left figure is 100 times of photos; Right figure is 2000 times of photos.
The specific embodiment:
Embodiment 1
(1) matrix used is the 316L porous stainless steel of external diameter 20mm, wall thickness 3mm, and average pore size is 30 μ m.Adopt the soda acid ultrasonic cleaning respectively, use washed with de-ionized water, drying for standby again.
(2) 100g 316L stainless steel powder (particle size range 20～50 μ m) being mixed also with the PVA solution of 100ml 5%, strong agitation forms slip, slip evenly is sprayed at matrix surface, form the powder of stainless steel layer of thickness 200 μ m, 120 ℃ of dryings are 2 hours in baking oven.
(3) 1g PEI and 0.5g silicone defoaming agent being joined 100ml concentration is to mix in 5% the PVA solution, slowly adds the Al of 30g average grain diameter 1 μ m
2O
3Powder adds distilled water diluting again to 200ml, through ultrasonic dispersion supending.It is sprayed at the powder of stainless steel laminar surface of matrix, forms the ceramic powders layer of thickness 50 μ m, room temperature is dried and 120 ℃ of dryings 2 hours.
(4) the gained composite is heated to 400 ℃ with the speed of 0.5 ℃/min, is incubated 2 hours and carries out organic matter and remove, then with the 1200 ℃ of insulations 5 hours down in vacuum drying oven of the heating rate of 2 ℃/min.The stainless ceramic compound membrane that obtains at last, thickness is even, zero defect.
Embodiment 2
(1) employing diameter 30mm, thickness 2mm, average pore size are that the 304L type porous stainless steel disk of 30 μ m is a matrix, adopt the soda acid ultrasonic cleaning respectively, use washed with de-ionized water, drying for standby again.
(2) 300g 316L stainless steel powder (particle size range 20～50 μ m) being mixed also with the PVA solution of 100ml 5%, strong agitation forms slip, slip is evenly brushed in matrix surface, form the powder of stainless steel layer of thickness 500 μ m, 120 ℃ of dryings are 2 hours in baking oven.
(3) with the step (3) of embodiment 1, thickness is 200 μ m.
(4) step (4) sintering temperature with embodiment 1 is 1300 ℃ of following insulations 1 hour.
Embodiment 3
(1) matrix used is the 316L porous stainless steel of external diameter 20mm, wall thickness 3mm, and average pore size is 10 μ m.Adopt the soda acid ultrasonic cleaning respectively, use washed with de-ionized water, drying for standby again.
(2) 10g 316L stainless steel powder (particle size range 1～5 μ m) is mixed with the PVA solution of 100ml 3% and strong agitation forms slip, slip is evenly brushed in matrix surface, form the powder of stainless steel layer of thickness 50 μ m, 120 ℃ of dryings are 2 hours in baking oven.
(3) with 1g PEI, 1g MC and 0.5g silicone defoaming agent joined in the 200ml district ionized water mix, slowly add the TiO of 10g average grain diameter 0.2 μ m
2Powder is through ultrasonic dispersion supending.It is sprayed at the powder of stainless steel laminar surface of matrix, forms the ceramic powders layer of thickness 20 μ m, room temperature is dried and 120 ℃ of dryings 2 hours.
(4) the gained composite is heated to 500 ℃ gradually with the heating rate of 0.5 ℃/min, is incubated 0.5 hour, again with the heating rate of 1 ℃/min with base substrate 1050 ℃ of 1 hour sintering of insulation down in vacuum drying oven, make intact stainless ceramic compound membrane.
Embodiment 4
(1) with the step (1) of embodiment 3.
(2) with the step (2) of embodiment 3, but metal dust changes the nickel powder of particle size range 1-10 μ m into.
(3) with the step (3) of embodiment 3, but ceramic powder changes the SiO of average grain diameter 1 μ m into
2
(4) with the step (4) of embodiment 3,, sintering condition is incubated 5 hours for following 700 ℃ but changing hydrogen atmosphere into.
Above embodiment is used for illustrating the present invention, and the variation of any equivalence of being done under the situation that does not break away from spirit of the present invention all belongs to the scope of claim of the present invention.
Claims (10)
1, a kind of porous stainless steel---the preparation technology of Ceramic Composite membrane material, its concrete steps are: the preparation of A. metal dust tack coat: metal-powder is mixed forming suspension with additive, be coated on the porous stainless steel base surface, drying for standby gets the metal dust adhesive linkage; B. the preparation of porous ceramic layer: ceramic powder and additive are mixed and made into suspension, and the suspension that will contain ceramic powder is coated on the above-mentioned metal dust adhesive linkage, gets the composite membrane base substrate; C. behind the composite membrane blank sintering, metal powder layer combines matrix and ceramic layer, makes composite film material; Organic matter contains a kind of in dispersant, thickener or the defoamer at least in the wherein said additive, organic quality percentage composition is 1～5% in the additive solution, described dispersant is polyethylene glycol, polymine, polymethylacrylic acid or ammonium citrate, thickener is carboxymethyl cellulose, methylcellulose or polyvinyl alcohol, and defoamer is a silicone defoaming agent.
2, preparation technology according to claim 1 is characterized in that described metal-powder is monometallic or alloy.
3, preparation technology according to claim 2 is characterized in that described monometallic is nickel, iron or copper powder; Alloy is a stainless steel.
4, preparation technology according to claim 1 is characterized in that ceramic powder is TiO among the step B
2, Al
2O
3, ZrO
2, SiO
2Or among the YSZ any one.
5, preparation technology according to claim 1 is characterized in that the metal-powder particle diameter is 1～50 μ m, and the metal dust adhesive layer thickness is 20～500 μ m.
6, preparation technology according to claim 1, the granularity that it is characterized in that ceramic powder are 0.01～5 μ m; Coating thickness is 5-200 μ m.
7, preparation technology according to claim 1, the granularity that it is characterized in that ceramic powder are 0.1～5 μ m.
8, preparation technology according to claim 1 is characterized in that the painting method among steps A and the B is brushing, dipping or spraying.
9, preparation technology according to claim 1 is characterized in that sintering is to carry out under vacuum or reducing atmosphere, sintering temperature is 600～1400 ℃.
10, preparation technology according to claim 1, elder generation is heated to 350～500 ℃ with the heating rate of 0.5～2 ℃/min when it is characterized in that sintering, be incubated 0.5～2 hour, the heating rate with 0.5～5 ℃/min is heated to 600～1400 ℃ again, is incubated 0.5～5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100203180A CN100563799C (en) | 2008-02-29 | 2008-02-29 | A kind of preparation technology of porous stainless steel-ceramic compound film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100203180A CN100563799C (en) | 2008-02-29 | 2008-02-29 | A kind of preparation technology of porous stainless steel-ceramic compound film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101234296A CN101234296A (en) | 2008-08-06 |
| CN100563799C true CN100563799C (en) | 2009-12-02 |
Family
ID=39918355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2008100203180A Active CN100563799C (en) | 2008-02-29 | 2008-02-29 | A kind of preparation technology of porous stainless steel-ceramic compound film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100563799C (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102836642B (en) * | 2011-06-22 | 2015-04-01 | 南京髙谦功能材料科技有限公司 | Preparation method of porous ceramic-metal composite film material |
| CN102389715B (en) * | 2011-10-18 | 2014-06-11 | 南京工业大学 | Method for preparing porous inorganic membrane by particle sintering technology assisted by carbon skeleton |
| CN103157389B (en) * | 2011-12-14 | 2016-03-02 | 南京髙谦功能材料科技有限公司 | A kind of preparation method of asymmetric porous metal film |
| CN103432828B (en) * | 2013-09-23 | 2015-05-13 | 西北有色金属研究院 | Preparation method of porous metal film |
| CN103752185B (en) * | 2014-01-24 | 2015-09-30 | 成都新柯力化工科技有限公司 | Charged ceramic super-filtering film of a kind of magnetic induction and preparation method thereof |
| CN105013346B (en) * | 2014-04-22 | 2017-09-05 | 成都百途医药科技有限公司 | A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film |
| CN105013350B (en) * | 2014-04-22 | 2017-09-05 | 成都百途医药科技有限公司 | A kind of preparation method of super-hydrophobic polytetrafluoroethylfiber fiber film |
| CN104128101A (en) * | 2014-07-18 | 2014-11-05 | 南京工业大学 | Silver doped metal ceramic composite membrane and preparation method thereof |
| CN105268247B (en) * | 2014-07-23 | 2017-02-15 | 上海一鸣过滤技术有限公司 | Nanoscale porous metal filter medium and preparation method thereof |
| CN104403644B (en) * | 2014-11-03 | 2017-03-01 | 席君杰 | From dissolved material and preparation method thereof |
| CN104846301B (en) * | 2015-05-21 | 2017-03-15 | 西北有色金属研究院 | A kind of preparation method of low frequency absorption material |
| CN105127431B (en) * | 2015-08-26 | 2017-09-22 | 西北有色金属研究院 | A kind of preparation method of low frequency absorption material |
| CN105220141B (en) * | 2015-10-16 | 2018-06-12 | 北京有色金属研究总院 | A kind of cermet porous layer and preparation method thereof |
| CN105369202A (en) * | 2015-11-20 | 2016-03-02 | 沈阳黎明航空发动机(集团)有限责任公司 | Method for preparing thermal barrier coating on heavy gas turbine blade |
| CN105533118A (en) * | 2016-01-20 | 2016-05-04 | 山东禹王生态食业有限公司 | Technology for refining soybean protein according to membrane method |
| CN109200831A (en) * | 2017-06-30 | 2019-01-15 | 上海清粼环保科技有限公司 | A kind of preparation method of single side film flat ceramic filtration membrane |
| US11298663B2 (en) * | 2018-08-28 | 2022-04-12 | Molecule Works Inc. | Thin metal/ceramic hybrid membrane sheet and filter |
| CN110252156B (en) * | 2019-07-09 | 2022-04-05 | 湖南中天元环境工程有限公司 | Metal composite ceramic membrane and preparation method thereof |
| CN112468636B (en) * | 2019-09-06 | 2022-09-02 | 北京小米移动软件有限公司 | Housing and processing method thereof |
| CN115592120B (en) * | 2022-11-30 | 2023-05-19 | 江苏七禾新材料科技有限公司 | Repair process of metal-based ceramic composite membrane |
-
2008
- 2008-02-29 CN CNB2008100203180A patent/CN100563799C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101234296A (en) | 2008-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100563799C (en) | A kind of preparation technology of porous stainless steel-ceramic compound film | |
| CN102836642B (en) | Preparation method of porous ceramic-metal composite film material | |
| Will et al. | Fabrication of thin electrolytes for second-generation solid oxide fuel cells | |
| CN101183716B (en) | Method of producing three-in-one electrode of solid oxide fuel battery | |
| US20040265484A1 (en) | High power density solid oxide fuel cells and methods of fabrication | |
| CN103691329B (en) | A kind of preparation method of porous stainless steel membrane | |
| JP5252380B2 (en) | Composite structure and manufacturing method thereof | |
| CN103691330B (en) | A kind of preparation technology of porous stainless steel membrane | |
| CN110252156A (en) | A kind of metal composite ceramal film and preparation method thereof | |
| CN105239356A (en) | Composite ceramic coating for surface of SiC fiber and preparation method thereof | |
| CN110429225A (en) | A kind of preparation method of lithium ion battery ceramic coating membrane | |
| TW202015504A (en) | Shell of electronic equipment, electronic equipment and complex | |
| CN105198501A (en) | Preparation method of carbon/carbon composite material surface metal tungsten gradient coating | |
| CN109468639A (en) | A kind of ultralimit zircaloy and preparation method thereof | |
| CN112546734A (en) | Method for manufacturing filter material | |
| CN107523827A (en) | A kind of high temperature solar energy selective composite coating for absorbing and preparation method thereof | |
| CN109554707A (en) | A kind of ultralimit aluminium alloy and preparation method thereof | |
| CN104437112A (en) | Method for preparing porous metal supporting ceramic membrane based on static induced type nanometer particle coating | |
| CN102219523A (en) | Low-temperature co-firing ceramic wave-absorbing material and preparation method thereof | |
| CN110205626A (en) | A kind of functionally gradient thermal barrier coating and preparation method thereof | |
| CN103585897B (en) | Multi-channel ceramic/metal composite membrane and preparation method thereof | |
| CN102389715B (en) | Method for preparing porous inorganic membrane by particle sintering technology assisted by carbon skeleton | |
| JP6285684B2 (en) | Paint for forming structure and surface coating layer | |
| JP6411931B2 (en) | Composite hollow particles | |
| CN209472775U (en) | The micro- heating plate of ceramics of multilayer beam type structure |
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 |