CN104630771B - A kind of method for preparing porous oxide film in metal carrier surface - Google Patents
A kind of method for preparing porous oxide film in metal carrier surface Download PDFInfo
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Abstract
The invention discloses a kind of method for preparing porous oxide film in metal carrier surface, the method is：First, the oxide skin and impurity of surface treatment removal metal carrier surface are carried out to metallic carrier；2nd, according to porous oxide film selective oxidation thing to be prepared and oxide sol, then raw material is well mixed and is made slurry；3rd, slurry is covered in the metal carrier surface after surface treated；4th, it is placed in sintering furnace after drying, heat preservation sintering, the porous oxide film that thickness is not more than 100 μm is obtained after furnace cooling in metal carrier surface under reducing atmosphere.The method improve in film forming procedure porous oxide metal carrier surface filming performance, avoid may be due to causing electrochemical reaction to cause the problems such as corroding during film layer is dried using hydrosol system, shorten the film layer dry process time, and the sintering temperature of film layer is reduced, porous oxide film and the metallic matrix of preparation are well combined.
Description
Technical field
The invention belongs to porous oxide technical field of film preparation, and in particular to a kind of many in metal carrier surface preparation
The method of orifice oxide film.
Background technology
Metal carrier surface porous oxide thin-film material has reliability high, solderable, high temperature resistant, corrosion-resistant, radiating
Property good and good thermal shock the features such as, the filtering material that is widely used as in the industries such as high-precision food, petrochemical industry, chemistry are urged
Agent carrier etc..At present, preparing the common process of such material has following several classes：
(1) sol-gel process (SOL-GEL methods)
The method is hydrolyzed at a certain temperature using metal alkoxide, forms the colloidal sol of stabilization, is added in colloidal sol make afterwards
Hole agent, then coats film forming in metal carrier surface, and metal film is obtained with high-temperature roasting through drying.The inoranic membrane that the method is obtained
Layer aperture and porosity is controllable within the specific limits, pore-size distribution is narrow, may be used to prepare ultrafiltration and nanofiltration film layer.At present,
Domestic many research units make porous oxide film layer (such as northwest agricultural university and south using the method on ceramic matrix surface
Capital polytechnical university), part has been applied to mass production (such as Jiangsu companies are thought by my company and nine long).What the method was present asks
Topic is to be difficult to prepare porous membrane layer of the aperture in 0.01 μm~3 μ ms, and film layer to reach certain thickness more difficult.
(2) solid phase particles sintering process (slipeasting)
Powder particle and decentralized medium are mixed to form suspension by the method, and suspension is coated in into metal carrier surface,
Sinter at a certain temperature after drying, powder particle stacking overlaps to form hole, the part for contacting with each other forms sintering neck and carries
For intensity.The method can be by adjusting control and adjustment apertures rate and the pore size such as particle diameter, addition of powder particle；And can
By adjusting the content and related process parameters of viscosity-controlling agent in slurry, the thickness of film layer is controlled.But the method is due to wetting
The reason for property, slurry is difficult to effectively be attached to metal base surface, every physical particularly between oxide and matrix
The difference (such as thermal expansion coefficient difference and thermal coefficient differences) of energy, easily causes the cracking of film layer in subsequent treatment；Together
When, the sintering sex differernce that foreign material is present also results in the production that the method is difficult to use in continuous metal film.
(3) chemical vapour deposition technique
The method forms oxide using such as metal chloride, vapor, air raw material by chemical method, and will
Be deposited on matrix micropore surface or inside.By controlling reaction condition and sedimentation time, obtain thickness and compactness is controllable
Oxide porous film layer.The area of current this method film forming is smaller, is generally used to modify the aperture of perforated membrane.
(4) cement-dipping method is improved
Model benefit group et al. of Nanjing University of Technology is in order to improve profit of the oxide slurry to matrix in solid phase particles sintering process
It is moist, this method is employed at first (see membrane science and technology, the 3rd phase in 2011, to be improved cement-dipping method and prepare titanium oxide/porous
Titanium composite micro-filtration membrane).This method solve slurry present in dip-coating poor with matrix wetability, metallic matrix aperture mistake
The problem for being difficult to greatly match with film layer.In the work, its basic thought is to replace water as dispersant by the use of the hydrosol, but by
Do not consider to solve in hydrosol system is still present the problem poor with metal surface wellability, the particularly technique follow-up
The problems such as film layer season cracking and inadequate film substrate bond strength for easily occurring in technical process.
The content of the invention
The technical problems to be solved by the invention are for above-mentioned the deficiencies in the prior art, there is provided one kind is in metallic carrier
The method that surface prepares porous oxide film.The method uses oxide and oxide sol, in sintering process, oxide
Colloidal sol is changed into oxide particle of the granularity at several nanometers, as one of the main source of liquid phase during follow-up sintering, changes
The filming performance in metal carrier surface in porous oxide it has been apt in film forming procedure, it is to avoid film layer may be due to during drying
The problems such as causing electrochemical reaction to cause corrosion using hydrosol system, the film layer dry process time is shortened, and reduce
The sintering temperature of film layer, is well combined between the porous oxide film and metallic matrix of preparation；Oxide is then by the heap of particle
Pile and overlap joint form hole, and its granularity can adjust the viscosity of slurry with changes of contents, and adjust porous oxide film Hole
Aperture and porosity.And by adding the additive of proper content in the slurry, the surface energy of slurry can be reduced, alleviate dry
The cracking that the volatilization of capillary internal solvent is caused during dry, it is ensured that the filter effect of the porous oxide film of preparation, meanwhile, protect
Demonstrate,prove the stability of colloidal sol；By adding the dispersant of proper content in the slurry, the modified raising in surface can be carried out to oxide
The dispersiveness of oxide, it is ensured that the uniformity and stability of slurry；On the other hand, dispersant can also provide the extra porosity.
In order to solve the above technical problems, the technical solution adopted by the present invention is：One kind prepares porous in metal carrier surface
The method of sull, it is characterised in that comprise the following steps：
Step one, oxide skin and impurity that surface treatment removal metal carrier surface is carried out to metallic carrier；
Step 2, according to porous oxide film selective oxidation thing to be prepared and oxide sol, then will be following
Raw material by mass percentage is well mixed to be made slurry：Oxide 20%~30%, oxide sol 40%~50%, point
Powder 5%~35%, additive 2%~25%, sintering aid 0~15%；The dispersant be polyethylene glycol, polyacrylic acid,
One or more in stearic acid, polyethyleneimine and 12- hydroxy stearic acids；The additive is for concentration of volume percent
5%~10% glycerin solution, the PVB solution that mass percent concentration is 0.2%~5% or mass percent concentration are
The alcoholic solution of 5%~10% thermosetting resin, the sintering aid is boron oxide, cupric oxide, borate, cupric alkoxide or titanium alcohol
Salt；
Step 3, slurry described in step 2 is covered into the metal carrier surface in step one after surface treated；
Step 4, will be covered in step 3 have slurry metallic carrier dry after be placed in sintering furnace, under reducing atmosphere,
600 DEG C~1300 DEG C heat preservation sintering 0.5h~4h are heated to, thickness are obtained in metal carrier surface after furnace cooling and is not more than 100
μm porous oxide film.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step one
The metallic carrier is not less than 20% Lacunaris metal carrier for porosity.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 2
Following raw material by mass percentage is well mixed and is made slurry：Oxide 22%~28%, oxide sol 43%~
46%, dispersant 15%~25%, additive 5%~10%, sintering aid 1%~10%.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 2
The oxide is one or more in titanium dioxide, alundum (Al2O3), zirconium dioxide and silica.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 2
The oxide sol is in TiO 2 sol, alundum (Al2O3) colloidal sol, zirconia sol and silicon dioxide gel
Plant or several, the concentration of oxide is 0.025mol/L~3mol/L in oxide sol.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 2
The thermosetting resin is phenolic resin, polymethyl methacrylate or polybutadiene epoxy resin.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 3
Slurry is covered in the metal carrier surface after surface treated using the method for physical film deposition.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 3
The dry temperature is 60 DEG C~100 DEG C, and the dry time is 12h~36h.
A kind of above-mentioned method for preparing porous oxide film in metal carrier surface, it is characterised in that in step 3
The temperature of heat preservation sintering is 600 DEG C~1100 DEG C, and the time of heat preservation sintering is 1h~2h.
The present invention has advantages below compared with prior art：
1st, the present invention uses oxide and oxide sol, and in sintering process, oxide sol is changed into granularity several
The oxide particle of individual nanometer, as one of the main source of liquid phase during follow-up sintering, improves porous in film forming procedure
Filming performance of the oxide in metal carrier surface, it is to avoid film layer may be due to cause electricity during drying using hydrosol system
The problems such as chemical reaction causes corrosion, shortens the film layer dry process time, and reduces the sintering temperature of film layer, preparation
It is well combined between porous oxide film and metallic matrix；Oxide then forms hole by the stacking and overlap joint of particle, its grain
Degree can adjust the viscosity of slurry with changes of contents, and adjust aperture and the porosity of porous oxide film Hole.
2nd, the additive and sintering aid etc. for being added in slurry of the present invention, substantially increase the continuous of film layer after film forming
Property, integrality, and improve the combination of film layer and matrix.
3rd, the physical film deposition method such as the preferred spraying of the present invention or Best-Effort request, with low for equipment requirements, low cost, technique
Simple the characteristics of, be conducive to carrying out the popularization of the large-scale industrial production and correlation technique of film material.
4th, the additive that the present invention passes through addition proper content in the slurry, can reduce the surface energy of slurry, alleviate dry
The cracking that the volatilization of capillary internal solvent is caused during dry, it is ensured that the filter effect of the porous oxide film of preparation, meanwhile, protect
Demonstrate,prove the stability of colloidal sol.
5th, the dispersant that the present invention passes through addition proper content in the slurry, can carry out the modified raising in surface to oxide
The dispersiveness of oxide, it is ensured that the uniformity and stability of slurry；On the other hand, dispersant can also provide the extra porosity.
With reference to the accompanying drawings and examples, technical solution of the present invention is described in further detail.
Brief description of the drawings
Fig. 1 is the SEM figures on porous titania thin films surface prepared by the embodiment of the present invention 1.
Fig. 2 is that the section SEM of the POROUS TITANIUM that surface prepared by the embodiment of the present invention 1 has porous titania thin films schemes.
Fig. 3 is the XRD of porous titania thin films prepared by the embodiment of the present invention 1.
Specific embodiment
Embodiment 1
Porous titania thin films are prepared on the POROUS TITANIUM surface that porosity is 20%, specific method is comprised the following steps：
Step one, oxide skin and impurity that conventional pickling processes removal POROUS TITANIUM surface is carried out to POROUS TITANIUM；
Step 2, according to porous titania thin films selective oxidation thing (titanium dioxide) to be prepared and oxide sol
, then be well mixed for following raw material by mass percentage and be made slurry by (TiO 2 sol)：Titanium dioxide 20%, two
Titanium oxide sol 45%, polyethylene glycol (PEG2000) 25%, mass percent concentration is 0.2% PVB ethanol solutions 8%, body
Product percent concentration is the ethanol solution 1.5% of 5% glycerine, boron oxide 0.5%；Titanium dioxide in the TiO 2 sol
The concentration of titanium is 0.5mol/L；
Step 3, using spraying by the way of slurry described in step 2 is covered it is many after surface treated in step one
Hole titanium surface；
Step 4, the POROUS TITANIUM for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace,
In a hydrogen atmosphere, 1100 DEG C of heat preservation sintering 1.5h are heated to, obtaining thickness on POROUS TITANIUM surface after furnace cooling is about 25 μm
Porous titania thin films.
Tested through Vesicular protein and SEM, the porosity of porous titania thin films manufactured in the present embodiment is 36%, average pore size
It is 0.2 μm；Through XRD analysis (see Fig. 3), the main component of the porous titania thin films of preparation is TiOx(1<x<And rutile 2)
The TiO of phase2。
From figure 1 it appears that porous titania thin films manufactured in the present embodiment itself are without substantially cracking, distribution of pores is equal
Even, the porous titania thin films prepared have narrower pore-size distribution, can be used for high-precision filtration application.Can be with from Fig. 2
Find out, after being broken by external force, peeling off do not occur with metallic carrier in porous titania thin films manufactured in the present embodiment, film
Layer is still covered in metal carrier surface, and porous titania thin films and metallic carrier prepared by this explanation have good combination energy
Power；Other part slurry forms mechanical snap in penetrating into the hole of metallic carrier, and this will further improve film and is carried with metal
The combination of body.
Embodiment 2
Porous alumina membrane is prepared in the 316L stainless steel surfaces that porosity is 30%, specific method includes following step
Suddenly：
Step one, commercial blast (ball) the treatment removal oxide skin of 316L stainless steel surfaces and miscellaneous is carried out to 316L stainless steels
Matter；
Step 2, according to porous alumina membrane selective oxidation thing (alundum (Al2O3)) to be prepared and oxide sol
, then be well mixed for following raw material by mass percentage and be made slurry by (alundum (Al2O3) colloidal sol)：Alundum (Al2O3)
30%, alundum (Al2O3) colloidal sol 50%, polyethyleneimine 15%, mass percent concentration is 0.2% PVB ethanol solutions 5%；
The concentration of alundum (Al2O3) is 0.025mol/L in the alundum (Al2O3) colloidal sol；
Step 3, by the way of Best-Effort request slurry described in step 2 is covered in step one after surface treated
316L stainless steel surfaces；
Step 4, the 316L stainless steels for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace
In, in a hydrogen atmosphere, 1300 DEG C of heat preservation sintering 1h being heated to, obtaining thickness in 316L stainless steel surfaces after furnace cooling is about
90 μm of porous alumina membrane.
Tested through nitrogen adsorption methods and SEM, the average pore size of porous alumina membrane manufactured in the present embodiment is 3 μm；Through
XRD analysis, the main component of the porous alumina membrane of preparation is Al2O3。
Scanned electron microscope observation, porous alumina membrane manufactured in the present embodiment itself is without substantially cracking, hole
It is evenly distributed, the porous alumina membrane prepared has narrower pore-size distribution, can be used for high-precision filtration application.It is being subject to
After external force fracture, peeling off does not occur with metallic carrier in porous alumina membrane manufactured in the present embodiment, and pellicle film is still in metal
Carrier surface is covered, and porous alumina membrane prepared by this explanation has good binding ability with metallic carrier；Other part
Slurry forms mechanical snap in penetrating into the hole of metallic carrier, and this will further improve the combination of film and metallic carrier.
Embodiment 3
Porous zirconia film is prepared on the Porous Cu surface that porosity is 25%, specific method is comprised the following steps：
Step one, oxide skin and impurity that conventional pickling processes removal Porous Cu surface is carried out to Porous Cu；
Step 2, according to porous zirconia film selective oxidation thing (zirconium dioxide) to be prepared and oxide sol
, then be well mixed for following raw material by mass percentage and be made slurry by (zirconia sol)：Zirconium dioxide 20%, two
Zirconia sol 50%, stearic acid 15%, mass percent concentration is the ethanol solution 10% of 10% phenolic resin, cupric oxide
5%；The concentration of zirconium dioxide is 1mol/L in the zirconia sol；
Step 3, using spraying by the way of slurry described in step 2 is covered it is many after surface treated in step one
Hole copper surface；
Step 4, the Porous Cu for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace,
In a hydrogen atmosphere, 600 DEG C of heat preservation sintering 1h are heated to, obtaining thickness on Porous Cu surface after furnace cooling is about 65 μm many
Hole zirconia film.
Tested through nitrogen adsorption methods and SEM, the average pore size of porous zirconia film manufactured in the present embodiment is 50nm；Through
XRD analysis, the main component of the porous zirconia film of preparation is ZrO2。
Scanned electron microscope observation, porous zirconia film itself manufactured in the present embodiment is without substantially cracking, hole
It is evenly distributed, the porous zirconia film prepared has narrower pore-size distribution, can be used for high-precision filtration application.It is being subject to
After external force fracture, peeling off does not occur with metallic carrier in porous zirconia film manufactured in the present embodiment, and pellicle film is still in metal
Carrier surface is covered, and porous zirconia film prepared by this explanation has good binding ability with metallic carrier；Other part
Slurry forms mechanical snap in penetrating into the hole of metallic carrier, and this will further improve the combination of film and metallic carrier.
Embodiment 4
Porous silicon oxide membrane is prepared on the POROUS TITANIUM surface that porosity is 20%, specific method is comprised the following steps：
Step one, oxide skin and impurity that conventional polishing removal POROUS TITANIUM surface is carried out to POROUS TITANIUM；
Step 2, according to porous silicon oxide membrane selective oxidation thing (silica) to be prepared and oxide sol
, then be well mixed for following raw material by mass percentage and be made slurry by (silicon dioxide gel)：Silica 27%, two
Silica sol 43%, polyacrylic acid 5%, 12- hydroxy stearic acids 10%, mass percent concentration be 0.2% PVB ethanol it is molten
Liquid 5%, butyl titanate 10%；The concentration of silica is 0.05mol/L in the silicon dioxide gel；
Step 3, by the way of Best-Effort request slurry described in step 2 is covered in step one after surface treated
POROUS TITANIUM surface；
Step 4, the POROUS TITANIUM for having slurry will be covered in step 3 dry 36h at 60 DEG C, be subsequently placed in sintering furnace,
In a hydrogen atmosphere, 900 DEG C of heat preservation sintering 2h are heated to, obtaining thickness on POROUS TITANIUM surface after furnace cooling is about 36 μm many
Hole silicon oxide film.
Tested through Vesicular protein and SEM, the porosity of microporous silica film manufactured in the present embodiment is 38%, average hole
Footpath is 0.5 μm；Through XRD analysis, the main component of the porous silicon oxide membrane of preparation is SiO2。
Scanned electron microscope observation, porous silicon oxide membrane manufactured in the present embodiment itself is without substantially cracking, hole
It is evenly distributed, the porous silicon oxide membrane prepared has narrower pore-size distribution, can be used for high-precision filtration application.It is being subject to
After external force fracture, peeling off does not occur with metallic carrier in porous silicon oxide membrane manufactured in the present embodiment, and pellicle film is still in metal
Carrier surface is covered, and porous silicon oxide membrane prepared by this explanation has good binding ability with metallic carrier；Other part
Slurry forms mechanical snap in penetrating into the hole of metallic carrier, and this will further improve the combination of film and metallic carrier.
Embodiment 5
Woelm Alumina-titanium oxide composite film, specific method are prepared in the 316L stainless steel surfaces that porosity is 20%
Comprise the following steps：
Step one, oxide skin and impurity that conventional bead removal 316L stainless steel surfaces are carried out to 316L stainless steels；
Step 2, according to Woelm Alumina to be prepared-titanium oxide composite film selective oxidation thing (alundum (Al2O3) and
Titanium dioxide) and oxide sol (alundum (Al2O3) colloidal sol and TiO 2 sol), then by it is following by mass percentage
Raw material well mixed be made slurry：Alundum (Al2O3) 10%, titanium dioxide 12%, alundum (Al2O3) colloidal sol 20%, titanium dioxide
Titanium colloidal sol 26%, stearic acid 10%, polyethyleneimine 15%, mass percent concentration is 5% PVB ethanol solutions 4%, quality
Percent concentration is the ethanol solution 2% of 10% polymethyl methacrylate, methoxyl group copper 1%；The alundum (Al2O3) is molten
The concentration of alundum (Al2O3) is 0.05mol/L in glue, and the concentration of titanium dioxide is 0.05mol/L in TiO 2 sol；
Step 3, by the way of Best-Effort request slurry described in step 2 is covered in step one after surface treated
316L stainless steel surfaces；
Step 4, the 316L stainless steels for having slurry will be covered in step 3 dry 12h at 100 DEG C, be subsequently placed in sintering
In stove, in a hydrogen atmosphere, 1000 DEG C of heat preservation sintering 1.5h are heated to, thickness is obtained in 316L stainless steel surfaces after furnace cooling
About 16 μm of Woelm Alumina-titanium oxide composite film.
Tested through nitrogen adsorption methods and SEM, the average hole of Woelm Alumina-titanium oxide composite film manufactured in the present embodiment
Footpath is 0.3 μm；Through XRD analysis, the main component of the Woelm Alumina-titanium oxide composite film of preparation is Al2O3And TiOx(1<x
<2), wherein Al2O3Mass content be about 44%, TiOxMass content be about 53%.
Scanned electron microscope observation, Woelm Alumina-titanium oxide composite film manufactured in the present embodiment itself is without bright
Aobvious cracking, even pore distribution, the Woelm Alumina-titanium oxide composite film prepared has narrower pore-size distribution, can use
In high-precision filtration application.After being broken by external force, Woelm Alumina-titanium oxide composite film manufactured in the present embodiment with gold
Peeling off does not occur in category carrier, and pellicle film is still covered in metal carrier surface, and Woelm Alumina-titanium oxide prepared by this explanation is multiple
Close film has good binding ability with metallic carrier；Other part slurry forms machinery in penetrating into the hole of metallic carrier
Occlusion, this will further improve the combination of film and metallic carrier.
Embodiment 6
Woelm Alumina-silica-titania laminated film is prepared on the Porous Cu surface that porosity is 25%, specific side
Method is comprised the following steps：
Step one, oxide skin and impurity that conventional pickling processes removal Porous Cu surface is carried out to Porous Cu；
Step 2, according to Woelm Alumina to be prepared-silica-titania laminated film selective oxidation thing (three oxygen
Change two aluminium, silica and titanium dioxide) and oxide sol (alundum (Al2O3) colloidal sol, TiO 2 sol and silica
Colloidal sol), then following raw material by mass percentage is well mixed and is made slurry：Alundum (Al2O3) 6%, silica
11%, titanium dioxide 11%, alundum (Al2O3) colloidal sol 10%, TiO 2 sol 20%, silicon dioxide gel 15%, poly- second two
Alcohol (PEG2000) 5%, polyacrylic acid 5%, stearic acid 10%, mass percent concentration is 8% polybutadiene epoxy resin
Ethanol solution 2%, concentration of volume percent is 7% glycerine ethanol solution 3%, sodium tetraborate 2%；The alundum (Al2O3)
The concentration of alundum (Al2O3) is 1.5mol/L in colloidal sol, and the concentration of titanium dioxide is 2mol/L, titanium dioxide in TiO 2 sol
The concentration of silica is 1mol/L in Ludox；
Step 3, using spraying by the way of slurry described in step 2 is covered it is many after surface treated in step one
Hole copper surface；
Step 4, the Porous Cu for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace,
In a hydrogen atmosphere, 600 DEG C of heat preservation sintering 1h are heated to, obtaining thickness on Porous Cu surface after furnace cooling is about 10 μm many
Porous aluminum oxide-silica-titania laminated film.
Tested through nitrogen adsorption methods and SEM, Woelm Alumina manufactured in the present embodiment-silica-titania laminated film
Average pore size be 20nm；Through XRD analysis, the main component of the Woelm Alumina-silica-titania laminated film of preparation is
Al2O3、SiO2And TiOx(1<x<2), wherein the mass content of each main component is respectively Al2O3About 22%, SiO2About 39%,
TiOxAbout 34%.
Scanned electron microscope observation, Woelm Alumina manufactured in the present embodiment-silica-titania laminated film is certainly
Without substantially cracking, even pore distribution, the Woelm Alumina prepared-silica-titania laminated film has narrower body
Pore-size distribution, can be used for high-precision filtration application.After being broken by external force, Woelm Alumina-oxidation manufactured in the present embodiment
Peeling off does not occur with metallic carrier in silicon-titanium oxide composite film, and pellicle film is still covered in metal carrier surface, prepared by this explanation
Woelm Alumina-silica-titania laminated film and metallic carrier have good binding ability；Other part slurry oozes
Enter and form mechanical snap in the hole of metallic carrier, this will further improve the combination of film and metallic carrier.
Embodiment 7
Porous oxidation titania-zirconia laminated film is prepared on the POROUS TITANIUM surface that porosity is 20%, specific method includes
Following steps：
Step one, oxide skin and impurity that conventional polishing removal POROUS TITANIUM surface is carried out to POROUS TITANIUM；
Step 2, according to porous oxidation titania-zirconia laminated film selective oxidation thing (titanium dioxide) to be prepared and
, then be well mixed for following raw material by mass percentage and be made slurry by oxide sol (zirconia sol)：Dioxy
Change titanium 20%, zirconia sol 48%, 12- hydroxy stearic acids 5%, mass percent concentration is 0.2% PVB ethanol solutions
10%, concentration of volume percent is 10% glycerine ethanol solution 5%, and mass percent concentration is 8% phenolic resin second
Alcoholic solution 10%, cupric oxide 2%；The concentration of zirconium dioxide is 1mol/L in the zirconia sol；
Step 3, using spraying by the way of slurry described in step 2 is covered it is many after surface treated in step one
Hole titanium surface；
Step 4, the POROUS TITANIUM for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace,
In a hydrogen atmosphere, 1100 DEG C of heat preservation sintering 1.5h are heated to, obtaining thickness on POROUS TITANIUM surface after furnace cooling is about 38 μm
Porous oxidation titania-zirconia laminated film.
Tested through Vesicular protein and SEM, the porosity of porous oxidation titania-zirconia laminated film manufactured in the present embodiment is
32%, average pore size is 0.4 μm；Through XRD analysis, the main component of the porous oxidation titania-zirconia laminated film of preparation is
ZrO2And TiOx(1<x<2), wherein the mass content of each main component is respectively ZrO2About 37% and TiOxAbout 53%.
Scanned electron microscope observation, porous oxidation titania-zirconia laminated film itself manufactured in the present embodiment is without bright
Aobvious cracking, even pore distribution, the porous oxidation titania-zirconia laminated film prepared has narrower pore-size distribution, can use
In high-precision filtration application.After being broken by external force, porous oxidation titania-zirconia laminated film manufactured in the present embodiment with gold
Peeling off does not occur in category carrier, and pellicle film is still covered in metal carrier surface, and porous oxidation titania-zirconia prepared by this explanation is answered
Close film has good binding ability with metallic carrier；Other part slurry forms machinery in penetrating into the hole of metallic carrier
Occlusion, this will further improve the combination of film and metallic carrier.
Embodiment 8
Woelm Alumina-silica-titania-zirconia is prepared in the 316L stainless steel surfaces that porosity is 30% to be combined
Film, specific method is comprised the following steps：
Step one, oxide skin and impurity that conventional pickling processes removal 316L stainless steel surfaces are carried out to 316L stainless steels；
Step 2, according to Woelm Alumina to be prepared-silica-titania-zirconia laminated film selective oxidation
Thing (alundum (Al2O3), silica and zirconium dioxide) and oxide sol (TiO 2 sol), then by following by quality
The raw material of percentages is well mixed to be made slurry：Alundum (Al2O3) 5%, silica 1 0%, zirconium dioxide 5%, titanium dioxide
Titanium colloidal sol 40%, polyacrylic acid 15%, polyethyleneimine 20%, mass percent concentration is 3% PVB ethanol solutions 2%, matter
Amount percent concentration is 5% polybutadiene epoxy resin ethanol solution 3%；The concentration of titanium dioxide in the TiO 2 sol
It is 3mol/L；
Step 3, by the way of Best-Effort request slurry described in step 2 is covered in step one after surface treated
316L stainless steel surfaces；
Step 4, the 316L stainless steels for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace
In, in a hydrogen atmosphere, 1300 DEG C of heat preservation sintering 1h being heated to, obtaining thickness in 316L stainless steel surfaces after furnace cooling is about
65 μm of Woelm Alumina-silica-titania-zirconia laminated film.
Tested through nitrogen adsorption methods and SEM, Woelm Alumina-silica-titania-zirconia manufactured in the present embodiment is multiple
The average pore size for closing film is 0.7 μm；Through XRD analysis, the Woelm Alumina-silica-titania-zirconia THIN COMPOSITE of preparation
The main component of film is AlO3、SiO2、TiOx(1<x<And ZrO 2)2, wherein the mass content of each main component is respectively Al2O3About
12.5%, TiOxAbout 50%, SiO2About 25%, ZrO2About 12.5%.
Scanned electron microscope observation, Woelm Alumina-silica-titania-zirconia manufactured in the present embodiment is multiple
Film itself is closed without substantially cracking, even pore distribution, the Woelm Alumina-silica-titania-zirconia prepared is combined
Film has narrower pore-size distribution, can be used for high-precision filtration application.It is manufactured in the present embodiment many after being broken by external force
Peeling off does not occur with metallic carrier in porous aluminum oxide-silica-titania-zirconia laminated film, and pellicle film is still carried in metal
Body surface face covers, and Woelm Alumina-silica-titania-zirconia laminated film prepared by this explanation has with metallic carrier
Good binding ability；Other part slurry forms mechanical snap in penetrating into the hole of metallic carrier, and this will further improve
The combination of film and metallic carrier.
Embodiment 9
Porous zirconia film is prepared on the Porous Cu surface that porosity is 25%, specific method is comprised the following steps：
Step one, oxide skin and impurity that conventional pickling processes removal Porous Cu surface is carried out to Porous Cu；
Step 2, according to porous zirconia film selective oxidation thing (zirconium dioxide) to be prepared and oxide sol
, then be well mixed for following raw material by mass percentage and be made slurry by (zirconia sol)：Zirconium dioxide 25%, two
Zirconia sol 40%, stearic acid 15%, mass percent concentration is the ethanol solution 5% of 10% phenolic resin, cupric oxide
15%；The concentration of zirconium dioxide is 1mol/L in the zirconium dioxide；
Step 3, using spraying by the way of slurry described in step 2 is covered it is many after surface treated in step one
Hole copper surface；
Step 4, the Porous Cu for having slurry will be covered in step 3 dry 24h at 80 DEG C, be subsequently placed in sintering furnace,
In a hydrogen atmosphere, 600 DEG C of heat preservation sintering 1h are heated to, obtaining thickness on Porous Cu surface after furnace cooling is about 30 μm many
Hole zirconia film.
Tested through nitrogen adsorption methods and SEM, the average pore size of porous zirconia film manufactured in the present embodiment is 200nm；
Through XRD analysis, the main component of the porous zirconia film of preparation is ZrO2。
Scanned electron microscope observation, porous zirconia film itself manufactured in the present embodiment is without substantially cracking, hole
It is evenly distributed, the porous zirconia film prepared has narrower pore-size distribution, can be used for high-precision filtration application.It is being subject to
After external force fracture, peeling off does not occur with metallic carrier in porous zirconia film manufactured in the present embodiment, and pellicle film is still in metal
Carrier surface is covered, and porous zirconia film prepared by this explanation has good binding ability with metallic carrier；Other part
Slurry forms mechanical snap in penetrating into the hole of metallic carrier, and this will further improve the combination of film and metallic carrier.
The above, is only presently preferred embodiments of the present invention, and any limitation is not done to the present invention, every according to invention skill
Any simple modification, change and equivalent structure change that art is substantially made to above example, still fall within the technology of the present invention
In the protection domain of scheme.
Claims (8)
1. a kind of method for preparing porous oxide film in metal carrier surface, it is characterised in that comprise the following steps：
Step one, oxide skin and impurity that surface treatment removal metal carrier surface is carried out to metallic carrier；The metallic carrier
20% Lacunaris metal carrier is not less than for porosity；
Step 2, according to porous oxide film selective oxidation thing to be prepared and oxide sol, then will be by following matter
The raw material of amount percentages is well mixed to be made slurry：Oxide 20%~30%, oxide sol 40%~50%, dispersant
5%~35%, additive 2%~25%, sintering aid 0~15%；The dispersant is polyethylene glycol, polyacrylic acid, tristearin
One or more in acid, polyethyleneimine and 12- hydroxy stearic acids；The additive be concentration of volume percent be 5%~
10% glycerin solution, the PVB solution that mass percent concentration is 0.2%~5% or mass percent concentration be 5%~
The alcoholic solution of 10% thermosetting resin, the sintering aid is boron oxide, cupric oxide, borate, cupric alkoxide or Titanium alkoxides；
Step 3, slurry described in step 2 is covered into the metal carrier surface in step one after surface treated；
Step 4, will be covered in step 3 have slurry metallic carrier dry after be placed in sintering furnace, under reducing atmosphere, heating
Thickness is obtained in metal carrier surface be not more than 100 μm to 600 DEG C~1300 DEG C heat preservation sintering 0.5h~4h, after furnace cooling
Porous oxide film.
2. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1, its feature exists
In each raw material is made into slurry according to following mass percent is well mixed in step 2：Oxide 22%~28%, oxide
Colloidal sol 43%~46%, dispersant 15%~25%, additive 5%~10%, sintering aid 1%~10%.
3. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1 or 2, it is special
Levy and be, oxide described in step 2 is the one kind or several in titanium dioxide, alundum (Al2O3), zirconium dioxide and silica
Kind.
4. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1 or 2, it is special
Levy and be, oxide sol described in step 2 is TiO 2 sol, alundum (Al2O3) colloidal sol, zirconia sol and dioxy
One or more in SiClx colloidal sol, the concentration of oxide is 0.025mol/L~3mol/L in oxide sol.
5. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1 or 2, it is special
Levy and be, thermosetting resin described in step 2 is phenolic resin, polymethyl methacrylate or polybutadiene epoxy resin.
6. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1 or 2, it is special
Levy and be, the method in step 3 using physical film deposition covers in the metal carrier surface after surface treated slurry.
7. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1 or 2, it is special
Levy and be, dry temperature described in step 4 is 60 DEG C~100 DEG C, the dry time is 12h~36h.
8. a kind of method for preparing porous oxide film in metal carrier surface according to claim 1 or 2, it is special
Levy and be, the temperature of heat preservation sintering is 600 DEG C~1100 DEG C in step 4, the time of heat preservation sintering is 1h~2h.
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| CN101027428A (en) * | 2004-06-03 | 2007-08-29 | 卢瓦塔奥公司 | Method for reducing metal oxide powder and attaching it to a heat transfer surface and the heat transfer surface |
| CN102380321A (en) * | 2011-09-07 | 2012-03-21 | 三达膜科技（厦门）有限公司 | Method for preparing coating of alumina ceramic membrane |
| CN102500748A (en) * | 2011-10-25 | 2012-06-20 | 中南大学 | Method for preparing aluminum silicon carbide composite material |
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| CN101027428A (en) * | 2004-06-03 | 2007-08-29 | 卢瓦塔奥公司 | Method for reducing metal oxide powder and attaching it to a heat transfer surface and the heat transfer surface |
| CN102380321A (en) * | 2011-09-07 | 2012-03-21 | 三达膜科技（厦门）有限公司 | Method for preparing coating of alumina ceramic membrane |
| CN102500748A (en) * | 2011-10-25 | 2012-06-20 | 中南大学 | Method for preparing aluminum silicon carbide composite material |
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