CN102500245A - Preparation method of metal-base ceramic composite filter membrane - Google Patents
Preparation method of metal-base ceramic composite filter membrane Download PDFInfo
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- CN102500245A CN102500245A CN201110393344XA CN201110393344A CN102500245A CN 102500245 A CN102500245 A CN 102500245A CN 201110393344X A CN201110393344X A CN 201110393344XA CN 201110393344 A CN201110393344 A CN 201110393344A CN 102500245 A CN102500245 A CN 102500245A
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Abstract
The invention discloses a preparation method of a metal-base ceramic composite filter membrane. The method includes steps: firstly, uniformly coating powder on the surface of a porous matrix, and obtaining a porous metal membrane layer by means of sintering; secondly, soaking the porous metal membrane layer into electrolyte to be anodized and obtaining a transition layer; thirdly, adding oxide powder into dispersing agent to obtain coating liquid; fourthly, coating the coating liquid onto the transition layer and sintering the transition layer after the transition layer is dried; and fifthly, repeating the fourth step for a product after being sintered until a porous ceramic filtering membrane with the thickness ranging from 2mum to 80mum is obtained, and obtaining the metal-base ceramic composite filtering membrane. The problem that bonding is not firm enough when metal and ceramic are compounded is resolved, the effective transition layer is formed on the metal matrix, so that a ceramic layer is firmly bonded with the metal matrix, processability of the prepared composite filter membrane is good, and the composite filter membrane can be used for preparing filtering devices in various shapes, simultaneously, has excellent chemical attack resistance, is high in pressure resistance and stable in repeatability, and can be used as a key component for micro-nano filtering and separating.
Description
Technical field
The invention belongs to technology field of membrane materials, be specifically related to the preparation method of the compound filter membrane of a kind of ceramic on metal.
Background technology
Membrane technology is contemporary new and effective isolation of purified technology, economizes on resources and eco-friendly characteristic with it, becomes one of general character support technology that solves the significant problems such as resource and environment coordinated development that current mankind faces.Than organic film material; With metal and pottery be that the inorganic material film because high temperature resistant, corrosion-resistant, anti-of representative washes away, mechanical strength greatly, advantages such as Stability Analysis of Structures, the deep purifying field in HTHP and corrosive atmosphere shows wide application prospect.
Than the ceramic membrane material; The metal membrane material comprehensive mechanical property is better, can under higher pressure, use, and metal film has good heat-conductive characteristic and excellent heat-sinking capability; Reduce the thermal stress of membrane module, effectively improved the thermal shock resistance and the service life of membrane module.The good welding performance of metal film assembly makes it have excellent sealing property and pulse cleaning performance in addition.Yet traditional metal polyporous material aperture overwhelming majority is in the micron order scope, and filtering accuracy is 2 μ m～50 μ m, is mainly used in coarse filtration.In recent years, external GKN company adopts the submicron order metal dust, utilizes powder wet spray technology to be shaped, and makes the submicron order metal film that the aperture is about 0.5 micron through sintering at the antipriming pipe outer wall.The metal inner surface film pipe of the centrifugal classification deposition formation technology preparation of domestic Xibei Inst. of Non-Ferrous Metals exploitation, its aperture is about 1 micron.Because the feed metal powder is difficult to reach the nanoscale scope, the aperture of above metal film can only reach submicron order.
Summary of the invention
Technical problem to be solved by this invention is the deficiency to above-mentioned prior art; A kind of good processability is provided; Compressive resistance is high, and repeat performance is stable, can be used as the preparation method of micro-nano size filtered and the compound filter membrane of ceramic on metal of the critical component that separates.Exist when this method is directed against metal, Ceramic Composite and combine firm inadequately problem; Through on metallic matrix, forming a kind of effective transition zone; On transition zone, apply then and obtain the ceramic layer filter membrane; Obtain the metallic matrix/Ceramic Composite filter membrane through the transition zone strong bonded, the compound filter membrane aperture of acquisition is 10nm～500nm.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is: the preparation method of the compound filter membrane of a kind of ceramic on metal is characterized in that this method may further comprise the steps:
Step 1, to select the aperture for use be that the metal polyporous material of 5 μ m～35 μ m is a matrix; On matrix surface, evenly applying granularity is the powder of 1 μ m～5 μ m; The matrix that will be coated with powder then is sintering 1h～3h under 700 ℃～1200 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous metals rete of 0.8 μ m～2.5 μ m; Said powder is hydride powder, titanium alloy powder, nickel powder, nickel alloy powder, stainless steel powder, FeCrAl alloyed powder, NiCrAlFe alloyed powder or FeAl alloyed powder, and the coating thickness of powder is 6 μ m～80 μ m;
Step 2, the rete of porous metals described in the step 1 is immersed anodic oxidation 5min～30min in the electrolyte, obtain oxidate nano loose structure transition zone;
Step 3, be that the oxide powder of 5nm～300nm adds in the dispersant with particle diameter, stirring obtains the coating liquid that oxide powder concentration is 0.05g/mL～0.2g/mL; Said oxide powder is titanium dioxide powder, alumina powder or Zirconium oxide powder; Said dispersant is TiO
2The colloidal sol or the PVA aqueous solution;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 10min～50min under 400 ℃～900 ℃ conditions; The coating thickness of said coating liquid is 0.15 μ m～2.5 μ m;
Step 5, be the porous ceramics filter membrane of 2 μ m～80 μ m until obtaining thickness, obtain the compound filter membrane of ceramic on metal the product repeating step four behind the sintering in the step 4.
The preparation method of the above-mentioned compound filter membrane of a kind of ceramic on metal, when powder described in the step 1 was hydride powder or titanium alloy powder, electrolyte described in the step 2 was the mixed aqueous solution of hydrofluoric acid and nitric acid, said oxidation voltage is 5V～20V; The concentration of volume percent of hydrofluoric acid is 0.3%～1.1% in the said mixed aqueous solution, and the concentration of volume percent of nitric acid is 1.0%～2.0%.
The preparation method of the above-mentioned compound filter membrane of a kind of ceramic on metal; When powder described in the step 1 is stainless steel powder, FeCrAl alloyed powder, NiCrAlFe alloyed powder or FeAl alloyed powder; Electrolyte described in the step 2 is the mixed solution of ammonium fluoride, water and ethylene glycol, and said oxidation voltage is 10V～80V; The concentration of ammonium fluoride is 0.05M～0.15M in the said mixed solution, and the concentration of water is 0.2M～1.0M.
The preparation method of the above-mentioned compound filter membrane of a kind of ceramic on metal; When powder described in the step 1 is nickel powder, NiCrAlFe alloyed powder or nickel alloy powder; Electrolyte described in the step 2 is that concentration is the aqueous solution of nitric acid of 0.1M～0.6M, and said oxidation voltage is 1V～20V.
The preparation method of the above-mentioned compound filter membrane of a kind of ceramic on metal, TiO described in the step 3
2The concentration of colloidal sol is 0.3M～0.7M, and the mass concentration of the said PVA aqueous solution is 2%～10%.
The present invention compared with prior art has the following advantages:
1, preparation technology of the present invention is easy and simple to handle and reasonable in design, the raw material wide material sources, is easy to get, and cost is lower, can realize the mass preparation of the compound filter membrane of ceramic on metal.
2, the filter membrane processability of the present invention's preparation is good, can process the filtration of different shape and use device, has good resistance to chemical attack simultaneously, and compressive resistance is high, and repeat performance is stable, can be used as micro-nano size filtered and the critical component that separates.
3, the compound filter membrane of ceramic on metal of the present invention can be processed, and can weld, and can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Exist when 4, the present invention is directed to metal, Ceramic Composite and combine firm inadequately problem; Through on metallic matrix, forming a kind of effective transition zone; On transition zone, apply then and obtain the ceramic layer filter membrane; Obtain the metallic matrix/Ceramic Composite filter membrane through the transition zone strong bonded, the compound filter membrane aperture of acquisition is 10nm～500nm.
Through embodiment, technical scheme of the present invention is done further to describe in detail below.
The specific embodiment
Embodiment 1
Step 1, to select the aperture for use be that the Titanium porous material of 35 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 20 μ m on matrix surface then is the hydride powder of 2 μ m; The matrix that will be coated with hydride powder then is sintering 1h under 900 ℃ the vacuum condition in temperature, and obtaining the aperture is the POROUS TITANIUM metallic diaphragm of 1.5 μ m;
Step 2, the metallic diaphragm of POROUS TITANIUM described in the step 1 being immersed in the electrolyte, is anodic oxidation 5min under the condition of 20V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is the mixed aqueous solution of hydrofluoric acid and nitric acid, and the concentration of volume percent of hydrofluoric acid is 0.3% in the mixed aqueous solution, and the concentration of volume percent of nitric acid is 2.0%;
Step 3, be that to add concentration be the TiO of 0.3M for the titanium dioxide powder of 60nm with particle diameter
2In the colloidal sol, stirring obtains the coating liquid that titanium dioxide powder concentration is 0.05g/mL;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 50min under 400 ℃ of conditions; The coating thickness of said coating liquid is 0.15 μ m;
Step 5, be the porous ceramics filter membrane of 2 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 50nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 2
Present embodiment is identical with embodiment 1, and wherein difference is: used powder is the titanium alloy powder; Used oxide powder is alumina powder or Zirconium oxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 3
Step 1, to select the aperture for use be that the 316L stainless steel porous material of 28 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 30 μ m on matrix surface then is the stainless steel powder of 1.6 μ m; The matrix that will be coated with stainless steel powder then is sintering 3h under 1000 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous stainless steel metallic diaphragm of 0.8 μ m;
Step 2, the metallic diaphragm of porous stainless steel described in the step 1 being immersed in the electrolyte, is anodic oxidation 20min under the condition of 30V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is the mixed solution of ammonium fluoride, water and ethylene glycol, and the concentration of ammonium fluoride is 0.15M in the mixed solution, and the concentration of water is 1.0M;
Step 3, be that to add concentration be the TiO of 0.7M for the titanium dioxide powder of 10nm with particle diameter
2In the colloidal sol, stirring obtains the coating liquid that titanium dioxide powder concentration is 0.2g/mL;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 10min under 900 ℃ of conditions; The coating thickness of said coating liquid is 1 μ m;
Step 5, be the porous ceramics filter membrane of 15 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 10nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 4
Present embodiment is identical with embodiment 3, and wherein difference is: used powder is FeCrAl alloyed powder, NiCrAlFe alloyed powder or FeAl alloyed powder; Used oxide powder is alumina powder or Zirconium oxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 5
Step 1, to select the aperture for use be that the porous Ni-base alloy material of 5 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 6 μ m on matrix surface then is the nickel powder of 1 μ m; The matrix that will be coated with nickel powder then is sintering 2h under 800 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous nickel metal rete of 0.8 μ m;
Step 2, the rete of porous nickel metal described in the step 1 being immersed in the electrolyte, is anodic oxidation 30min under the condition of 1V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is that concentration is the aqueous solution of nitric acid of 0.1M;
Step 3, be that to add concentration be the TiO of 0.5M for the titanium dioxide powder of 300nm with particle diameter
2In the colloidal sol, stirring obtains the coating liquid that titanium dioxide powder concentration is 0.1g/mL;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 20min under 800 ℃ of conditions; The coating thickness of said coating liquid is 0.2 μ m;
Step 5, be the porous ceramics filter membrane of 2 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 360nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 6
Present embodiment is identical with embodiment 5, and wherein difference is: used powder is NiCrAlFe alloyed powder or other nickel alloy powder; Used oxide powder is alumina powder or Zirconium oxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 7
Step 1, to select the aperture for use be that the Titanium porous material of 28 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 10 μ m on matrix surface then is the hydride powder of 2 μ m; The matrix that will be coated with hydride powder then is sintering 1h under 1200 ℃ the vacuum condition in temperature, and obtaining the aperture is the POROUS TITANIUM metallic diaphragm of 1.5 μ m;
Step 2, the metallic diaphragm of POROUS TITANIUM described in the step 1 being immersed in the electrolyte, is anodic oxidation 30min under the condition of 5V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is the mixed aqueous solution of hydrofluoric acid and nitric acid, and the concentration of volume percent of hydrofluoric acid is 1.1% in the mixed aqueous solution, and the concentration of volume percent of nitric acid is 1.0%;
Step 3, be that to add mass concentration be that stirring obtains the coating liquid that Zirconium oxide powder concentration is 0.2g/mL in 10% the PVA aqueous solution for the Zirconium oxide powder of 50nm with particle diameter;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 30min under 600 ℃ of conditions; The coating thickness of said coating liquid is 2 μ m;
Step 5, be the porous ceramics filter membrane of 18 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 28nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 8
Present embodiment is identical with embodiment 7, and wherein difference is: used powder is the titanium alloy powder; Used oxide powder is alumina powder or titanium dioxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 9
Step 1, to select the aperture for use be that the 316L stainless steel porous material of 33 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 80 μ m on matrix surface then is the stainless steel powder of 5 μ m; The matrix that will be coated with stainless steel powder then is sintering 3h under 700 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous stainless steel metallic diaphragm of 2.5 μ m;
Step 2, the metallic diaphragm of porous stainless steel described in the step 1 being immersed in the electrolyte, is anodic oxidation 30min under the condition of 10V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is the mixed solution of ammonium fluoride, water and ethylene glycol, and the concentration of ammonium fluoride is 0.05M in the mixed solution, and the concentration of water is 0.2M;
Step 3, be that to add concentration be that mass concentration is that stirring obtains the coating liquid that alumina powder concentration is 0.2g/mL in 6% the PVA aqueous solution for the alumina powder of 300nm with particle diameter;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 50min under 400 ℃ of conditions; The coating thickness of said coating liquid is 2.5 μ m;
Step 5, be the porous ceramics filter membrane of 80 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 500nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 10
Present embodiment is identical with embodiment 9, and wherein difference is: used powder is FeCrAl alloyed powder, NiCrAlFe alloyed powder or FeAl alloyed powder; Used oxide powder is titanium dioxide powder or Zirconium oxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 11
Step 1, to select the aperture for use be that the 316L stainless steel porous material of 33 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 50 μ m on matrix surface then is the FeCrAl alloyed powder of 2.5 μ m; The matrix that will be coated with the FeCrAl alloyed powder then is sintering 2h under 1000 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous iron-based alloying metal rete of 2 μ m;
Step 2, porous iron-based alloying metal rete described in the step 1 being immersed in the electrolyte, is anodic oxidation 5min under the condition of 80V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is the mixed solution of ammonium fluoride, water and ethylene glycol, and the concentration of ammonium fluoride is 0.1M in the mixed solution, and the concentration of water is 0.5M;
Step 3, be that to add concentration be that mass concentration is that stirring obtains the coating liquid that titanium dioxide powder concentration is 0.08g/mL in 2% the PVA aqueous solution for the titanium dioxide powder of 5nm with particle diameter;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 40min under 700 ℃ of conditions; The coating thickness of said coating liquid is 0.5 μ m;
Step 5, be the porous ceramics filter membrane of 30 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 10nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 12
Present embodiment is identical with embodiment 11, and wherein difference is: used powder is stainless steel powder, NiCrAlFe alloyed powder or FeAl alloyed powder; Used oxide powder is alumina powder or Zirconium oxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 13
Step 1, to select the aperture for use be that the Titanium porous material of 35 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 10 μ m on matrix surface then is the hydride powder of 3 μ m; The matrix that will be coated with hydride powder then is sintering 3h under 700 ℃ the vacuum condition in temperature, and obtaining the aperture is the POROUS TITANIUM metallic diaphragm of 3 μ m;
Step 2, the metallic diaphragm of POROUS TITANIUM described in the step 1 being immersed in the electrolyte, is anodic oxidation 15min under the condition of 15V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is the mixed aqueous solution of hydrofluoric acid and nitric acid, and the concentration of volume percent of hydrofluoric acid is 0.5% in the mixed aqueous solution, and the concentration of volume percent of nitric acid is 1.5%;
Step 3, be that to add concentration be that mass concentration is that stirring obtains the coating liquid that alumina powder concentration is 0.15g/mL in 5% the PVA aqueous solution for the alumina powder of 20nm with particle diameter;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 30min under 700 ℃ of conditions; The coating thickness of said coating liquid is 2 μ m;
Step 5, be the porous ceramics filter membrane of 50 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 25nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 14
Present embodiment is identical with embodiment 13, and wherein difference is: used powder is the titanium alloy powder; Used oxide powder is Zirconium oxide powder or titanium dioxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 15
Step 1, to select the aperture for use be that the porous Ni-base alloy material of 10 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 8 μ m on matrix surface then is the NiCrAlFe alloyed powder of 1 μ m; The matrix that will be coated with the NiCrAlFe alloyed powder then is sintering 2h under 800 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous nickel metal rete of 0.8 μ m;
Step 2, the rete of porous nickel metal described in the step 1 being immersed in the electrolyte, is anodic oxidation 5min under the condition of 20V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is that concentration is the aqueous solution of nitric acid of 0.4M;
Step 3, be that to add concentration be the TiO of 0.6M for the titanium dioxide powder of 300nm with particle diameter
2In the colloidal sol, stirring obtains the coating liquid that titanium dioxide powder concentration is 0.1g/mL;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 20min under 800 ℃ of conditions; The coating thickness of said coating liquid is 0.2 μ m;
Step 5, be the porous ceramics filter membrane of 2 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 360nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 16
Present embodiment is identical with embodiment 15, and wherein difference is: used powder is nickel powder or nickel alloy powder; Used oxide powder is alumina powder or Zirconium oxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 17
Step 1, to select the aperture for use be that the porous Ni-base alloy material of 20 μ m is a matrix; Matrix is cleaned up the back oven dry; The granularity that even coating one layer thickness is 10 μ m on matrix surface then is the nickel powder of 2 μ m; The matrix that will be coated with nickel powder then is sintering 3h under 700 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous nickel metal rete of 1.5 μ m;
Step 2, the rete of porous nickel metal described in the step 1 being immersed in the electrolyte, is anodic oxidation 30min under the condition of 10V at oxidation voltage, obtains oxidate nano loose structure transition zone; Said electrolyte is that concentration is the aqueous solution of nitric acid of 0.6M;
Step 3, be that to add mass concentration be that stirring obtains the coating liquid that Zirconium oxide powder concentration is 0.2g/mL in 8% the PVA colloidal sol for the Zirconium oxide powder of 100nm with particle diameter;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 10min under 900 ℃ of conditions; The coating thickness of said coating liquid is 2 μ m;
Step 5, be the porous ceramics filter membrane of 20 μ m to the product repeating step four behind the sintering in the step 4 until obtaining thickness, obtaining the aperture is the compound filter membrane of ceramic on metal of 120nm.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 18
Present embodiment is identical with embodiment 17, and wherein difference is: used powder is NiCrAlFe alloyed powder or other nickel alloy powder; Used oxide powder is alumina powder or titanium dioxide powder.
The compound filter membrane processability of ceramic on metal of present embodiment preparation is good; Can process the filtration of different shape and use device; Have good resistance to chemical attack simultaneously, compressive resistance is high, and repeat performance is stable; Can be used as micro-nano size filtered and the critical component that separates, can be widely used in fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
The above; It only is preferred embodiment of the present invention; Be not that the present invention is done any restriction, every according to inventing technical spirit to any simple modification, change and equivalent structure variation that above embodiment did, all still belong in the protection domain of technical scheme of the present invention.
Claims (5)
1. the preparation method of the compound filter membrane of ceramic on metal is characterized in that, this method may further comprise the steps:
Step 1, to select the aperture for use be that the metal polyporous material of 5 μ m～35 μ m is a matrix; On matrix surface, evenly applying granularity is the powder of 1 μ m～5 μ m; The matrix that will be coated with powder then is sintering 1h～3h under 700 ℃～1200 ℃ the vacuum condition in temperature, and obtaining the aperture is the porous metals rete of 0.8 μ m～2.5 μ m; Said powder is hydride powder, titanium alloy powder, nickel powder, nickel alloy powder, stainless steel powder, FeCrAl alloyed powder, NiCrAlFe alloyed powder or FeAl alloyed powder, and the coating thickness of powder is 6 μ m～80 μ m;
Step 2, the rete of porous metals described in the step 1 is immersed anodic oxidation 5min～30min in the electrolyte, obtain oxidate nano loose structure transition zone;
Step 3, be that the oxide powder of 5nm～300nm adds in the dispersant with particle diameter, stirring obtains the coating liquid that oxide powder concentration is 0.05g/mL～0.2g/mL; Said oxide powder is titanium dioxide powder, alumina powder or Zirconium oxide powder; Said dispersant is TiO
2The colloidal sol or the PVA aqueous solution;
Step 4, coating liquid described in the step 3 is coated to described in the step 2 on the transition zone oven dry back sintering 10min～50min under 400 ℃～900 ℃ conditions; The coating thickness of said coating liquid is 0.15 μ m～2.5 μ m;
Step 5, be the porous ceramics filter membrane of 2 μ m～80 μ m until obtaining thickness, obtain the compound filter membrane of ceramic on metal the product repeating step four behind the sintering in the step 4.
2. the preparation method of the compound filter membrane of a kind of ceramic on metal according to claim 1; It is characterized in that; When powder described in the step 1 was hydride powder or titanium alloy powder, electrolyte described in the step 2 was the mixed aqueous solution of hydrofluoric acid and nitric acid, and said oxidation voltage is 5V～20V; The concentration of volume percent of hydrofluoric acid is 0.3%～1.1% in the said mixed aqueous solution, and the concentration of volume percent of nitric acid is 1.0%～2.0%.
3. the preparation method of the compound filter membrane of a kind of ceramic on metal according to claim 1; It is characterized in that; When powder described in the step 1 is stainless steel powder, FeCrAl alloyed powder, NiCrAlFe alloyed powder or FeAl alloyed powder; Electrolyte described in the step 2 is the mixed solution of ammonium fluoride, water and ethylene glycol, and said oxidation voltage is 10V～80V; The concentration of ammonium fluoride is 0.05M～0.15M in the said mixed solution, and the concentration of water is 0.2M～1.0M.
4. the preparation method of the compound filter membrane of a kind of ceramic on metal according to claim 1; It is characterized in that; When powder described in the step 1 is nickel powder, NiCrAlFe alloyed powder or nickel alloy powder; Electrolyte described in the step 2 is that concentration is the aqueous solution of nitric acid of 0.1M～0.6M, and said oxidation voltage is 1V～20V.
5. the preparation method of the compound filter membrane of a kind of ceramic on metal according to claim 1 is characterized in that TiO described in the step 3
2The concentration of colloidal sol is 0.3M～0.7M, and the mass concentration of the said PVA aqueous solution is 2%～10%.
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