CN102500245B - 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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- CN102500245B CN102500245B CN 201110393344 CN201110393344A CN102500245B CN 102500245 B CN102500245 B CN 102500245B CN 201110393344 CN201110393344 CN 201110393344 CN 201110393344 A CN201110393344 A CN 201110393344A CN 102500245 B CN102500245 B CN 102500245B
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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 a kind of preparation method of metal-base ceramic composite filter membrane.
Background technology
Membrane technology is contemporary new and effective isolation of purified technology, economizes on resources and eco-friendly feature 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, because advantages such as high temperature resistant, corrosion-resistant, resistance to erosion, mechanical strength are large, Stability Analysis of Structures, the deep purifying field in HTHP and corrosive atmosphere shows wide application prospect take metal and pottery as the inorganic material film of representative.
Than ceramic membrane materials, the metal membrane material comprehensive mechanical property is better, can use under higher pressure, and metal film has good heat-conductive characteristic and excellent heat-sinking capability, reduced the thermal stress of membrane module, Effective Raise 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 by 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 for above-mentioned the deficiencies in the prior art, a kind of good processability is provided, compressive resistance is high, and repeat performance is stable, can be used as the micro-nano size and filters preparation method with the metal-base ceramic composite filter membrane of the critical component that separates.The method exists during for metal, Ceramic Composite in conjunction with problem not firmly, by forming a kind of effective transition zone at metallic matrix, then apply at transition zone and obtain the ceramic layer filter membrane, obtain the metallic matrix/Ceramic Composite filter membrane by the transition zone strong bonded, the composite filter membrane aperture of acquisition is 10nm～500nm.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of preparation method of metal-base ceramic composite filter membrane, it is characterized in that, and the method may further comprise the steps:
Step 1, to select the aperture be that the metal polyporous material of 5 μ m～35 μ m is matrix, evenly applying granularity on matrix surface is the powder of 1 μ m～5 μ m, the matrix that then will be coated with powder 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; Described powder is hydride powder, Titanium 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 electrolyte Anodic Oxidation 5min～30min, 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; Described oxide powder is titanium dioxide powder, alumina powder or Zirconium oxide powder; Described dispersant is TiO
2Colloidal 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, after the oven dry under 400 ℃～900 ℃ conditions sintering 10min～50min; The coating thickness of described coating liquid is 0.15 μ m～2.5 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 2 μ m～80 μ m, obtain metal-base ceramic composite filter membrane.
The preparation method of above-mentioned a kind of metal-base ceramic composite filter membrane, when powder described in the step 1 was hydride powder or Titanium Powder, electrolyte described in the step 2 was the mixed aqueous solution of hydrofluoric acid and nitric acid, described oxidation voltage is 5V～20V; The concentration of volume percent of hydrofluoric acid is 0.3%～1.1% in the described mixed aqueous solution, and the concentration of volume percent of nitric acid is 1.0%～2.0%.
The preparation method of above-mentioned a kind of metal-base ceramic composite filter membrane, 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 described oxidation voltage is 10V～80V; The concentration of ammonium fluoride is 0.05M～0.15M in the described mixed solution, and the concentration of water is 0.2M～1.0M.
The preparation method of above-mentioned a kind of metal-base ceramic composite filter membrane, 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 described oxidation voltage is 1V～20V.
The preparation method of above-mentioned a kind of metal-base ceramic composite filter membrane, TiO described in the step 3
2The concentration of colloidal sol is 0.3M～0.7M, and the mass concentration of the described 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 extensive preparation of metal-base ceramic composite filter membrane.
2, the filter membrane processability of the present invention's preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, and compressive resistance is high, and repeat performance is stable, can be used as the micro-nano size and filters and the critical component that separates.
3, metal-base ceramic composite filter membrane of the present invention can be processed, and can weld, and can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
There is not firmly problem of combination when 4, the present invention is directed to metal, Ceramic Composite, by forming a kind of effective transition zone at metallic matrix, then apply at transition zone and obtain the ceramic layer filter membrane, obtain the metallic matrix/Ceramic Composite filter membrane by the transition zone strong bonded, the composite filter membrane aperture of acquisition is 10nm～500nm.
Below by embodiment, technical scheme of the present invention is described in further detail.
The specific embodiment
Embodiment 1
Step 1, to select the aperture be that the Titanium porous material of 35 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 20 μ m on matrix surface is the hydride powder of 2 μ m, the matrix that then will be coated with hydride powder is sintering 1h under 900 ℃ the vacuum condition in temperature, and obtaining the aperture is the Porous titanium rete of 1.5 μ m;
Step 2, the rete 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; Described 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, after the oven dry under 400 ℃ of conditions sintering 50min; The coating thickness of described coating liquid is 0.15 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 2 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 50nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 2
The present embodiment is identical with embodiment 1, and wherein difference is: used powder is Titanium Powder; Used oxide powder is alumina powder or Zirconium oxide powder.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 3
Step 1, to select the aperture be that the 316L stainless steel porous material of 28 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 30 μ m on matrix surface is the stainless steel powder of 1.6 μ m, the matrix that then will be coated with stainless steel powder 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; Described 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, after the oven dry under 900 ℃ of conditions sintering 10min; The coating thickness of described coating liquid is 1 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 15 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 10nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 4
The 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 metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 5
Step 1, to select the aperture be that the porous Ni-base alloy material of 5 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 6 μ m on matrix surface is the nickel powder of 1 μ m, the matrix that then will be coated with nickel powder 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; Described 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, after the oven dry under 800 ℃ of conditions sintering 20min; The coating thickness of described coating liquid is 0.2 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 2 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 360nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 6
The 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 metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 7
Step 1, to select the aperture be that the Titanium porous material of 28 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 10 μ m on matrix surface is the hydride powder of 2 μ m, the matrix that then will be coated with hydride powder is sintering 1h under 1200 ℃ the vacuum condition in temperature, and obtaining the aperture is the Porous titanium rete of 1.5 μ m;
Step 2, the rete 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; Described 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, after the oven dry under 600 ℃ of conditions sintering 30min; The coating thickness of described coating liquid is 2 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 18 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 28nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 8
The present embodiment is identical with embodiment 7, and wherein difference is: used powder is Titanium Powder; Used oxide powder is alumina powder or titanium dioxide powder.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 9
Step 1, to select the aperture be that the 316L stainless steel porous material of 33 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 80 μ m on matrix surface is the stainless steel powder of 5 μ m, the matrix that then will be coated with stainless steel powder 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; Described 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, after the oven dry under 400 ℃ of conditions sintering 50min; The coating thickness of described coating liquid is 2.5 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 80 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 500nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 10
The 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 metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 11
Step 1, to select the aperture be that the 316L stainless steel porous material of 33 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 50 μ m on matrix surface is the FeCrAl alloyed powder of 2.5 μ m, the matrix that then will be coated with the FeCrAl alloyed powder 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; Described 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, after the oven dry under 700 ℃ of conditions sintering 40min; The coating thickness of described coating liquid is 0.5 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 30 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 10nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 12
The 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 metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 13
Step 1, to select the aperture be that the Titanium porous material of 35 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 10 μ m on matrix surface is the hydride powder of 3 μ m, the matrix that then will be coated with hydride powder is sintering 3h under 700 ℃ the vacuum condition in temperature, and obtaining the aperture is the Porous titanium rete of 3 μ m;
Step 2, the rete 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; Described 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, after the oven dry under 700 ℃ of conditions sintering 30min; The coating thickness of described coating liquid is 2 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 50 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 25nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 14
The present embodiment is identical with embodiment 13, and wherein difference is: used powder is Titanium Powder; Used oxide powder is Zirconium oxide powder or titanium dioxide powder.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 15
Step 1, to select the aperture be that the porous Ni-base alloy material of 10 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 8 μ m on matrix surface is the NiCrAlFe alloyed powder of 1 μ m, the matrix that then will be coated with the NiCrAlFe alloyed powder 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; Described 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, after the oven dry under 800 ℃ of conditions sintering 20min; The coating thickness of described coating liquid is 0.2 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 2 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 360nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 16
The 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 metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 17
Step 1, to select the aperture be that the porous Ni-base alloy material of 20 μ m is matrix, matrix is cleaned up post-drying, then the granularity that even coating a layer thickness is 10 μ m on matrix surface is the nickel powder of 2 μ m, the matrix that then will be coated with nickel powder 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; Described 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, after the oven dry under 900 ℃ of conditions sintering 10min; The coating thickness of described coating liquid is 2 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 20 μ m, obtain the metal-base ceramic composite filter membrane that the aperture is 120nm.
The metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the fields such as the energy, machinery, electronics, chemical industry, atomic energy, medical and health.
Embodiment 18
The 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 metal-base ceramic composite filter membrane processability of the present embodiment preparation is good, can make the filtration device of various shapes, has simultaneously good resistance to chemical attack, compressive resistance is high, repeat performance is stable, can be used as the micro-nano size and filter and the critical component that separates, can be widely used in the 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 any simple modification, change and equivalent structure of above embodiment being done according to the invention technical spirit changes, and all still belongs in the protection domain of technical solution of the present invention.
Claims (5)
1. the preparation method of a metal-base ceramic composite filter membrane is characterized in that, the method may further comprise the steps:
Step 1, to select the aperture be that the metal polyporous material of 5 μ m～35 μ m is matrix, evenly applying granularity on matrix surface is the powder of 1 μ m～5 μ m, the matrix that then will be coated with powder 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; Described powder is hydride powder, Titanium 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 electrolyte Anodic Oxidation 5min～30min, 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; Described oxide powder is titanium dioxide powder, alumina powder or Zirconium oxide powder; Described dispersant is TiO
2Colloidal 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, after the oven dry under 400 ℃～900 ℃ conditions sintering 10min～50min; The coating thickness of described coating liquid is 0.15 μ m～2.5 μ m;
Step 5, to the product repeating step four behind the sintering in the step 4 until to obtain thickness be the porous ceramics filter membrane of 2 μ m～80 μ m, obtain metal-base ceramic composite filter membrane.
2. the preparation method of a kind of metal-base ceramic composite filter membrane according to claim 1, it is characterized in that, when powder described in the step 1 was hydride powder or Titanium Powder, electrolyte described in the step 2 was the mixed aqueous solution of hydrofluoric acid and nitric acid, and oxidation voltage is 5V～20V; The concentration of volume percent of hydrofluoric acid is 0.3%～1.1% in the described mixed aqueous solution, and the concentration of volume percent of nitric acid is 1.0%～2.0%.
3. the preparation method of a kind of metal-base ceramic composite filter membrane 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 oxidation voltage is 10V～80V; The concentration of ammonium fluoride is 0.05M～0.15M in the described mixed solution, and the concentration of water is 0.2M～1.0M.
4. the preparation method of a kind of metal-base ceramic composite filter membrane 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 oxidation voltage is 1V～20V.
5. the preparation method of a kind of metal-base ceramic composite filter membrane 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 described PVA aqueous solution is 2%～10%.
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| CN103432828B (en) * | 2013-09-23 | 2015-05-13 | 西北有色金属研究院 | Preparation method of porous metal film |
| CN103464000B (en) * | 2013-09-26 | 2015-04-01 | 西北有色金属研究院 | Preparation method of hydrophobic and oleophobic ZrO2 nanofiltration membrane |
| 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 |
| CN105080365B (en) * | 2015-09-02 | 2017-05-10 | 西安建筑科技大学 | Integrated micro-nano filtering membrane and production method thereof |
| CN108115143B (en) * | 2017-12-22 | 2021-03-09 | 苏州第一元素纳米技术有限公司 | Preparation method of filter device |
| CN108704487A (en) * | 2018-05-25 | 2018-10-26 | 哈尔滨工业大学 | A kind of filter membrane method of modifying based on metal oxide particle |
| CN109267332B (en) * | 2018-08-22 | 2021-01-08 | 至玥腾风科技投资集团有限公司 | Preparation method of metal-based carbon fiber composite material and ceramic |
| CN110252157B (en) * | 2019-07-09 | 2022-04-05 | 湖南中天元环境工程有限公司 | Reinforced metal composite ceramic membrane and preparation method thereof |
| 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 |
| CN110408922A (en) * | 2019-08-29 | 2019-11-05 | 西安石油大学 | A kind of preparation method of gradient composite porous membrane tube |
| CN115445445A (en) * | 2022-10-05 | 2022-12-09 | 南通江森电子科技有限公司 | Method for preparing porous nano metal film |
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