CN115847867A - Preparation method of dry-pressed co-fired metal-based ceramic composite membrane - Google Patents
Preparation method of dry-pressed co-fired metal-based ceramic composite membrane Download PDFInfo
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- CN115847867A CN115847867A CN202211631390.3A CN202211631390A CN115847867A CN 115847867 A CN115847867 A CN 115847867A CN 202211631390 A CN202211631390 A CN 202211631390A CN 115847867 A CN115847867 A CN 115847867A
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Abstract
The invention belongs to the field of preparation of membrane materials, and particularly relates to a preparation method of a dry-pressed co-fired metal-based ceramic composite membrane. The invention mixes alloy powder and ceramic powder to prepare metal matrix blank by compression molding, then combines pressure molding technology and screen technology, firstly uniformly distributes the ceramic powder on the surface of the metal matrix blank by the screen technology, then presses the ceramic powder into the pores on the surface layer of the metal matrix blank by pressure, forms a flat and uniform coating on the surface of the metal matrix, and finally prepares the metal matrix ceramic composite membrane by heat treatment. The invention simplifies the preparation process, shortens the film forming time, and has repeatability, simple operation and controllable conditions.
Description
Technical Field
The invention belongs to the field of preparation of membrane materials, and particularly relates to a preparation method of a dry-pressed co-fired metal-based ceramic composite membrane.
Background
The membrane filtration separation technology occupies an important position in filtration separation processes such as gas-solid separation, liquid separation, separation and purification of chemical products and biochemical products, and is widely applied to the fields of chemical flue gas dust removal, industrial sewage treatment, metallurgy, petrifaction, new energy, biomedicine and the like. The inorganic membrane material comprises a metal membrane and a ceramic membrane, and the ceramic membrane has the advantages of high temperature resistance, high pressure resistance, corrosion resistance and the like, but has low mechanical strength, is easy to break and is not easy to connect. The metal film has high mechanical strength, good weldability and sealing performance, but the pore diameter is generally difficult to control, and the usability is limited. In order to realize the advantage complementation of the metal film and the ceramic film and meet the requirement of industrial special working conditions on high-performance film materials, researchers develop metal-based ceramic composite film materials.
The metal-based ceramic composite membrane material is a composite material with porous metal as a matrix and a ceramic coating as a membrane layer, combines the advantages of a metal membrane and a ceramic membrane, and has the advantages of good machining performance, welding performance and sealing performance, good chemical stability, high temperature resistance, high pressure resistance, long service life, environmental protection and easy cleaning. At present, the method is widely applied to the industrial fields of aerospace, aviation, national defense, chemical machinery and the like. However, due to the difference in material quality between the metal substrate and the ceramic coating, and the difference in thermo-physical properties between the metal substrate and the ceramic coating, the film layer is prone to cracking and falling off during the sintering process, and the yield in the actual production process is low.
In order to solve the above problems, in patent CN114618316A, titanium powder and stainless steel powder are mixed to prepare a metal matrix, and a ceramic film layer is composited on the surface of the metal matrix to prepare the metal matrix ceramic composite film. In the technology, a certain amount of active metal titanium is added, so that the difference of thermal expansion coefficients between the metal substrate and the ceramic film layer is reduced, and the tendency of cracking and stripping in the film layer preparation process is reduced. And the combination of the metal matrix and the ceramic film layer is molecular force combination, so that the combination strength is low. Patent CN102500245A uniformly coats powder on the surface of a porous metal matrix, increases the bonding strength of the metal matrix and a ceramic coating, obtains a transition layer through anodic oxidation of electrolyte, and repeatedly coats coating liquid until obtaining a metal matrix ceramic composite membrane with the thickness of 2-80 mu m. The method can improve the binding force between the metal substrate and the ceramic film, but has the problem of film uniformity, and the film thickness is difficult to control and easy to crack when the coating liquid is repeatedly coated. Patent CN110252157A discloses a preparation method of a reinforced metal composite ceramic membrane, which comprises coating a layer of elemental metal or alloy powder on the surface of a metal substrate, sintering with composite or mixed ceramic powder to form a transition layer, sintering a precision layer with alkali metal oxide doped ceramic powder, and preparing a metal-based porous ceramic membrane through ion exchange of molten salt on the outer side. Although the method can improve the bonding strength of the metal matrix and the ceramic film layer, the process is complicated, and the molten salt ion exchange outside the precision layer is difficult to completely replace, so that the corrosion resistance of the film layer is influenced. In a word, the prior art has the problems of complex operation, higher cost, difficult industrialization and the like.
Disclosure of Invention
In order to improve the defects of the existing metal-based ceramic composite membrane preparation technology, the invention combines the prior art technology and improves the prior art technology, thereby improving the binding force of the metal matrix and the ceramic membrane layer, simplifying the preparation technology and reducing the production cost.
The invention aims to provide a simple, effective and low-cost preparation method of a metal-based ceramic composite membrane. According to the invention, the alloy powder and the ceramic powder are mixed, pressed and formed to prepare the metal matrix green body, and the ceramic powder is introduced into the metal matrix, so that the difference of the thermal expansion coefficients of the metal matrix and the ceramic film layer during high-temperature sintering is reduced. And then combining a pressure forming technology and a screen technology, uniformly distributing ceramic powder on the surface of the metal matrix green body by the screen technology, pressing the ceramic powder into pores on the surface layer of the metal matrix green body by using pressure, forming a flat and uniform coating on the surface of the metal matrix, and finally preparing the metal matrix ceramic composite membrane by heat treatment. In the high-temperature sintering process, the alloy powder can be used as a binder and can also provide support for the ceramic film layer.
The technical scheme of the invention is as follows:
a preparation method of a dry-pressed co-fired metal matrix ceramic composite membrane comprises the following steps:
step 1: grinding and mixing the alloy powder and the ceramic powder A with certain particle sizes in proportion uniformly, and pouring the mixture into a mould for pressing and forming;
step 2: taking out the mold base in the step 1, performing semi-demolding, wherein the metal-based ceramic green surface in contact with the mold base faces upwards and the mold is not exposed;
and step 3: mixing and stirring the ceramic powder B and the binder solution uniformly according to a certain proportion, drying and then grinding uniformly to prepare uniformly dispersed membrane-making powder;
and 4, step 4: placing a screen mesh on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a certain mode, placing a protective layer on the film-making powder, finally placing a base into the mold, and performing compression molding to obtain a metal-based ceramic semi-finished film;
and 5: and (4) carrying out heat treatment on the metal-based ceramic semi-finished film obtained in the step (4) under a certain atmosphere condition to prepare the metal-based ceramic composite film.
Preferably, the alloy powder in the step 1 is one of stainless steel, titanium alloy, nickel alloy and NiCrAlFe alloy powder, and the average grain size is 5-300 mu m.
Preferably, the ceramic powder A in the step 1 is zirconia, alumina, titania or yttrium stabilized zirconia, and the average grain diameter is 1-10 μm; the ratio of the alloy powder to the ceramic powder A is 1-3.
Preferably, the compression molding manner in step 1 is die pressing or cold isostatic pressing.
Preferably, in the step 3, the ceramic powder B is: alumina, titanium oxide, zirconium oxide or yttrium oxide, the average grain diameter is 0.1-10 μm; the binder solution is selected from one of polyimide, PVA, PVB, methyl cellulose and sodium carboxymethyl cellulose; the mass fraction of the binder solution is 1% -5%.
Preferably, the ratio of the ceramic powder B to the binder solution in the step 3 is 1-10.
Preferably, the mesh number of the screen in the step 4 is 50-200 meshes. The method for tiling the molding powder on the surface of the metal ceramic green body comprises the following steps: vibrating or reciprocating the screen.
Preferably, the protective layer in the step 4 is one of a polytetrafluoroethylene film, silicone oil paper and glutinous rice paper; the compression molding mode is the same as that in the step 1.
Preferably, the heat treatment operation conditions in the step 5 are sintering at 1000-1500 ℃ under vacuum, reduction and inert atmosphere conditions, and heat preservation is carried out for 1-3 hours.
The invention has the following beneficial effects:
1. the metal matrix ceramic composite membrane is prepared by one-step dry-pressing and co-firing of the metal matrix and the ceramic membrane powder, and has the advantages of simple process, low cost and contribution to industrial production.
2. According to the invention, the alloy powder and the ceramic powder A are mixed in proportion and pressed to form the metal matrix green body, so that the difference of the thermal expansion coefficients of the metal matrix and the ceramic membrane layer material can be reduced, and the combination of the ceramic membrane layer and the metal matrix is facilitated.
3. The ceramic powder B and the binder solution are uniformly mixed, dried and ground to obtain the molding powder, the molding powder is filled in pores and surface defects of a metal matrix green body by pressure, and a flat and uniform coating is formed on the surface of the metal matrix green body.
4. According to the invention, the film-making powder is used for preparing the film layer on the surface of the metal matrix blank under pressure, the film layer is not required to be prepared by film-making liquid coating, the particles of the film layer can be effectively prevented from permeating into the surface of the metal matrix blank, the metal matrix ceramic composite film is prepared by one-step dry pressing and co-firing, the cost is low, and the structure is controllable.
5. The invention combines the pressure forming technology and the screen technology, and directly co-burns the metal matrix green blank and the film-making powder by dry pressing to obtain a complete and uniform metal matrix ceramic composite film. The preparation process is simplified, the film forming time is shortened, the repeatability is high, the operation is simple, and the condition is controllable.
Drawings
FIG. 1 is a SEM image of the surface of a dry-pressed co-fired metal matrix ceramic composite film in example 1.
FIG. 2 is a graph showing the pore size distribution of the dry-pressed co-fired metal matrix ceramic composite film of example 1.
Detailed Description
Example 1
Step 1: grinding and uniformly mixing stainless steel powder with the average particle size of 5 microns and zirconia powder with the average particle size of 2.5 microns according to the proportion of 1: 1, pouring the mixture into a mould, and performing mould pressing and forming;
step 2: taking out the die base in the step 1, performing semi-demolding, wherein the metal matrix ceramic green body surface in contact with the die base faces upwards and does not expose out of the die;
and step 3: uniformly mixing and stirring alumina powder with the average particle size of 0.1 mu m and 5% of PVA binder solution according to the proportion of 10: 1, drying and uniformly grinding to prepare uniformly dispersed membrane-making powder;
and 4, step 4: placing a 200-mesh screen on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a mode of returning to a moving screen, placing silicone oil paper on the film-making powder, finally placing a base into the mold, and performing compression molding to obtain a metal-based ceramic semi-finished film;
and 5: and (4) sintering the metal-based ceramic semi-finished film obtained in the step (4) at 1200 ℃ under the vacuum atmosphere condition, and preserving heat for 2 hours to obtain the dry-pressed co-fired metal-based ceramic composite film.
Example 2
Step 1: grinding and uniformly mixing titanium alloy powder with the average particle size of 25 mu m and alumina powder with the average particle size of 8 mu m according to the proportion of 1.5: 1, and pouring into a mould for cold isostatic pressing;
step 2: taking out the die base in the step 1, performing semi-demolding, wherein the metal matrix ceramic green body surface in contact with the die base faces upwards and does not expose out of the die;
and step 3: mixing titanium oxide powder with the average particle size of 5 microns and a polyimide solution with the mass fraction of 1% according to the proportion of 1: 1, uniformly stirring, drying, and uniformly grinding to obtain uniformly dispersed membrane preparation powder;
and 4, step 4: placing a 150-mesh screen on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a vibration screen mode, putting a polytetrafluoroethylene film on the film-making powder, finally putting a base into the mold, and performing cold isostatic pressing to obtain a metal-based ceramic semi-finished film;
and 5: and (4) sintering the metal-based ceramic semi-finished film obtained in the step (4) at 1300 ℃ under the inert atmosphere condition, and preserving heat for 2.5 hours to obtain the dry-pressed co-fired metal-based ceramic composite film.
Example 3
Step 1: grinding and uniformly mixing NiCrAlFe alloy powder with the average grain size of 300 mu m and titanium oxide powder with the average grain size of 10 mu m according to the proportion of 3: 1, pouring the mixture into a mould, and carrying out mould pressing and forming;
step 2: taking out the mold base in the step 1, performing semi-demolding, wherein the metal-based ceramic green surface in contact with the mold base faces upwards and the mold is not exposed;
and step 3: uniformly mixing and stirring zirconium oxide powder with the average particle size of 10 mu m and a PVB solution with the mass fraction of 1.5% according to the proportion of 5: 1, drying and uniformly grinding to prepare uniformly dispersed film-making powder;
and 4, step 4: placing a 50-mesh screen on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a mode of returning to a moving screen, placing glutinous rice paper on the film-making powder, finally placing a base into the mold, and performing compression molding to obtain a metal-based ceramic semi-finished film;
and 5: and (4) sintering the metal-based ceramic semi-finished film obtained in the step (4) at 1500 ℃ under the reducing atmosphere condition, and preserving heat for 3 hours to obtain the dry-pressed co-fired metal-based ceramic composite film.
Example 4
Step 1: grinding and uniformly mixing nickel alloy powder with the average particle size of 100 mu m and yttrium-stabilized zirconia powder with the average particle size of 1 mu m according to the ratio of 2: 1, pouring the mixture into a mould, and performing mould pressing and forming;
step 2: taking out the mold base in the step 1, performing semi-demolding, wherein the metal-based ceramic green surface in contact with the mold base faces upwards and the mold is not exposed;
and step 3: uniformly mixing and stirring yttrium oxide powder with the average particle size of 1 mu m and a methyl cellulose solution with the mass fraction of 3% according to the proportion of 8: 1, drying, and uniformly grinding to prepare uniformly dispersed film-making powder;
and 4, step 4: placing a 180-mesh screen on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a mode of returning to a moving screen, placing silicone oil paper on the film-making powder, finally placing a base into the mold, and performing compression molding to obtain a metal-based ceramic semi-finished film;
and 5: and (4) sintering the metal-based ceramic semi-finished film obtained in the step (4) at 1000 ℃ under the vacuum atmosphere condition, and preserving heat for 1 h to obtain the dry-pressed co-fired metal-based ceramic composite film.
Example 5
Step 1: grinding and uniformly mixing titanium alloy powder with the average particle size of 80 microns and titanium oxide powder with the average particle size of 2 microns according to the ratio of 2.5: 1, pouring into a mold, and performing cold isostatic pressing;
step 2: taking out the mold base in the step 1, performing semi-demolding, wherein the metal-based ceramic green surface in contact with the mold base faces upwards and the mold is not exposed;
and step 3: uniformly mixing and stirring zirconium oxide powder with the average particle size of 8 mu m and sodium carboxymethyl cellulose solution with the mass fraction of 2.5% according to the proportion of 6: 1, drying and uniformly grinding to prepare uniformly dispersed film-making powder;
and 4, step 4: placing a 80-mesh screen on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a mode of returning to a moving screen, placing sticky rice paper on the film-making powder, finally placing a base into the mold, and performing cold isostatic pressing to form to obtain a metal-based ceramic semi-finished film;
and 5: and (5) sintering the metal-based ceramic semi-finished film obtained in the step (4) at 1400 ℃ under the vacuum atmosphere condition, and preserving heat for 2.5 hours to obtain the dry-pressed co-fired metal-based ceramic composite film.
Claims (9)
1. A preparation method of a dry-pressed co-fired metal-based ceramic composite membrane comprises the following steps:
step 1: grinding and mixing the alloy powder and the ceramic powder A with certain particle sizes in proportion uniformly, and pouring the mixture into a mould for pressing and forming;
and 2, step: taking out the mold base in the step 1, performing semi-demolding, wherein the metal-based ceramic green surface in contact with the mold base faces upwards and the mold is not exposed;
and step 3: mixing and stirring the ceramic powder B and the binder solution uniformly according to a certain proportion, drying and then grinding uniformly to prepare uniformly dispersed membrane-making powder;
and 4, step 4: placing a screen on the semi-demolding metal-based ceramic green body surface mold prepared in the step 2, uniformly paving the film-making powder obtained in the step 3 on the surface of the metal-based ceramic green body in a certain mode, placing a protective layer on the film-making powder, finally placing a base into the mold, and performing compression molding to obtain a metal-based ceramic semi-finished film;
and 5: and (4) carrying out heat treatment on the metal-based ceramic semi-finished film obtained in the step (4) under a certain atmosphere condition to prepare the metal-based ceramic composite film.
2. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the alloy powder in the step 1 is one of stainless steel, titanium alloy, nickel alloy and NiCrAlFe alloy powder, and the average particle size is 5-300 μm.
3. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the ceramic powder A in the step 1 is zirconia, alumina, titania or yttrium-stabilized zirconia, and the average particle size is 1-10 μm; the ratio of the alloy powder to the ceramic powder A is 1-3.
4. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the press forming manner in the step 1 is die pressing or cold isostatic pressing.
5. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the ceramic powder B in the step 3 is: alumina, titanium oxide, zirconium oxide or yttrium oxide, the average grain diameter is 0.1-10 μm; the binder solution is selected from one of polyimide, PVA, PVB, methyl cellulose and sodium carboxymethyl cellulose; the mass fraction of the binder solution is 1% -5%.
6. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the ratio of the ceramic powder B to the binder solution in the step 3 is 1-10.
7. The preparation method of the dry-pressed co-fired metal-based ceramic composite membrane according to claim 1, wherein the mesh number of the screen in the step 4 is 50-200 meshes; the method for tiling the molding powder on the surface of the metal ceramic green body comprises the following steps: vibrating or reciprocating the screen.
8. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the protective layer in the step 4 is one of a polytetrafluoroethylene film, silicone oil paper and glutinous rice paper; the compression molding mode is the same as that in the step 1.
9. The method for preparing the dry-pressed co-fired metal-based ceramic composite film according to claim 1, wherein the heat treatment in the step 5 is sintering at 1000-1500 ℃ under vacuum, reducing and inert atmosphere conditions, and keeping the temperature for 1-3 h.
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