CN114558463A - Preparation method of metal-based porous ceramic composite membrane - Google Patents
Preparation method of metal-based porous ceramic composite membrane Download PDFInfo
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Abstract
The invention provides a preparation method of a metal-based porous ceramic composite membrane, which comprises the following steps: s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of the porous ceramic tube to form a ceramic inner coating; s2, wrapping a metal wire mesh outside the porous metal punching pipe, inserting the porous ceramic pipe into the punching pipe, arranging a connecting piece at one end of the punching pipe, and forming a cavity among the outer wall of the porous ceramic pipe, the inner wall of the wire mesh and the connecting piece; s3, filling metal powder in the cavity, and plugging the other end of the punching tube to form a combined piece; s4, sintering the assembly, forming a ceramic film layer in the ceramic coating, forming a metal film layer by metal powder, and removing the metal wire mesh to obtain the metal-based porous ceramic composite film. The metal wire mesh serves as an outer die, mutual diffusion occurs between the metal powder and the punching pipe at high temperature, and the punching pipe and the wire mesh play a role in positioning the metal powder; only the wire mesh is removed, and the composite membrane with the punched tube has higher mechanical strength and complete membrane layer.
Description
Technical Field
The invention belongs to the technical field of preparation of powder metallurgy porous materials, and particularly relates to a preparation method of a metal-based porous ceramic composite membrane and the metal-based porous ceramic composite membrane.
Background
Membranes used in membrane separation equipment can be classified into two types, namely organic membranes and inorganic membranes according to the materials of the membranes, wherein the inorganic membranes can be classified into ceramic membranes and metal membranes.
The organic film is easy to be corroded by organic solvent, is not resistant to corrosion of strong acid and strong base, is not resistant to temperature and has short service life in the using process; compared with an organic membrane, the ceramic membrane serving as a commonly used membrane material at present has the advantages of good chemical stability, high mechanical strength, high temperature resistance, high separation efficiency and the like. But the ceramic membrane has low thermal conductivity and poor thermal shock resistance, and is easy to break when used at high temperature; the metal film has the advantages of high strength, weldability, corrosion resistance and the like, but the metal film has low filtration precision and cannot be used for separating micro particles. The metal ceramic composite membrane can combine the advantages of ceramic membranes and metal membranes, and becomes a novel membrane material.
The most common method for preparing the metal ceramic composite membrane material is to prepare a ceramic layer on the surface of a porous metal material, such as CN102154675A, CN104437112A, CN107297151A and the like, and prepare a coating on the surface of the porous metal material by adopting the processes of electropulse deposition, spraying and the like, and then obtain the metal ceramic composite membrane material by heat treatment. The quality of the membrane material prepared by the technology is directly related to the aperture and uniformity of the porous metal; the film layer prepared by the substrate adopting the small-aperture porous metal or the polishing treatment has good uniformity, but the bonding degree of the metal surface and the ceramic is limited just because the metal surface is flat or smooth. In patent CN108144457A, in order to improve the bonding force, different mixed coating materials are prepared from metal powder and ceramic powder, and the mixed coating materials are prepared on the surface of the porous metal layer by layer. Although the bonding strength is improved by the method, the process is complex and high in cost, and because the particle sizes of the powder of each coating are different, the sintering shrinkage conditions are different, cracks are easy to generate after sintering, so that the yield is low, and the production cost is high. The CN102836642A and CN103585897A patents adopt a technique of forming metal powder and ceramic powder at one time, and then sintering them by a co-sintering technique to form a high-strength composite film material. The binding force between the metal and the ceramic layer of the membrane material produced by the process is improved, but the uniformity of the membrane layer needs to be improved, and the performance of the membrane material is still in a large gap with that of the ceramic membrane material.
In order to further improve the performance of the composite membrane, patent CN111229058B discloses a preparation process of a ceramic composite membrane with a metal protective layer, which comprises a ceramic membrane, a rigid outer mold and an end enclosure. The ceramic membrane protective layer is prepared and put into a mould consisting of a ceramic membrane, a high-temperature-resistant rigid outer mould and an end enclosure, the ceramic membrane protective layer is sintered at high temperature in vacuum or reducing atmosphere, the outer mould is removed to form the ceramic composite membrane material with the metal protective layer, and the method can obtain the high strength of metal while ensuring the performance of the ceramic membrane layer. However, in this method, if a metal outer mold is used, the metal powder is easily sintered together by the mold, and the mold is difficult to remove; the ceramic mould is adopted, powder sintering shrinkage occurs in the sintering process, axial tensile stress can be generated, the metal film layer is easy to crack, effective protection effect on the ceramic film cannot be generated, internal stress can be generated, and the risk of ceramic tube breakage is easy to occur; even if the two problems do not occur, the mold can generate creep deformation under the high-temperature condition, the mold can not be reused, and the production cost is high.
Patent CN110899703A discloses a method for preparing a high porosity metal film, which is to fill in metal, and etch off the metal mold by acid solution after sintering to obtain the metal film, although the method is suitable for preparing the metal film, in order to improve the strength of the mold, the wall thickness of the metal outer mold is large, and due to the tightness of the structure, the corrosion will start from the outer layer of the outer mold and the inner side of the inner mold, if a complete metal film is obtained, the mold will need to be completely corroded, and this will necessitate a large amount of acid for corrosion.
In view of the above problems, there is a need for a method for preparing a composite film with simple process and low cost and a composite film with high strength.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a metal-based porous ceramic composite membrane, which is simple in process and cost-saving, has high strength, can be directly welded and connected, has high membrane layer precision and good performance, and is completely suitable for separation processes under severe systems such as high temperature, high pressure and high viscosity in the field of petrochemical industry.
The invention aims to provide a preparation method of a metal-based porous ceramic composite membrane, which comprises the following steps:
s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of the porous ceramic tube to form a ceramic inner coating, thereby obtaining the porous ceramic tube with the ceramic inner coating;
s2, preparing a porous metal punching pipe, wrapping a metal wire mesh outside the porous metal punching pipe, inserting the porous ceramic pipe with a ceramic inner coating into the porous metal punching pipe, arranging an annular connecting piece at one end of the porous metal punching pipe, and forming a cavity among the outer wall of the porous ceramic pipe, the inner wall of the metal wire mesh and the annular connecting piece;
s3, filling metal powder into the cavity formed in the step S2, and arranging another annular connecting piece at the other end of the porous metal punching tube for plugging so as to form an assembly;
s4, sintering the assembly in a high-temperature furnace in vacuum or inert atmosphere, forming a ceramic film layer in the ceramic inner coating, forming the metal film layer by the metal powder, and removing the metal wire mesh to obtain the metal-based porous ceramic composite film.
Specifically, the metal powder is made of stainless steel or titanium, and the particle size of the metal powder is 5-200 microns.
Specifically, the thickness of the metal film layer is 0.2-5 mm. The thickness of the metal film layer refers to the thickness of the sintered metal powder between the punching tube and the ceramic tube, and does not include the thickness of the punching tube.
Specifically, the aperture range of the ceramic film layer is 0.01-0.5 μm, and the thickness is 2-200 μm.
Specifically, the porous ceramic tube is a single-channel or multi-channel tube, the average pore diameter of multiple pores on the tube wall is 0.05-5 μm, the outer diameter of the single-channel porous ceramic tube is 4-50 mm, and the wall thickness is 0.2-2 mm; the outer diameter of the multi-channel porous ceramic tube is 4-50 mm, and the opening area of the cross section accounts for 35-75%. The process mainly relies on the metal film layer to provide the strength and the weldability, so the wall thickness of the porous ceramic tube is smaller than that of the conventional ceramic membrane, and the thickness of the single-channel porous ceramic tube can be reduced by over 75 percent (for example, the wall thickness of the conventional porous ceramic tube is 2 mm and can be reduced to be less than 0.5 mm). The proportion of the open area of the cross section of the current commercial multi-channel porous ceramic membrane tube is 30%, and the proportion of the open area of the cross section can be increased to 75% by reducing the hole spacing.
Specifically, the annular connecting piece is made of ceramic or metal, the sintering temperature is 700-1350 ℃, and the heat preservation time is 0.5-5 h.
Specifically, the mesh number of the meshes of the metal wire mesh is 80-1000 meshes. The wire mesh is provided for the purpose of preventing the metal powder from flowing out of the holes of the perforated metal pipe.
Specifically, the material of the porous metal punching pipe is the same as that of the metal powder, and is stainless steel or titanium, so that the porous metal punching pipe is favorably connected with the porous metal punching pipe in a sintering manner.
Specifically, the inner diameter of the porous metal punching pipe is 5-60 mm, the wall thickness is 0.5-3 mm, and the pore diameter of a plurality of pores on the pipe wall is 0.3-5 mm; the aperture of the porous metal punching pipe is far larger than the particle size of the metal powder, so that the metal powder can smoothly exist in the pore canal of the porous metal punching pipe and can generate intermetallic diffusion with the porous metal punching pipe in the sintering process to realize sintering.
It is known that sintering shrinkage occurs during sintering of metal powder, and it has been found through the above sintering experiment that the position of the metal powder is kept relatively fixed by the above sintering process, so that the porosity under loose packing condition can be maintained, and the metal film layer of the composite film material has better permeability. The invention overcomes the defect of high cost of the external mold used in the prior art, improves the mechanical strength of the composite film by introducing the punching tube, provides a new preparation process, and has the following advantages:
1. according to the invention, the metal wire mesh is wrapped outside the porous metal punching pipe and serves as an outer mold, mutual diffusion occurs between metal powder and the porous metal punching pipe under a high-temperature condition, and the porous metal punching pipe and the metal wire mesh both play a good positioning role on the metal powder, so that a uniform metal film layer is favorably formed; only the metal wire mesh is removed finally, and the composite membrane with the porous metal punching tube has higher mechanical strength and complete membrane layer;
2. the method has the advantages that an outermost layer die in the prior art is not needed, the process is simple, the co-firing of the ceramic film layer and the metal film layer is realized through the co-firing technology, and the cost is saved.
3. The thickness of the metal film layer is replaced by the porous metal punching pipe, the strength of the porous metal punching pipe is higher under the same thickness in the aspect of strength, and the cost of the porous metal punching pipe is more advantageous than the cost of metal powder in the aspect of raw material cost.
Drawings
FIG. 1 is a cross-sectional view of a metal-based porous ceramic composite membrane according to example 1;
FIG. 2 is a side view of a metal-based porous ceramic composite membrane of example 1;
FIG. 3 is a side view of the ceramic film after multiple thermal shock tests of comparative example 3;
FIG. 4 is a side view of the sintered cermet composite membrane of comparative example 4;
wherein, 1-wire mesh; 2-punching a porous metal hole punching pipe; 3-a porous ceramic tube; 4-a ceramic membrane layer; 5-metal film layer.
Detailed Description
In order to solve the above problems in the prior art, it is urgent to develop a method for preparing a metal-ceramic composite membrane with simple process and low cost, and it is desired to obtain a metal-based porous ceramic composite membrane with high strength and complete membrane layer. The invention provides a preparation method of a metal-based porous ceramic composite membrane, which comprises the following steps:
s1, obtaining a suspension containing ceramic powder (generally prepared by ceramic powder, a binder, a dispersant and a solvent in proportion; the suspension containing ceramic powder can be prepared by adopting a formula in the prior art); coating the suspension on the inner surface of a porous ceramic tube 3 (a single-channel or multi-channel porous ceramic tube 3 has a porous average pore diameter of 0.05-5 mu m on the tube wall, and has an outer diameter of 4-50 mm and a wall thickness of 0.2-2 mm; and has an outer diameter of 4-50 mm and a cross-sectional opening area of 35-75%) to form a ceramic inner coating, thereby obtaining the porous ceramic tube 3 with the ceramic inner coating;
s2, preparing a porous metal punching tube 2 (made of stainless steel or titanium, the inner diameter of the porous metal punching tube 2 is 5-60 mm, the wall thickness of the porous metal punching tube 2 is 0.5-3 mm, the pore diameter of a plurality of pores on the tube wall of the porous metal punching tube 2 is 0.3-5 mm), wrapping a metal wire mesh 1 outside the porous metal punching tube 2 (made of stainless steel or titanium, the mesh number of the meshes of the metal wire mesh 1 is 80-1000 meshes), plugging the porous ceramic tube 3 with a ceramic inner coating into the porous metal punching tube 2, arranging an annular connecting piece (made of ceramic or metal) at one end of the porous metal punching tube 2, and forming a cavity among the outer wall of the porous ceramic tube 3, the inner wall of the metal wire mesh 1 and the annular connecting piece;
s3, filling metal powder (made of stainless steel or titanium and having a particle size of 5-200 μm) into the cavity formed in the step S2, and arranging another annular connecting piece at the other end of the porous metal punching tube 2 for plugging so as to form an assembly;
s4, placing the assembly in a high-temperature furnace, sintering in vacuum or inert atmosphere (the sintering temperature is 700-1350 ℃, and the heat preservation time is 0.5-5 h), forming a ceramic film layer 4 (the aperture range is 0.01-0.5 mu m, the thickness is 2-200 mu m) in the ceramic inner coating layer, forming the metal film layer 5 (the thickness is 0.2-5 mm) by using metal powder, and removing the metal wire mesh 1 to obtain the metal-based porous ceramic composite film.
As shown in the cross-sectional view of fig. 1, the multi-channel, i.e., ceramic substrate, has a plurality of flow channels therein, similar to the honeycomb coal, which can increase the flow area.
The porous ceramic tube 3 in the present invention has a single-layer or multi-layer structure. The process of the present invention relies primarily on the metal film layer to provide strength and weldability characteristics so that the wall thickness of the porous ceramic tube 3 can be made smaller than that of conventional ceramic membranes.
The annular connecting piece is made of ceramic or metal. When the annular connecting piece is made of ceramic, high-temperature-resistant ceramic needs to be selected to ensure that the thickness of the annular connecting piece and the thickness of the metal powder layer are kept uniform; when the annular connecting piece is made of metal, the annular connecting piece made of the same or similar metal material as the metal powder needs to be selected and used, and can be integrally sintered with the metal powder, so that the annular connecting piece can be conveniently welded and connected with other metal pieces at a later stage.
The high-temperature sintering temperature in the present invention is related to the particle size of the metal powder. Generally, the sintering temperature of the metal powder having a larger particle size is higher than that of the metal powder having a smaller particle size, and the holding time is longer. If the metal powder with small particle size is sintered at a high temperature, it is too dense, thereby affecting the filtering effect.
And in the sintering process, the metal powder and the porous metal punched pipe 2 are subjected to intermetallic diffusion to realize sintering. The aperture of the porous metal punching tube 2 is generally larger, and basically larger than 0.3 mm, while the metal powder is smaller, and if the metal powder with the average particle size of 5-200 mu m is selected in the application, the metal powder can leak out from the porous metal punching tube 2 and cannot be formed. In order to prevent the metal powder from flowing out of the holes of the perforated metal pipe 2, the perforated metal pipe 2 is externally coated with a wire mesh 1. The invention can also realize the wrapping of the porous metal punching pipe 2 by wrapping the multi-layer metal wire mesh 1 according to the actual requirement.
It is known that sintering shrinkage occurs during sintering of metal powder, and it has been found through the above sintering experiment that the position of the metal powder can be kept relatively fixed by the above sintering process, so that the porosity under loose packing condition can be maintained, and the metal film layer of the composite film material has better permeability.
The invention also provides a metal-based porous ceramic composite membrane prepared by the preparation method.
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions not noted are conventional conditions in the industry.
Example 1
The embodiment provides a preparation method of a metal-based porous ceramic composite membrane, which comprises the following steps:
s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of a porous ceramic tube 3 (19 channels, the outer diameter is 31 mm, the open pore of the cross section accounts for 59.8%; the average pore diameter of the pores on the wall of the porous ceramic tube 3 is 5 μm) to form a ceramic inner coating, and obtaining the porous ceramic tube 3 with the ceramic inner coating;
s2, preparing a porous metal punching tube 2 (stainless steel, the inner diameter is 36 mm, the wall thickness is 2 mm, and the aperture on the tube wall of the porous metal punching tube 2 is 3 mm), wrapping a metal wire mesh 1 (stainless steel, the mesh number of holes is 200 meshes) outside the porous metal punching tube 2, inserting a porous ceramic tube 3 with a ceramic inner coating into the porous metal punching tube 2, arranging an annular connecting piece (metal) at one end of the porous metal punching tube 2, and forming a cavity among the outer wall of the porous ceramic tube 3, the inner wall of the metal wire mesh 1 and the annular connecting piece;
s3, filling metal powder (stainless steel, the grain diameter is 100 mu m) into the cavity formed in the step S2, and arranging another annular connecting piece at the other end of the porous metal punching pipe 2 for plugging so as to form an assembly;
s4, placing the assembly in a high-temperature furnace (the sintering temperature is 1300 ℃) and sintering in vacuum or inert atmosphere (the heat preservation time is 3 h), forming a ceramic film layer 4 (the thickness is 100 mu m and the pore diameter is 0.2 mu m) in the ceramic inner coating, forming a metal film layer 5 (the thickness is 2.5 mm) by metal powder, and removing the metal wire mesh 1 to obtain the metal-based porous ceramic composite film.
Example 2
The embodiment provides a preparation method of a metal-based porous ceramic composite membrane, which comprises the following steps:
s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of a porous ceramic tube 3 (61 channels, the outer diameter is 50 mm, the open pore ratio of the cross section is 73.8 percent, and the average pore diameter of the pores on the tube wall of the porous ceramic tube 3 is 3 mu m) to form a ceramic inner coating, thereby obtaining the porous ceramic tube 3 with the ceramic inner coating;
s2, preparing a porous metal punching tube 2 (stainless steel, the inner diameter is 60 mm, the wall thickness is 2 mm, and the aperture on the tube wall of the porous metal punching tube 2 is 3 mm), wrapping a metal wire mesh 1 (stainless steel, the mesh number of holes is 200) outside the porous metal punching tube 2, inserting a porous ceramic tube 3 with a ceramic inner coating into the porous metal punching tube 2, arranging an annular connecting piece (metal) at one end of the porous metal punching tube 2, and forming a cavity among the outer wall of the porous ceramic tube 3, the inner wall of the metal wire mesh 1 and the annular connecting piece;
s3, filling metal powder (stainless steel, with the grain diameter of 200 μm) into the cavity formed in the step S2, and arranging another annular connecting piece at the other end of the porous metal punching pipe 2 for plugging so as to form an assembly;
s4, placing the assembly in a high-temperature furnace (the sintering temperature is 1350 ℃) and sintering in vacuum or inert atmosphere (the heat preservation time is 5 hours), forming a ceramic film layer 4 (the thickness is 200 mu m and the pore diameter is 0.5 mu m) in the ceramic inner coating, forming a metal film layer 5 (the thickness is 5 mm) by metal powder, and removing the metal wire mesh 1 to obtain the metal-based porous ceramic composite film.
Example 3
The embodiment provides a preparation method of a metal-based porous ceramic composite membrane, which comprises the following steps:
s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of a porous ceramic tube 3 (a single channel, the outer diameter of the tube is 4 mm, the wall thickness of the tube is 0.2 mm, and the average pore diameter of the pores on the wall of the porous ceramic tube 3 is 1 mu m) to form a ceramic inner coating, so as to obtain the porous ceramic tube 3 with the ceramic inner coating;
s2, preparing a porous metal punching tube 2 (made of stainless steel, the inner diameter of the porous metal punching tube is 5 mm, the wall thickness of the porous metal punching tube is 0.5 mm, and the aperture of the tube wall of the porous metal punching tube 2 is 0.3 mm), wrapping a metal wire mesh 1 (made of stainless steel and the mesh number of holes is 300) outside the porous metal punching tube 2, inserting a porous ceramic tube 3 with a ceramic inner coating into the porous metal punching tube 2, arranging an annular connecting piece (metal) at one end part of the porous metal punching tube 2, and forming a cavity among the outer wall of the porous ceramic tube 3, the inner wall of the metal wire mesh 1 and the annular connecting piece;
s3, filling metal powder (stainless steel, the grain diameter is 50 μm) into the cavity formed in the step S2, and arranging another annular connecting piece at the other end of the porous metal punching pipe 2 for plugging so as to form an assembly;
s4, placing the assembly in a high temperature furnace (the sintering temperature is 850 ℃) to sinter in vacuum or inert atmosphere (the heat preservation time is 3 h), forming a ceramic film layer 4 (the thickness is 40 mu m and the aperture is 0.1 mu m) in the ceramic inner coating layer, forming a metal film layer 5 (the thickness is 0.5 mm) in the metal powder, and removing the metal wire mesh 1 to obtain the metal-based porous ceramic composite film.
Example 4
This example provides a method for preparing a metal-based porous ceramic composite membrane, which is substantially the same as in example 1, except that: the percentage of open pores on the cross section is 35 percent, the mesh number of the holes of the metal wire mesh 1 is 800 meshes, the particle size of the metal powder is 20 mu m, the sintering temperature is 800 ℃, the heat preservation time is 2.5 hours, and the average pore size of the prepared ceramic film layer is 0.03 mu m.
Example 5
This example provides a method for preparing a metal-based porous ceramic composite membrane, which is substantially the same as in example 1, except that: the percentage of open pores on the cross section is 45 percent, the mesh number of the holes of the metal wire mesh 1 is 1000 meshes, the particle size of the metal powder is 5 mu m, the sintering temperature is 700 ℃, the heat preservation time is 0.5 h, and the average pore diameter of the prepared ceramic film layer is 0.01 mu m.
Example 6
This example provides a method for preparing a metal-based porous ceramic composite membrane, which is substantially the same as in example 1, except that: the percentage of open pores on the cross section is 60 percent, the mesh number of the holes of the metal wire mesh 1 is 1000 meshes, the particle size of the metal powder is 10 mu m, the sintering temperature is 750 ℃, the heat preservation time is 1 h, and the average pore diameter of the prepared ceramic film layer is 0.05 mu m.
Example 7
This example provides a method for preparing a metal-based porous ceramic composite membrane, which is substantially the same as in example 1, except that: the percentage of open pores on the cross section is 75 percent, the mesh number of the holes of the metal wire mesh 1 is 100 meshes, the particle size of the metal powder is 150 mu m, the sintering temperature is 1300 ℃, the heat preservation time is 5 hours, and the average pore diameter of the prepared ceramic film layer is 0.4 mu m.
Comparative example 1
This comparative example provides a method of preparing a metal-based porous ceramic composite membrane, which is substantially the same as example 1 except that: in S2, the step of adding the wire mesh is not performed, and the metal powder leaks from the holes of the porous metal punched tube, and thus the production of the composite film cannot be completed.
Comparative example 2
This comparative example provides a method of preparing a metal-based porous ceramic composite membrane, which is substantially the same as example 1 except that: in S2, if a porous metal punched tube is not added, the composite film cannot be prepared.
Comparative example 3
This comparative example provides a ceramic membrane preparation method, which is substantially the same as example 1 except that: without the steps of S2 and S3, i.e., without the steps of using the porous metal punched tube, the wire mesh, and adding the metal powder, only the porous ceramic tube 3 having the ceramic membrane layer 4 remains. As shown in fig. 3, the ceramic film prepared in comparative example 3 was broken by the thermal shock resistance test.
Comparative example 4
The comparative example provides a preparation method of a metal-based porous ceramic composite membrane in the prior art, which comprises the following steps:
s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of the porous ceramic tube (same as example 1) to obtain a porous ceramic tube having a ceramic coating;
s2, enabling the porous ceramic tube with the ceramic membrane layer to penetrate through the hollow part of the cylindrical die formed in the step S2, arranging an annular connecting piece at one end of the cylindrical die, and forming a cavity among the outer wall of the porous ceramic tube, the inner wall of the cylindrical die and the annular connecting piece;
s3, filling metal powder into the cavity formed in the step S2 (same as the embodiment 1), and arranging another annular connecting piece at the other end of the cylindrical mold for plugging so as to form an assembly;
s4, sintering the assembly in a sintering furnace in vacuum atmosphere (same as in example 1), forming a ceramic film on the ceramic coating, forming a metal film on the metal powder, removing the cylindrical mold to obtain a metal-based porous ceramic composite film, and cracking the metal film, as shown in fig. 4.
The samples of the above examples 1 to 7 and comparative examples 1 to 4 were subjected to pore size measurement by a bubble point method, porosity measurement by an archimedes principle method, and thermal shock resistance measurement (the method comprises heating the sample to 500 ℃, keeping the temperature for 30 min, then rapidly cooling the sample in cold water, and observing whether cracks or fractures appear on the surface of the sample after a plurality of cycles), and the obtained data are as follows:
comparing examples 1 to 7 with comparative example 1, it can be seen that in comparative example 1, since there is no step of adding a wire mesh, metal powder leaks out of the holes of the porous metal punched tube, and thus the preparation of the composite film cannot be completed.
Comparing examples 1-7 with comparative example 2, we can see that comparative example 2 cannot complete the preparation of the composite membrane because no porous metal punched tube is added.
Comparing examples 1 to 7 with comparative example 3, we can see that comparative example 3 has only a porous ceramic tube due to no addition of metal powder, porous metal punched tube and wire mesh, and comparative example 3 has poor thermal shock resistance, and cracks appear on the surface of the ceramic film layer after 3 cycles of testing.
Comparing examples 1-7 with comparative example 4, we can see that the outermost layer of comparative example 4 is a metal layer, and the surface of the metal film layer has cracks after the porous-metal-free punched pipe is arranged and sintered.
From the results of the above-described tests of examples and comparative examples, it can be seen that:
1. according to the invention, the metal wire mesh is wrapped outside the porous metal punching pipe and serves as an outer mold, mutual diffusion occurs between metal powder and the porous metal punching pipe under a high-temperature condition, and the porous metal punching pipe and the metal wire mesh both play a good positioning role on the metal powder, so that a uniform metal film layer is favorably formed; only the metal wire mesh is removed finally, and the composite membrane with the porous metal punching tube has higher mechanical strength and complete membrane layer;
2. the outermost layer of the die in the prior art is not needed, the process is simple, and the cost is saved;
3. the thickness of the metal film layer is replaced by the porous metal punching pipe, the strength of the porous metal punching pipe is higher under the same thickness in the aspect of strength, and the cost of the porous metal punching pipe is more advantageous than the cost of metal powder in the aspect of raw material cost;
4. the silk screen can be reused, and can be repaired and reused even if the silk screen is damaged after being stripped.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A preparation method of a metal-based porous ceramic composite membrane is characterized by comprising the following steps:
s1, obtaining a suspension containing ceramic powder; coating the suspension on the inner surface of the porous ceramic tube to form a ceramic inner coating, thereby obtaining the porous ceramic tube with the ceramic inner coating;
s2, preparing a porous metal punching pipe, wrapping a metal wire mesh outside the porous metal punching pipe, inserting the porous ceramic pipe with a ceramic inner coating into the porous metal punching pipe, arranging an annular connecting piece at one end of the porous metal punching pipe, and forming a cavity among the outer wall of the porous ceramic pipe, the inner wall of the metal wire mesh and the annular connecting piece;
s3, filling metal powder into the cavity formed in the step S2, and arranging another annular connecting piece at the other end of the porous metal punching tube for plugging so as to form an assembly;
and S4, placing the assembly in a high-temperature furnace to sinter in vacuum or inert atmosphere, forming a ceramic film layer in the ceramic inner coating, forming a metal film layer by using the metal powder, and removing the metal wire mesh to obtain the metal-based porous ceramic composite film.
2. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the metal powder is made of stainless steel or titanium, and the particle size of the metal powder is 5-200 mu m.
3. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the thickness of the metal film layer is 0.2-5 mm.
4. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the ceramic film layer has a pore diameter of 0.01-0.5 μm and a thickness of 2-200 μm.
5. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the porous ceramic tube is a single channel or a plurality of channels, the average pore diameter of a plurality of pores on the tube wall is 0.05-5 mu m, the outer diameter of the single channel porous ceramic tube is 4-50 mm, and the wall thickness is 0.2-2 mm; the outer diameter of the multi-channel porous ceramic tube is 4-50 mm, and the opening area of the cross section accounts for 35-75%.
6. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the annular connecting piece is made of ceramic or metal.
7. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the sintering temperature is 700-1350 ℃, and the heat preservation time is 0.5-5 h.
8. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the mesh number of the meshes of the metal wire mesh is 80-1000 meshes.
9. The method of preparing the metal-based porous ceramic composite membrane of claim 1, wherein: the porous metal punching pipe is made of stainless steel or titanium.
10. The method of preparing a metal-based porous ceramic composite membrane according to claim 1, wherein: the inner diameter of the porous metal punching pipe is 5-60 mm, the wall thickness is 0.5-3 mm, and the pore diameter of the porous metal punching pipe on the pipe wall is 0.3-5 mm.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003105411A (en) * | 2001-09-24 | 2003-04-09 | Advanced Materials Technologies Pte Ltd | Process for manufacturing compound sintered article |
| CN110216277A (en) * | 2019-06-13 | 2019-09-10 | 金堆城钼业股份有限公司 | A kind of preparation method of refractory metal composite pipe |
| CN113290248A (en) * | 2021-05-07 | 2021-08-24 | 南京工业大学 | Preparation method of metal capillary core with multilayer structure |
| CN113432467A (en) * | 2021-08-27 | 2021-09-24 | 南京工业大学苏州传感与纳米产业技术研究院 | Preparation method of metal ceramic composite capillary core |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003105411A (en) * | 2001-09-24 | 2003-04-09 | Advanced Materials Technologies Pte Ltd | Process for manufacturing compound sintered article |
| CN110216277A (en) * | 2019-06-13 | 2019-09-10 | 金堆城钼业股份有限公司 | A kind of preparation method of refractory metal composite pipe |
| CN113290248A (en) * | 2021-05-07 | 2021-08-24 | 南京工业大学 | Preparation method of metal capillary core with multilayer structure |
| CN113432467A (en) * | 2021-08-27 | 2021-09-24 | 南京工业大学苏州传感与纳米产业技术研究院 | Preparation method of metal ceramic composite capillary core |
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