CN116920628A - Nanoscale metal filtering membrane and preparation method and application thereof - Google Patents
Nanoscale metal filtering membrane and preparation method and application thereof Download PDFInfo
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- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
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- B01D67/0039—Inorganic membrane manufacture
- B01D67/0053—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0058—Inorganic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
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Abstract
The application belongs to the technical field of porous materials, and particularly relates to a nanoscale metal filtering membrane, a preparation method and application thereof, wherein the preparation method comprises the following steps: s1, mixing metal powder, an aqueous solvent and a dispersing agent, and then adding the mixture into a high-speed grinding and dispersing machine for dispersing to obtain suspension slurry, wherein the average particle size of the metal powder is 100 nm-5 mu m; s2, spraying the suspension slurry on a porous support body to form a metal powder coating on the porous support body, and then drying to obtain a nanoscale metal filtering membrane precursor, wherein the porous support body is the same as the metal powder in material; and S3, sintering the precursor of the nano-scale metal filtering membrane under a vacuum condition to obtain the nano-scale metal filtering membrane. The nano-scale metal filter membrane prepared by the application has higher filter precision, can meet the requirement of high filter precision in the separation and filter process, and is widely applied to the fields of semiconductors and the like.
Description
Technical Field
The application belongs to the technical field of porous materials, and particularly relates to a nanoscale metal filtering membrane, a preparation method and application thereof.
Background
Integrated circuit component sizes in semiconductors are typically on the order of microns and even nanometers, and if particles of similar dimensions settle down in an integrated circuit during fabrication of the integrated circuit, the microstructural integrity thereof is compromised, thereby rendering the device useless. One of the current methods for eliminating particle pollution is to add a nanoscale high-precision gas filter at the front end of the inlet of the preparation Cheng Zaiqi to intercept the particles and prevent the particles from depositing on an integrated circuit to form defects.
At present, the research on the filter mainly comprises an organic filter membrane and a ceramic filter membrane, the organic filter membrane is low in strength and not resistant to high temperature, the ceramic filter membrane is brittle and not resistant to thermal shock, therefore, the metal filter membrane is widely applied to the separation and filtration process of various industries, most of the traditional metal filter membranes are in micron level, the filtration precision is low, the requirements of nano-level filtration precision cannot be met, the research on the nano-level metal filter membrane in the prior art is less, and the nano-level metal filter membrane is prepared to meet the requirements of high filtration precision in the separation and filtration process, so that the nano-level metal filter membrane has important significance.
Disclosure of Invention
Aiming at the defects in the prior art, the application aims to provide a nano-scale metal filter membrane, a preparation method and application thereof, and the prepared nano-scale metal filter membrane has higher filter precision, can meet the requirements of high filter precision in the separation and filtration processes, and is widely applied to the fields of semiconductors and the like.
In order to achieve the above purpose, the present application adopts the following technical scheme:
in a first aspect, the present application provides a method for preparing a nano-scale metal filtration membrane, the method comprising the steps of:
s1, preparing suspension slurry: mixing metal powder, an aqueous solvent and a dispersing agent, and adding the mixture into a high-speed grinding and dispersing machine for dispersing to obtain suspension slurry, wherein the average particle size of the metal powder is 100 nm-5 μm (for example, 100nm, 300nm, 500nm, 700nm, 1 μm, 3 μm or 5 μm, etc.), preferably 100nm-1 μm;
s2, preparing a nano-scale metal filtering membrane precursor: spraying the suspension slurry on a porous support body to form a metal powder coating on the porous support body, and then drying to obtain a nanoscale metal filtering membrane precursor, wherein the porous support body is the same as the metal powder in material;
s3, preparing a nano-scale metal filtering membrane: sintering the nano-scale metal filtering membrane precursor under vacuum condition to obtain the nano-scale metal filtering membrane.
According to the application, the dispersing agent is added and the high-speed grinding and dispersing method is matched, so that the metal powder is uniformly dispersed, and the agglomeration phenomenon is avoided, thereby ensuring the filtering precision.
According to the application, the porous support is limited to be the same as the metal powder in material, so that good matching between the film layer and the support can be ensured, stripping does not occur in the drying and sintering processes, and the porous support has good bonding strength.
The nano-scale metal filter membrane prepared by the application has higher filter precision, can meet the requirement of high filter precision in the separation and filter process, and is widely applied to the fields of semiconductors and the like.
In the above method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the metal powder is made of stainless steel, nickel or nickel-based alloy.
In the above method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the aqueous solvent is water or an alcohol solvent, preferably isopropyl alcohol.
In the above method for preparing a nano-scale metal filtration membrane, as a preferred embodiment, the dispersing agent comprises at least one of polyvinyl alcohol, methylcellulose and polyethylene glycol. The addition of the dispersant has an important regulatory effect on the dispersion of the ultrafine powder.
In the above-mentioned method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the mass percentage of the metal powder in the suspension slurry is not less than 5% and not more than 20%, for example, may be 5%, 10%, 15% or 20%, etc., preferably 10%, based on 100% of the total mass of the suspension slurry. If the mass percentage of the metal powder in the suspension slurry is too large, the concentration of the suspension is too large to carry out ultrasonic spraying, and is too small, the concentration of the suspension is low, the drying time is long, and the film forming efficiency is low.
In the above method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the mass ratio of the dispersant to the aqueous solvent is (0.01 to 1): 100 may be, for example, 0.01:100, 0.2:100, 0.4:100, 0.6:100, 0.8:100 or 1:100, and if the dispersant is too much, the viscosity of the suspension is too high to be ultrasonically sprayed, and the dispersing effect is not good.
In the above-mentioned method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the rotation speed of the high-speed grinding dispersion machine is 2000 to 3500r/min (for example, 2000r/min, 2500r/min, 3000r/min, 3500r/min, etc.), preferably 3000r/min.
In the above-mentioned method for producing a nano-scale metal filtration membrane, as a preferred embodiment, in the step S1, the dispersing time is 2h to 4h.
In the above method for preparing a nano-scale metal filtration membrane, as a preferred embodiment, the porous support comprises a sheet-type support or a tube-type support, and for example, the porous support may be one of a sintered metal powder porous material, a sintered metal fiber mat porous material, and a filter tube.
In the above-mentioned method for producing a nano-scale metal filtration membrane, the average pore diameter of the porous support is preferably 5 to 30 μm (for example, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm or 30 μm, etc.), and more preferably 5 to 15 μm.
In the above method for producing a nano-scale metal filtration membrane, the thickness of the porous support may be, for example, 0.3mm, 1mm, 3mm, 5mm, 6mm, or the like, as a preferred embodiment.
In the above method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the porous support is made of stainless steel, nickel or nickel-based alloy.
In the above method for preparing a nano-scale metal filtration membrane, as a preferred embodiment, the spraying is ultrasonic spraying. Because of the specificity of superfine metal powder, the uniformity of a film layer and the thickness of a thin film layer cannot be ensured by traditional tape casting or wet spraying. Compared with the traditional wet spraying, the ultrasonic spraying method has the advantages of high uniformity of the coating, high utilization rate of raw materials, high control precision of the thickness of the coating, thinner thickness of the coating, few splashing, no blockage of a spray head, low maintenance cost and the like.
In the above method for preparing a nano-scale metal filtration membrane, as a preferred embodiment, the ultrasonic nozzle power of the ultrasonic spraying is 1-15w (for example, 1w, 3w, 5w, 7w, 10w, 13w or 15w, etc.), and the flow rate is 1mL/min-20mL/min (for example, 1mL/min, 5mL/min, 8mL/min, 10mL/min, 12mL/min, 16mL/min or 20mL/min, etc.).
In the above-mentioned method for producing a nano-scale metal filtration membrane, as a preferred embodiment, the thickness of the metal powder coating layer is 5 to 100 μm (for example, may be 5 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 80 μm or 100 μm, etc.), preferably 30 to 60 μm. If the coating thickness is too thick, the filtration flux is small, and if the coating thickness is too thin, the filtration accuracy cannot be ensured.
In the above-mentioned method for producing a nano-scale metal filtration membrane, in step S2, the temperature of the drying is 100 to 120 ℃ (for example, 100 ℃, 110 ℃, 120 ℃ or the like) and the time of the drying is 30 to 60 minutes (for example, 30 minutes, 40 minutes, 50 minutes, 60 minutes or the like).
In the above method for producing a nano-scale metal filtration membrane, in a preferred embodiment, in the step S3, the vacuum degree is less than 9X 10 during the sintering -3 And (5) a bracket.
In the above method for producing a nano-scale metal filtration membrane, as a preferred embodiment, in step S3, the sintering includes: heating to 400-500 ℃ at a heating rate of 2-10 ℃/min (such as 2 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min or 10 ℃/min, etc.), such as 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃ or 500 ℃ and the like, preserving heat for 1-2 hours, heating to 600-900 ℃ (such as 600 ℃, 700 ℃, 800 ℃ or 900 ℃ and the like) at a heating rate of 2 ℃/min-10 ℃/min (such as 2 ℃/min, 4 ℃/min, 6 ℃/min, 8 ℃/min or 10 ℃/min, etc.), preserving heat for 2-4 hours, and cooling with a furnace.
According to the application, the heat preservation in the time-division stage is limited, so that the dispersing agent can be volatilized as much as possible in the sintering process, and the dispersing agent is prevented from being remained to influence the performance of the film layer.
In the above method for preparing a nano-scale metal filtration membrane, as a preferred embodiment, in step S2, the number of spraying is a plurality of times, wherein after each spraying is completed, the precursor of the nano-scale metal filtration membrane is sintered under vacuum according to step S3, and then the next spraying is performed. The pore diameter and the permeability are a pair of contradictory performances, and the smaller the pore diameter is, the higher the permeability is, but the contradictory is, compared with the method for performing spraying sintering once only, the embodiment of the application has the advantages that the pore diameters are similar (the filtering precision is close) by adopting multiple spraying and sintering, but the permeability is improved.
In a second aspect, the present application provides a nano-scale metal filtration membrane made by the method of preparation provided in the first aspect. The nano-scale metal filter membrane provided by the application has higher filter precision, and the interception efficiency of impurity particles with the particle diameter of more than 80nm is more than 99.9%.
In the above nano-scale metal filtration membrane, as a preferred embodiment, the nano-scale metal filtration membrane comprises a porous support body having a supporting function and a metal membrane layer having a filtering function provided on the porous support body, wherein the pore diameter of the metal membrane layer is smaller than that of the porous support body, and the smaller the pore diameter of the metal membrane layer is, the higher the filtration accuracy is. The nano-scale metal filter membrane provided by the application is a nano-scale metal filter membrane with a gradient structure, namely, a porous material with the pore size changing along a certain direction, the gradient property endows the gradient porous material with the advantages that the larger filter flux can be ensured on the basis of smaller pore size, the structure and the performance which are not possessed by other porous materials with uniform structures are realized, and the filtering precision and the filtering efficiency can be greatly improved in the filtering and separating processes.
In a third aspect, the present application provides the use of a nano-scale metal filtration membrane according to the second aspect in a two-phase separation of any one of ambient temperature gas/solid, ambient temperature liquid/solid, high temperature gas/solid and high temperature liquid/solid.
Compared with the prior art, the application has the beneficial effects that at least one of the following is included:
(1) The nano-scale metal filter membrane prepared by the application has higher filter precision, has the filter efficiency of more than 99.9 percent for impurity particles with the particle diameter of more than 80nm, can meet the requirement of high filter precision in the separation and filtration process, and is widely applied to the fields of semiconductors, LEDs, photovoltaics and the like.
(2) According to the application, the dispersing agent is added and the high-speed grinding and dispersing method is matched, so that the metal powder is uniformly dispersed, the agglomeration phenomenon is avoided, the dispersing efficiency is high, and the particle size distribution on the prepared metal film layer is uniform; by limiting the porous support to be the same as the metal powder, the good matching between the film layer and the support can be ensured, and the porous support is not peeled off in the drying and sintering processes and has good bonding strength; the heat preservation in the time-division stage of the sintering is limited, so that the binder can be volatilized as much as possible in the sintering process, and the binder is prevented from being remained to influence the performance of the film.
(3) Compared with the traditional wet spraying, the ultrasonic spraying method has the advantages that the uniformity of the coating is high, the raw material utilization rate is high, the thickness control precision of the coating is high, the thickness of the coating is thinner, the thickness of the coating can reach tens of nanometers, the splashing is less, the spray head is not blocked, and the maintenance cost is low.
(4) Compared with the method of spraying and sintering for only one time, the method provided by the embodiment of the application has the advantages that the pore diameters are similar (the filtering precision is close) by adopting multiple spraying and sintering, but the permeability is improved.
(5) The nano-scale metal filter membrane provided by the application is a nano-scale metal filter membrane with a gradient structure, namely, the pore size of the nano-scale metal filter membrane is changed along a certain direction, the gradient property endows the gradient porous material with the advantages that the larger filter flux can be ensured on the basis of smaller pore size, the structure and the performance which are not possessed by other porous materials with uniform structures are realized, and the filtering precision and the filtering efficiency can be greatly improved in the filtering and separating processes; the nano metal film provided by the application can be applied to ultra-high precision filtration in the semiconductor industry, and has better temperature resistance and higher strength compared with a high polymer film, and has higher toughness compared with a ceramic film.
Drawings
FIG. 1 is a TEM image of the surface of a metal membrane layer on a nano-scale metal filtration membrane prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the application and are not to be construed as a specific limitation thereof. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The examples of the present application are implemented on the premise of the technical scheme of the present application, and detailed implementation modes and processes are given, but the protection scope of the present application is not limited to the following examples, in which the process parameters of specific conditions are not noted, and generally according to conventional conditions.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and the range or value should be understood to include values close to the range or value. For numerical ranges, one or more new numerical ranges may be obtained in combination with each other between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point values, and are to be considered as specifically disclosed in the present application.
In the present application, all values relating to the amounts of the components are "parts by weight" throughout unless specified and/or indicated otherwise. The process parameters for the specific conditions not noted in the examples below are generally as usual. The experimental reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the dosage of the experimental reagent is the dosage of the reagent in the conventional experimental operation unless specified otherwise, and the materials used are conventional materials purchased in the market unless specified otherwise.
In a first aspect, the present application provides a method for preparing a nano-scale metal filtration membrane, the method comprising the steps of:
s1, preparing suspension slurry: mixing metal powder, an aqueous solvent and a dispersing agent, adding the mixture into a high-speed grinding and dispersing machine to disperse for 2-4 h to obtain suspension slurry, wherein the average particle size of the metal powder is 100 nm-5 mu m, preferably 100nm-1 mu m, the metal powder is made of stainless steel, nickel or nickel-based alloy, the aqueous solvent is water or alcohol solvent, the dispersing agent comprises at least one of polyvinyl alcohol, methyl cellulose and polyethylene glycol, the mass percentage of the metal powder in the suspension slurry is not less than 5% and not more than 20%, and the mass ratio of the dispersing agent to the aqueous solvent is (0.01-1): 100, the rotating speed of the high-speed grinding dispersion machine is 2000-3500r/min.
S2, preparing a nano-scale metal filtering membrane precursor: spraying the suspension slurry on a porous support body in an ultrasonic spraying mode to form a metal powder coating on the porous support body, and then drying to obtain a nanoscale metal filtering membrane precursor, wherein the porous support body is made of the same material as the metal powder, the porous support body comprises a sheet type support body or a tubular type support body, the average pore diameter of the porous support body is 5-30 mu m, the thickness of the porous support body is 0.3-6 mm, the porous support body is made of stainless steel, nickel or nickel-based alloy, the ultrasonic spraying ultrasonic nozzle has the power of 1-15w, the flow rate of 1-20 mL/min, the thickness of the metal powder coating is 5-100 mu m, the drying temperature is 100-120 ℃, and the drying time is 30-60 min.
S3, preparing a nano-scale metal filtering membrane: the precursor of the nano-scale metal filtering membrane is processed under vacuum degree of less than 9 multiplied by 10 -3 Sintering under vacuum condition to obtain nanometer goldAnd a filter membrane, wherein the sintering comprises: heating to 400-500 ℃ at the heating rate of 2-10 ℃/min, preserving heat for 1-2 h, heating to 600-900 ℃ at the heating rate of 2-10 ℃/min, preserving heat for 2-4 h, and cooling with a furnace.
In the above method for preparing a nano-scale metal filtration membrane, as a preferred embodiment, in step S2, the number of spraying is multiple, wherein after each spraying is completed, the precursor of the nano-scale metal filtration membrane is sintered in segments under vacuum according to step S3, and then the next spraying is performed.
The application mainly aims at the requirement of high-precision filtration of carrier gas in the semiconductor industry, develops a nanoscale metal filter membrane with ultrahigh precision and ultrahigh filtration efficiency, thereby grasping the pretreatment technology of nanoscale raw materials, breaking through the matching design and preparation of the aperture and permeability of the nanoscale metal membrane, meeting the requirement of ultrahigh-purity gas purification in the semiconductor industry, and actually, high-precision filtration products are required in the production processes of LED, photovoltaic, MEMS equipment connection and the like.
At present, most of traditional metal filtering membranes are in a micron level and cannot meet the requirement of nano-scale filtering precision, so that the application mainly solves the technical problems of ultra-high precision metal filtering membrane filtering precision and flux matching and the technical problems of nano-scale powder coating preparation process. The preparation process of the ultra-high precision film layer has the difficulty that in order to obtain higher filtering precision, nano-scale powder is selected as the raw material of the surface film layer, but the ultra-fine metal powder has larger specific surface area and higher specific surface energy and is in a thermodynamically unstable state, and particles are easily coagulated, agglomerated and formed into secondary particles to enlarge the particle size in the processing process, so that the ultra-fine metal powder cannot be directly used and needs to be dispersed. At present, the ways of dispersing ultrafine powder particles are mainly ball milling method, ultrasonic method and the like, but the full dispersion of ultrafine metal particles cannot be realized. The traditional ball milling method has obvious effects of impact, shearing, compression, abrasion and the like on crushing and homogenizing micron-sized and coarser powder, and has limited effects on nano fine powder; the problem with ultrasonic vibration dispersion is that once ultrasonic vibration is stopped, superfine powder still can be agglomerated again, the particle size of particles cannot be further reduced after ultrasonic treatment for a period of time, and the agglomeration of superfine powder can be caused again after ultrasonic treatment is continued. The application adopts a high-speed grinding dispersion and dispersant regulation mode to disperse the superfine metal powder, and aims to uniformly disperse and stabilize the superfine metal powder, so that the dispersion effect is good, the dispersion efficiency is high, and the particle size distribution on the prepared filtering membrane layer is uniform.
The ultra-fine metal powder has small granularity, high surface energy, easy agglomeration, difficult preparation uniformity by adopting the traditional wet spraying and casting process, and low precision control of the thickness of the coating.
In a second aspect, the present application provides a nano-scale metal filtration membrane made by the preparation method provided in the first aspect, the nano-scale metal filtration membrane comprising a porous support for supporting and a metal membrane layer disposed on the porous support for filtering.
In order to improve the filtering precision of the nano-scale metal filtering membrane and simultaneously maintain higher permeability, the nano-scale metal filtering membrane prepared by the application adopts an asymmetric structure, ultrafine metal powder is selected as a membrane layer material, a thin surface membrane layer of the metal filtering membrane mainly plays a role in filtering, a framework layer mainly plays a role in supporting, and various micro-pore structures realize the filtering and purifying of nano-scale particles through multi-action principles such as interception, adsorption and the like.
In a third aspect, the present application provides the use of a nano-scale metal filtration membrane according to the second aspect in a two-phase separation of any one of ambient temperature gas/solid, ambient temperature liquid/solid, high temperature gas/solid and high temperature liquid/solid.
In order to further understand the present application, the nanoscale metal filtration membrane provided by the present application, and the preparation method and use thereof will be described in detail with reference to the following examples, to which the scope of the present application is not limited.
Example 1
The preparation method of the nanoscale metal filtering membrane provided by the embodiment comprises the following steps:
s0, preparing a porous support: and carrying out isostatic compaction on the nickel powder, and then carrying out high-temperature sintering to obtain the porous support body, wherein the porous support body is a nickel powder filter tube, the average pore diameter is 10 mu m, the thickness is 3mm, and the outer diameter is 18mm. The isostatic compaction comprises: filling nickel powder into a mould and uniformly vibrating on a vibrating platform, and then placing the mould into a cold isostatic press for compression molding, wherein the nickel powder has a screening particle size range of-150+250 meshes (capable of passing through a 150-mesh screen but incapable of passing through a 250-mesh screen), the vibrating powder filling time is 60s, the molding pressure is 60MPa, and the pressure maintaining time is 1min; the high temperature sintering comprises: placing the isostatically pressed green blank (tube blank) into a sintering boat, vertically standing the tube blank in the sintering boat to prevent longitudinal bending deformation, and burying flexible restraint material around the tube blank for vacuum high temperature restraint sintering, wherein the vacuum degree is 10 -2 Pa, the sintering process is that the temperature is firstly increased to 450 ℃ from room temperature at the heating rate of 7 ℃/min, the temperature is kept for 1h, then the temperature is increased to 900 ℃ at the heating rate of 15 ℃/min, the temperature is kept for 5h, then the heating is stopped, and the furnace is cooled.
S1, preparing suspension slurry: weighing metal powder, an aqueous solvent and a dispersing agent according to a proportion, stirring the metal powder, the aqueous solvent and the dispersing agent relatively uniformly, pouring the mixture into a high-speed grinding and dispersing machine for dispersing to obtain suspension slurry, wherein the rotating speed of the grinding and dispersing machine is 2000r/min, the dispersing time is 3h, and the aim of uniformly dispersing and stabilizing the metal powder is to obtain nickel powder, and the average particle size of the metal powder is 0.5 mu m; ethanol is selected as the aqueous solvent; the addition of the dispersing agent has an important regulating effect on the dispersion of the metal powder, and the dispersing agent is methyl cellulose; the mass ratio of the dispersing agent to the aqueous solvent is 0.05:100; the mass percent of the metal powder in the suspension slurry was 18% based on 100% of the total mass of the suspension slurry, i.e., the ratio of the mass of the metal powder to the total mass of the dispersant and the aqueous solvent was 18:82.
S2, preparing a nano-scale metal filtering membrane precursor: pouring the uniformly dispersed suspension slurry prepared in the step S1 into an ultrasonic dispersion sample injector of an ultrasonic spraying device, wherein the ultrasonic dispersion sample injector can realize on-line dispersion stirring liquid supply of the suspension slurry, powder sinking is avoided in the spraying process, the suspension slurry is uniformly sprayed on a porous support (nickel powder filter tube) prepared in the step S0 through the ultrasonic spraying device to form a metal powder coating with the thickness of 100 mu m on the outer surface of the porous support, and then the metal powder coating is dried at the temperature of 100 ℃ for 30min to obtain a nanoscale metal filter membrane precursor, the coating thickness is adjusted by adjusting the power of an ultrasonic spray head, the spraying flow and the spraying speed, the power of the ultrasonic spray head is 2w, and the spraying flow is 10mL/min.
S3, preparing a nano-scale metal filtering membrane: the precursor of the nano-scale metal filtering membrane prepared in the step S2 is processed in vacuum degree less than 9 multiplied by 10 -3 The sintering process is that the room temperature is heated to 400 ℃ at the heating rate of 6 ℃/min, the temperature is kept for 2 hours, then the temperature is heated to 600 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 4 hours, and then the nano-scale metal filtering membrane is obtained after cooling along with the furnace.
The nano-scale metal filtering membrane prepared in the embodiment comprises a porous support body with a supporting function and a metal membrane layer with a maximum pore diameter of 0.7 μm, wherein the metal membrane layer is arranged on the outer surface of the porous support body and has a permeability of about 8 x 10 -5 L/(cm 2 ·pa·min)。
Fig. 1 is a TEM image of the surface of a metal membrane layer on a nano-scale metal filtration membrane prepared in this embodiment, and as can be seen from fig. 1, the metal powder on the metal membrane layer has no agglomeration and is uniformly dispersed, so that the pore size is smaller, and the filtration accuracy is ensured.
Example 2
The preparation method of the nanoscale metal filtering membrane provided by the embodiment comprises the following steps:
s0, preparing a porous support: filling 316L stainless steel powder into a mould, uniformly vibrating on a vibrating platform, and then placing the mould into a cold isostatic press for compression molding, wherein the 316L stainless steel powderThe powder sieving granularity range is-50+150 meshes (can pass through a 50-mesh screen but cannot pass through a 150-mesh screen), the vibration powder loading time is 30s, the molding pressure is 150MPa, and the dwell time is 2min; the pressed green body, in this example, a tube blank, is charged into a firing boat, and in order to prevent longitudinal bending deformation of the tube blank, the tube blank is vertically erected in the firing boat and filled with flexible restraints around for vacuum high temperature restrained sintering, wherein the vacuum degree is 10 -2 Pa, the sintering process is that the room temperature is firstly heated to 500 ℃ at a heating rate of 8 ℃/min, the temperature is kept for 1h, the temperature is further heated to 900 ℃ at a heating rate of 7 ℃/min, the temperature is kept for 0.5h, the temperature is further heated to 1250 ℃ at a heating rate of 3 ℃/min, the temperature is kept for 4h, finally, the heating is stopped, the furnace is cooled to 500 ℃, and then N is filled into the furnace 2 The cooling speed is increased until the temperature is below 50 ℃, and a porous support body is obtained, wherein the porous support body is a 316L stainless steel powder filter tube, the average pore diameter of the porous support body is 13 mu m, the thickness of the porous support body is 3mm, and the outer diameter of the porous support body is 60mm.
S1, preparing suspension slurry: weighing metal powder, an aqueous solvent and a dispersing agent according to a proportion, stirring the metal powder, the aqueous solvent and the dispersing agent relatively uniformly, pouring the mixture into a high-speed grinding and dispersing machine for dispersing to obtain suspension slurry, wherein the rotating speed of the grinding and dispersing machine is 3000r/min, the dispersing time is 4h, and the aim of uniformly dispersing and stabilizing the metal powder is to obtain 316L stainless steel powder with an average particle size of 1 mu m; deionized water is selected as the aqueous solvent; the dispersant is polyethylene glycol; the mass ratio of the dispersing agent to the aqueous solvent is 0.5:100; the mass percentage of the metal powder in the suspension slurry was 10% based on 100% of the total mass of the suspension slurry, i.e., the ratio of the mass of the metal powder to the total mass of the dispersant and the aqueous solvent was 10:90.
S2, preparing a nano-scale metal filtering membrane precursor: pouring the uniformly dispersed suspension slurry prepared in the step S1 into an ultrasonic dispersion sample injector of an ultrasonic spraying device, wherein the ultrasonic dispersion sample injector can realize on-line dispersion stirring and liquid supply of the suspension slurry, so as to avoid powder sinking in the spraying process, uniformly spraying the suspension slurry on a porous support prepared in the step S0 through the ultrasonic spraying device to form a metal powder coating with the thickness of 30 mu m on the outer surface of the porous support, and then drying at 120 ℃ for 45min to obtain a nano-scale metal filtering membrane precursor, and adjusting the coating thickness by adjusting the power of an ultrasonic spray head, the spraying flow and the spraying speed, wherein the power of the ultrasonic spray head is 3w, and the spraying flow is 12mL/min.
S3, preparing a nano-scale metal filtering membrane: the precursor of the nano-scale metal filtering membrane prepared in the step S2 is processed in vacuum degree less than 9 multiplied by 10 -3 Sectional sintering is carried out in a vacuum furnace of a support, the sintering process is that the temperature is firstly increased to 450 ℃ from the room temperature at the heating rate of 7 ℃/min, the heat is preserved for 2 hours, then the temperature is increased to 900 ℃ at the heating rate of 4 ℃/min, the heat is preserved for 2 hours, and then the furnace is cooled to the room temperature;
and (3) repeating the sintering process of the step S2 and the step S3 once to obtain the nanoscale metal filtering membrane, wherein the thickness of the membrane layer is 60 mu m.
The nano-scale metal filtering membrane prepared in the embodiment comprises a porous support body with a supporting function and a metal membrane layer which is arranged on the outer surface of the porous support body and has a filtering function, wherein the maximum pore diameter of the metal membrane layer is 1.2 mu m, and the permeability of the nano-scale metal filtering membrane is about 6 x 10 -5 L/(cm 2 ·pa·min)。
The microstructure of the metal film layer on the obtained nano-scale metal filtering film is similar to that of the example 1, and the metal powder on the metal film layer is free from aggregation and uniformly dispersed.
Example 3
The preparation method of the nanoscale metal filtering membrane provided by the embodiment comprises the following steps:
s1, preparing suspension slurry: weighing metal powder (superfine metal powder), an aqueous solvent and a dispersing agent according to a proportion, stirring the metal powder and the aqueous solvent relatively uniformly, pouring the mixture into a high-speed grinding and dispersing machine for dispersing to obtain suspension slurry, wherein the rotating speed of the grinding and dispersing machine is 3500r/min, the dispersing time is 2h, and the aim of uniformly dispersing and stabilizing the metal powder is to obtain a metal powder which is made of 316L stainless steel and has an average particle size of 100nm; the aqueous solvent is isopropanol; the addition of the dispersing agent has an important regulating effect on the dispersion of the metal powder, and the dispersing agent is polyvinyl alcohol; the mass ratio of the dispersing agent to the aqueous solvent is 0.1:100; the mass percentage of the metal powder in the suspension slurry was 15% based on 100% of the total mass of the suspension slurry, i.e., the ratio of the mass of the metal powder to the total mass of the dispersant and the aqueous solvent was 15:85.
S2, preparing a nano-scale metal filtering membrane precursor: the suspension slurry which is uniformly dispersed and prepared in the step S1 is poured into an ultrasonic dispersion sample injector of an ultrasonic spraying device, the ultrasonic dispersion sample injector can realize on-line dispersion stirring and liquid supply of the suspension slurry, powder sinking is avoided in the spraying process, the suspension slurry is uniformly sprayed on a porous support body through the ultrasonic spraying device to form a metal powder coating with the thickness of 30 mu m on one surface of the porous support body, then the metal powder coating is dried at 120 ℃ for 30min to obtain a nanoscale metal filtering membrane precursor, the coating thickness is adjusted by adjusting the power, the spraying flow and the spraying speed (the spraying speed refers to the moving speed of the porous support body relative to ultrasonic spraying equipment), the ultrasonic spraying power is 4w, the spraying flow is 5mL/min, the porous support body is 316L stainless steel metal fiber felt purchased from the market, the thickness of the porous support body is 0.5mm, and the average pore diameter of the porous support body is 8 mu m.
S3, preparing a nano-scale metal filtering membrane: the precursor of the nano-scale metal filtering membrane (the filtering material support coated with the surface filtering membrane) prepared in the step S2 is processed in the vacuum degree of less than 9 multiplied by 10 -3 The sintering process is that the room temperature is heated to 500 ℃ at the heating rate of 8 ℃/min, the temperature is kept for 1h, then the temperature is heated to 700 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 2h, and then the nano-scale metal filtering membrane is obtained after cooling along with the furnace.
The nano-scale metal filter membrane prepared in this example comprises a porous support body with supporting function and a metal membrane layer arranged on one surface of the porous support body with filtering function, wherein the maximum pore diameter of the metal membrane layer is 0.3 μm, and the permeability of the nano-scale metal filter membrane is about 2×10 -5 L/(cm 2 ·pa·min)。
The microstructure of the metal film layer on the obtained nano-scale metal filtering film is similar to that of the example 1, and the metal powder on the metal film layer is free from aggregation and uniformly dispersed.
Comparative example 1
The preparation method of the nano-scale metal filtration membrane provided in this comparative example is basically the same as that of example 3, except that the dispersion is performed by a ball milling method in step S1, specifically comprising the steps of:
s1, preparing suspension slurry: weighing metal powder, an aqueous solvent and a dispersing agent according to a proportion, stirring the metal powder, the aqueous solvent and the dispersing agent relatively uniformly, pouring the mixture into a ball mill for dispersion, controlling the ball-material ratio to be 10:1, controlling the rotating speed of the ball mill to be 120rpm, and mixing the materials for 8 hours to uniformly mix the three components to obtain suspension slurry, wherein the metal powder is made of 316L stainless steel, and the average particle size is 100nm; the aqueous solvent is isopropanol; the addition of the dispersing agent has an important regulating effect on the dispersion of the metal powder, and the dispersing agent is polyvinyl alcohol; the mass ratio of the dispersing agent to the aqueous solvent is 0.1:100; the mass percentage of the metal powder in the suspension slurry was 15% based on 100% of the total mass of the suspension slurry, i.e., the ratio of the mass of the metal powder to the total mass of the dispersant and the aqueous solvent was 15:85.
S2, preparing a nano-scale metal filtering membrane precursor: after the suspension is prepared, the suspension is not uniformly dispersed, has high sedimentation speed, and cannot be sprayed by ultrasonic waves, and is sprayed by using a traditional spraying mode. Spraying the suspension slurry prepared in the step S1 on a porous support by using a spray gun to form a metal powder coating with the thickness of 50-100 mu m (a thinner coating cannot be formed due to low control accuracy of the coating thickness of traditional wet spraying and the thickness uniformity is poor) on one surface of the porous support, drying at 120 ℃ for 30min to obtain a nanoscale metal filtering membrane precursor, adjusting the coating thickness by adjusting the spraying pressure, the spraying flow and the spraying speed, controlling the spraying pressure to be 0.5MPa, the spraying amount to be 72mL/min, wherein the porous support is 316L stainless steel metal fiber felt purchased from the market, the thickness of the porous support is 0.5mm, and the average pore diameter of the porous support is 8 mu m.
S3 is the same as step S3 of example 3.
The nano-scale metal filtering membrane prepared in the comparative example comprises a porous supporting body with a supporting function and a metal membrane layer which is arranged on one surface of the porous supporting body and has a filtering function, and the observation shows that the surface uniformity of the metal membrane layer is poor, particles are agglomerated, the maximum aperture of the metal membrane layer is 8 mu m, and the filtering precision of the nano-scale metal filtering membrane is low.
Comparative example 2
The preparation method of the nano-scale metal filtering membrane provided in the present comparative example is basically the same as that of example 3, except that the conventional spraying method is adopted for spraying in step S2, and specifically includes the following steps:
s1 is the same as in step S1 of example 3.
S2, preparing a nano-scale metal filtering membrane precursor: spraying the suspension slurry prepared in the step S1 on a porous support by using a spray gun to form a metal powder coating with the thickness of 50-100 mu m on one surface of the porous support, drying at 120 ℃ for 30min to obtain a nano-scale metal filtering membrane precursor, regulating the coating thickness by regulating the spraying pressure, the spraying flow and the spraying speed, controlling the spraying pressure to be 0.5MPa, the spraying amount to be 72mL/min, wherein the porous support is a 316L stainless steel metal fiber felt purchased from the market, the thickness of the porous support is 0.5mm, and the average pore diameter of the porous support is 8 mu m.
S3, the same as in the step S3 of the embodiment 3.
The nano-scale metal filter membrane prepared in the comparative example comprises a porous support body with a supporting function and a metal membrane layer arranged on one surface of the porous support body with a filtering function, wherein the maximum pore diameter of the metal membrane layer is 2 mu m, and the permeability of the nano-scale metal filter membrane is about 1 x 10 -5 L/(cm 2 Pa.min), the thickness of the nano-scale metal filtration membrane layer is thick, the thickness is uneven, and the permeability is low.
Comparative example 3
The preparation method of the nano-scale metal filtering membrane provided in the comparative example is basically the same as that of example 2, except that only one spraying is performed, and specifically includes the following steps:
S0-S1 are the same as in steps S0-S1 of example 2.
S2, preparing a nano-scale metal filtering membrane precursor: pouring the uniformly dispersed suspension slurry prepared in the step S1 into an ultrasonic dispersion sample injector of an ultrasonic spraying device, wherein the ultrasonic dispersion sample injector can realize on-line dispersion stirring and liquid supply of the suspension slurry, so as to avoid powder sinking in the spraying process, uniformly spraying the suspension slurry on a porous support prepared in the step S0 through the ultrasonic spraying device to form a metal powder coating with the thickness of 60 mu m on the outer surface of the porous support, and then drying at 120 ℃ for 45min to obtain a nano-scale metal filtering membrane precursor, and adjusting the thickness of the coating by adjusting ultrasonic power, spraying flow and spraying speed, wherein the power of an ultrasonic spray head is 3w, and the spraying flow is 12mL/min.
S3, preparing a nano-scale metal filtering membrane: the precursor of the nano-scale metal filtering membrane prepared in the step S2 is processed in vacuum degree less than 9 multiplied by 10 -3 The sintering process is that the room temperature is heated to 450 ℃ at the heating rate of 7 ℃/min, the temperature is kept for 2 hours, then the temperature is heated to 900 ℃ at the heating rate of 4 ℃/min, the temperature is kept for 2 hours, and then the nano-scale metal filtering membrane is obtained after cooling along with the furnace.
The nano-scale metal filter membrane prepared in the comparative example comprises a porous support body with supporting function and a metal membrane layer arranged on the outer surface of the porous support body with filtering function, wherein the maximum pore diameter of the metal membrane layer is 1.2 mu m, and the permeability of the nano-scale metal filter membrane is about 4 x 10 -5 L/(cm 2 ·pa·min)。
Performance testing
And (3) testing the filtering precision: the metal filtration membranes prepared in each of examples and comparative examples were subjected to a filtration efficiency test according to: GB/T6165-2021 efficiency and resistance of high-efficiency air Filter Performance test method; test instrument, device: an H47-2 thermal type gas mass flowmeter, a T-H120 condensation nucleus particle counter and a T-H27 filter material detection device; dust source for detection: sodium chloride sol (particles most easily penetrating the filtration membrane) having a particle size of 80 nm; the number of particles upstream and downstream was measured with a particle counter, and the filtration efficiency= (1-C 1 /C 2 ) X 100%, where C 1 Represents the number of particles in downstream in units of one, C 2 The number of particles upstream is expressed in units of one. The test results are shown in Table 1.
TABLE 1
At least the following points can be seen from examples 1 to 3 and comparative examples 1 to 3 and Table 1 of the present application:
(1) The nano-scale metal filter membrane prepared in the embodiment 1-3 has the filtration efficiency of 99.99999% on sodium chloride sol with the particle size of 80nm, which shows that the nano-scale metal filter membrane prepared in the application has higher filtration precision.
(2) Comparative example 1 the nano-scale metal filtration membrane prepared in step S1 was dispersed by ball milling, the filtration efficiency was 90%, significantly lower than that of example 3, and the surface uniformity of the metal membrane layer was poor, and particle agglomeration was present, indicating that the present application, by adding the dispersing agent and matching with the high-speed milling dispersion method, uniformly dispersed the metal powder, without agglomeration phenomenon, high dispersion efficiency, improved filtration accuracy and filtration efficiency of the filtration membrane.
(3) Comparative example 2, which uses conventional wet spray to prepare a coating, has lower filtration efficiency, uneven film thickness, thicker film thickness and low permeability of the filter membrane compared with example 3, shows that the application has higher filtration efficiency, high uniformity of the coating thickness, high control accuracy of the coating thickness and thinner coating thickness by using ultrasonic spray.
(4) From comparative example 3 and example 2, it is understood that the filtration accuracy is not lowered when the one-shot spray sintering is adopted, but the permeability of the filtration membrane is lowered, indicating that the embodiment of the present application makes the pore diameters close (filtration accuracy is close) but the permeability is improved by adopting the multiple spray and sintering as compared with the one-shot spray sintering.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the application.
Claims (10)
1. A method for preparing a nano-scale metal filtration membrane, the method comprising the steps of:
s1, preparing suspension slurry: mixing metal powder, an aqueous solvent and a dispersing agent, and then adding the mixture into a high-speed grinding and dispersing machine for dispersing to obtain suspension slurry, wherein the average particle size of the metal powder is 100 nm-5 mu m;
s2, preparing a nano-scale metal filtering membrane precursor: spraying the suspension slurry on a porous support body to form a metal powder coating on the porous support body, and then drying to obtain a nanoscale metal filtering membrane precursor, wherein the porous support body is the same as the metal powder in material;
s3, preparing a nano-scale metal filtering membrane: sintering the nano-scale metal filtering membrane precursor under vacuum condition to obtain the nano-scale metal filtering membrane.
2. The method for preparing a nano-scale metal filtration membrane according to claim 1, wherein the metal powder is made of stainless steel, nickel or nickel-based alloy;
and/or the aqueous solvent is water or an alcohol solvent;
and/or the dispersing agent comprises at least one of polyvinyl alcohol, methyl cellulose and polyethylene glycol;
and/or, the mass percentage of the metal powder in the suspension slurry is not less than 5% and not more than 20% based on 100% of the total mass of the suspension slurry;
and/or the mass ratio of the dispersant to the aqueous solvent is (0.01-1): 100.
3. the method for producing a nano-scale metal filtration membrane according to claim 1, wherein the rotation speed of the high-speed grinding dispersion machine is 2000-3500r/min;
and/or, in step S1, the dispersing time is 2-4 h.
4. The method for producing a nano-scale metal filtration membrane according to claim 1, wherein the porous support comprises a sheet-type support or a tube-type support;
and/or the porous support has an average pore size of 5-30 μm;
and/or the thickness of the porous support is 0.3mm-6mm;
and/or the porous support body is made of stainless steel, nickel or nickel-based alloy.
5. The method for producing a nano-sized metal filtration membrane according to claim 1, wherein the spraying is ultrasonic spraying.
6. The method for preparing a nanofiltration membrane as claimed in claim 5, wherein the ultrasonic spray nozzle has a power of 1-15w and a flow rate of 1-20 mL/min.
7. The method for producing a nano-scale metal filtration membrane according to claim 1, wherein the thickness of the metal powder coating layer is 5 to 100 μm;
and/or in the step S2, the drying temperature is 100-120 ℃, and the drying time is 30-60 min;
and/or, in step S3, the degree of vacuum is < 9×10 during sintering -3 A support;
and/or, in step S3, the sintering comprises: heating to 400-500 ℃ at the heating rate of 2-10 ℃/min, preserving heat for 1-2 h, heating to 600-900 ℃ at the heating rate of 2-10 ℃/min, preserving heat for 2-4 h, and cooling with a furnace.
8. The method for preparing a nano-sized metal filtration membrane according to claim 1, wherein in the step S2, the number of spraying is a plurality of times, wherein after each spraying is completed, the precursor of the nano-sized metal filtration membrane is sintered under vacuum according to the step S3, and then the next spraying is performed.
9. A nanoscale metal filtration membrane, characterized in that it is made by the method of preparation of any one of claims 1-8.
10. Use of a nano-scale metal filtration membrane according to claim 9, wherein the nano-scale metal filtration membrane is used in two-phase separation of any one of a normal temperature gas/solid, a normal temperature liquid/solid, a high temperature gas/solid and a high temperature liquid/solid.
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