CN106693724A - Asymmetric structure in-situ ultrasonic anti-pollution membrane with piezoelectric material as separation layer and preparation method thereof - Google Patents
Asymmetric structure in-situ ultrasonic anti-pollution membrane with piezoelectric material as separation layer and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 76
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims description 38
- 238000002604 ultrasonography Methods 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 28
- 230000005684 electric field Effects 0.000 claims abstract description 27
- 230000010287 polarization Effects 0.000 claims abstract description 27
- 239000004020 conductor Substances 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000006260 foam Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- BOUHOYYXLIKKRM-UHFFFAOYSA-N [Pb].[Nb].[Mn] Chemical compound [Pb].[Nb].[Mn] BOUHOYYXLIKKRM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- 229910002113 barium titanate Inorganic materials 0.000 claims description 5
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 239000007888 film coating Substances 0.000 claims description 2
- 238000009501 film coating Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- -1 metaniobate Chemical compound 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract 1
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- 238000001914 filtration Methods 0.000 description 10
- 238000001471 micro-filtration Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
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- 239000002562 thickening agent Substances 0.000 description 6
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- 239000003344 environmental pollutant Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920002873 Polyethylenimine Polymers 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 239000002178 crystalline material Substances 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0041—Inorganic membrane manufacture by agglomeration of particles in the dry state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2603—Application of an electric field, different from the potential difference across the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to an asymmetric structure in-situ ultrasonic anti-pollution membrane with a piezoelectric material as a separation layer, which is characterized in that a support body is a porous conductive material, and the average pore diameter is 1-20 um; the separation layer is porous piezoelectric ceramic with an average pore diameter of 1-1000 nm. Preparing a separation layer on the surface of a conductive support body by taking a piezoelectric material as a raw material, airing, drying and calcining a wet film, and naturally cooling to prepare an asymmetric structure film; and (4) carrying out high-voltage polarization on the asymmetric membrane to obtain the in-situ ultrasonic anti-pollution membrane with the asymmetric structure. The aperture of the separation membrane prepared by the invention can be regulated and controlled within 1-1000nm so as to meet the requirements of different separation systems; meanwhile, under the action of an electric field, the piezoelectric separation layer can generate in-situ ultrasound in the separation process, and the anti-pollution effect is remarkable.
Description
Technical field
The present invention relates to ultrasound pollution-resistant membrane in situ and preparation method thereof, more particularly to conductive material as supporter, with
Piezoelectric is the unsymmetric structure of separating layer ultrasound pollution-resistant membrane in situ and preparation method thereof.
Background technology
Membrane separation technique applies certain motive force with selective permeable membrane as separating medium by film both sides, makes feed side
Film is passed through, to reach separating-purifying purpose compositional selecting.It has excellent without phase transformation, low energy consumption, high efficiency, process is simple etc.
Point, and inoranic membrane has the advantages that acid-alkali-corrosive-resisting, organic solvent-resistant, high temperature high voltage resistant, therefore should with boundless
Use prospect.However, the general character problem that fouling membrane is membrane separation technique to be faced in actual application, pollutant can be deposited in film
Fouling membrane phenomenon is caused in surface or fenestra road, not only makes Membrane Filtration Flux deep fades, it is also possible to influence film to separator
The cutoff performance of matter, directly affects the economy and reliability of membrane separating process.
Piezoelectric is that a class is under pressure when acting on and the crystalline material of voltage can occurs at two ends, and piezoelectric is through too high
The crystal grain of internal original random orientation can be oriented in applied field direction under DC voltage effect after pressure polarization, and be removed in electric field
The state for keeping both positive and negative polarity separate after pin.Now applying AC field at its two ends can make piezoelectric produce machinery to shake
It is dynamic, the characteristics of according to piezoelectric alternating current can be made to be converted to mechanical oscillation, piezoelectric can be prepared into seperation film, make
Membrane material turns into ultrasound emission source in situ, and mechanical oscillation are produced in separation process, and even fouling membrane is avoided so as to play to alleviate
Effect.
At present, mainly there are Darestani (J Membrane with the report that piezoelectric prepares anti-pollution separation membrane as raw material
Sci, 2013,435：Aperture 226-232) is prepared for as 220nm by raw material of PVDF, and thickness is 123 μm of symmetrical structure PVDF
Organic vibrating membrane；Qiu (J Membrane Sci, 2015,44:120-135) aperture is prepared for by raw material of lead zirconate-titanate ceramic
It is the symmetrical structure PZT electricity Tao Zhendong porcelain films of 365nm.The original position ultrasound film of both symmetrical structures shows good resisting
Pollutant performance, both films are all symmetrical structures, and the film of unsymmetric structure has more preferable permeance property and separating property, because
This prepares the original position ultrasound pollution-resistant membrane with unsymmetric structure has great meaning.
The content of the invention
The technical problems to be solved by the invention are：Existing mechanical oscillation film in situ is symmetrical structure, in order to improve
The separating property and permeance property of mechanical oscillation film are, it is necessary to prepare the mechanical oscillation film in situ of unsymmetric structure；It is thus provided that
Unsymmetric structure ultrasound pollution-resistant membrane in situ with piezoelectric as separating layer, it is former present invention also offers above-mentioned unsymmetric structure
The preparation and application of the ultrasonic pollution-resistant membrane in position, reduce the average pore size of film while ultrasound antifouling property in situ is ensured,
Improve the separation accuracy of film.
The technical scheme is that：With piezoelectric ceramics be raw material porous, electrically conductive supporting body surface preparative separation layer, change
Become piezoelectric particle size so as to adjust film layer pore size.Conductive support can provide mechanical strength higher, while
Electric action can be played as electrode；Piezoelectricity separating layer can improve the separation accuracy of anisotropic membrane, while by after polarization
Possess piezoelectric property, ultrasound in situ can be produced to play anti-pollution under DC Electric Field.
Concrete scheme of the invention is：A kind of unsymmetric structure with piezoelectric as separating layer ultrasound antipollution in situ
Film, it is characterised in that supporter is porous conductive material, average pore size is 1-20um；Separating layer is porous piezoceramics, averagely
Aperture is 1-1000nm.
It is preferred that above-mentioned porous conductive material is porous carbon, porous metals titanium, nickel foam, foam copper, foamed aluminium, stainless steel
Or the one kind in alloy；Supporter porous conductive material is sheet or tubular structure.Unsymmetric structure ultrasound pollution-resistant membrane in situ
Resonant frequency be 20-500kHz.
It is preferred that the material of above-mentioned porous piezoceramics be barium titanate, lead titanates, lead zirconate titanate, zinc oxide, metaniobate,
One kind or its mixture in manganese niobium lead acid, lead zinc niobate or quartz；The number of plies of separating layer is 1-5 layers.
Present invention also offers the preparation method of above-mentioned unsymmetric structure ultrasound pollution-resistant membrane in situ, its specific steps
For：A, porous piezoelectric film is prepared on supporter porous conductive material surface, be warming up to 300-1200 DEG C, calcining shaping in 1-4 hour,
Prepare porous piezoelectric film；The A1-4 porous piezoelectric film layer to prepare more small-bore of B or repeat step；C, by prepare it is many
Pore pressure electrolemma is polarized under high voltage electric field, porous piezoceramics separating layer is possessed piezoelectric property, and unsymmetric structure is obtained
Ultrasound pollution-resistant membrane in situ.
Calcination environment in preferred steps A is the one kind in air atmosphere, argon gas atmosphere, helium atmosphere or nitrogen atmosphere.
It is preferred that the above-mentioned preparation method that porous piezoelectric film is prepared on supporter porous conductive material surface is cement-dipping method, dry-pressing
One kind in method or wet-milling spray mo(u)lding method.
It is preferred that the piezoelectric ceramics average grain diameter for preparing porous piezoelectric film is 5-3000nm.
Above-mentioned cement-dipping method is to disperse to prepare finely dispersed preparation liquid in aqueous by piezoelectric ceramics and be coated in branch
Support body surface, wherein soaking paste preparation liquid quality solid content are 2-20%；Wet film coating time is 30-180s.
Above-mentioned wet-milling spraying process is that piezoelectric ceramics dispersion is prepared finely dispersed preparation liquid and sprayed in aqueous
In supporting body surface, wherein preparation liquid quality solid content is 2-20%；Spray time is 5-25s.
It is preferred that above-mentioned piezoelectric ceramics masking liquid and preparation method thereof, can add dispersant or dispersant to promote preparation liquid with thickener
It is uniformly dispersed, dispersant can be ammoniacal liquor or polyethyleneimine, and dispersant quality solid content is no more than 2.2%；Thickener is
One kind in hydroxymethyl cellulose, polyvinyl alcohol or ethylene glycol, thickener qualities solid content is no more than 2%.
The polarization condition of anisotropic membrane is in preferred steps C：Polarization environment is insulation white oil, insulation silicone oil or air；
Polarized electric field intensity is 1-3kV/mm；Poling temperature is 80-150 DEG C, polarization time 0.5-2h.
Unsymmetric structure ultrasound pollution-resistant membrane in situ prepared by the present invention can be in separation of solid and liquid, gas solid separation or liquid liquid point
Application in.Stabilized flux can lift 0.5-20 times.
It is preferred that wet film flash-off time is 10-20 hours；Dried at 60-120 DEG C 10-20 hours.
Unsymmetric structure ultrasound pollution-resistant membrane in situ prepared by the present invention has 1-5 tunics layer, and film layer has stronger
Piezoelectric property, can produce ultrasound in situ to play anti-pollution；Separating layer average pore size scope is 1-1000nm, can be met
The separation requirement of different systems.
Beneficial effect
1. the piezoelectricity separating layer in anisotropic membrane can convert electrical energy into mechanical energy after two ends apply alternating current, produce
Mechanical oscillation, can slow down the concentration polarization phenomenon of face, slow down the accumulation of pollutant, play anti-pollution.
2. anisotropic membrane is with porous conductive material as supporter, in the method that its surface passes through successively to prepare, it can be ensured that
The precision of separating layer, prevents the generation of defect.
3. use porous conductive material as the supporter mechanical strength higher for composite membrane is provided, can simultaneously serve as original
Position electrode plays electric action, it is to avoid additional traveling electrode.
Brief description of the drawings
The unsymmetric structure ultrasound pollution-resistant membrane in situ that it is supporter with piezoelectric as separating layer with conductive material that Fig. 1 is
And preparation method thereof schematic diagram.
Fig. 2 is that unsymmetric structure ultrasound pollution-resistant membrane (example one) vibration in situ that underwater ultrasound detector is detected is bent
Line.
Fig. 3 is unsymmetric structure ultrasound pollution-resistant membrane (example one) antipollution curve in situ.
The unsymmetric structure ultrasound pollution-resistant membrane in situ that it is supporter with piezoelectric as separating layer with conductive material that Fig. 4 is
Surface surface sweeping Electronic Speculum (SEM) photo of (example two).
Specific embodiment
Embodiment one：Lead zirconate titanate piezoelectric seperation film and its preparation with porous metals titanium as supporter
5g PZT powders (particle diameter 2-3um) is pressed by dry pressing in porous metals titanium (average pore size 20um)
Type is made, being warming up to 1200 DEG C under argon gas atmosphere protection calcines 4 hours, it is the double-deck knot of 1000nm to prepare average pore size
Structure microfiltration membranes, prepare sketch as shown in Figure 1.High voltage polarization, polarized electric field electricity are carried out during anisotropic membrane is insulated into silicone oil at 150 DEG C
It is 1kV/mm to press, and polarization obtains ultrasound pollution-resistant membrane in situ after 2 hours, piezoelectric film ultrasonic resonance frequency is as shown in Fig. 2 piezoelectric film
Ultrasonic resonance frequency is 190-210kHz.The piezoelectricity seperation film is carried out into filtration experiment in the particle aqueous solution, its permeance property
Change over time as shown in figure 3, piezoelectricity seperation film produces ultrasonic vibration under electric field action, embodied good resistance tocrocking
Can, stabilized flux lifts 6-7 times.
Embodiment two：Barium titanate piezoelectricity with porous metals titanium as supporter is separated and its prepared
On the basis of average pore size prepared by embodiment one is for the lead titanates microfiltration membranes of 1000nm, by 20g manganese niobium lead acid pressures
Electroceramics powder (particle diameter 900nm) is dispersed in the 100g aqueous solution, adds 2.2g ammoniacal liquor as dispersant, 1.5g ethylene glycol conducts
Thickener, prepares the preparation liquid that quality solid content is 20%, 3min is coated on the manganese niobium lead acid surface of 1000nm, by wet film
It is warming up to 100 DEG C to be dried 20 hours in hot air drier, then the film of drying is warming up to 800 DEG C in helium, calcines 2 hours
Prepare the manganese niobium lead acid microfiltration membranes that the average pore size with three-decker is 500nm, microfiltration membranes surface microscopic topographic such as Fig. 4
It is shown.Anisotropic membrane is carried out into high voltage polarization in 100 DEG C of insulation white oil environment, polarized electric field voltage is 2.5kV/mm, pole
Ultrasound pollution-resistant membrane in situ is obtained after changing 1.5 hours, piezoelectric film ultrasonic resonance frequency is 230-250kHz.By the piezoelectricity seperation film
Filtration experiment is carried out in profit system, piezoelectricity seperation film produces ultrasonic vibration under electric field action, embodied good resisting
Pollutant performance, stabilized flux lifts 8-10 times.
Embodiment three：Lead zinc niobate piezoelectricity seperation film and its preparation with porous metals titanium as supporter
On the basis of average pore size prepared by embodiment two is for the manganese niobium lead acid microfiltration membranes of 500nm, by 10g lead zinc niobate pressures
Electroceramics powder (particle diameter 200nm) is dispersed in 100g water, adds 1.2g polyethyleneimines as dispersant, and 1g polyvinyl alcohol is made
It is thickener, prepares the preparation liquid that quality solid content is 10%, is coated in the manganese niobium lead acid microfiltration membranes of 500nm
1.5min.Wet film is warming up into 90 DEG C to be dried 10 hours in hot air drier, then the film that will be dried is in atmosphere temperature rising to 650
DEG C, calcining prepares the lead zinc niobate milipore filter that the average pore size with four-layer structure is 50nm for 1 hour.Anisotropic membrane is existed
High voltage polarization is carried out in 100 DEG C of insulation white oil environment, polarized electric field voltage is 2kV/mm, and polarization obtains original position after 1.5 hours
Ultrasonic pollution-resistant membrane, piezoelectric film ultrasonic resonance frequency is 470-500kHz.The piezoelectricity seperation film is entered in nanometer dusty gas
Row filtration experiment, piezoelectricity seperation film produces ultrasonic vibration under electric field action, has embodied good antifouling property, and stabilization is logical
0.5-2 times of amount lifting.
Example IV：Metaniobate piezoelectricity seperation film and its preparation with porous metals titanium as supporter
On the basis of average pore size prepared by embodiment three is for the lead zinc niobate milipore filter of 50nm, by 6g lead meta-columbute piezoelectricity
Ceramic powder (particle diameter 20nm) is dispersed in 100g water, adds 1.2g polyethyleneimines as dispersant, 1g polyvinyl alcohol conducts
Thickener, prepares the preparation liquid that quality solid content is 6%, and 1min is coated on the lead zinc niobate milipore filter of 50nm.Will be wet
Film is warming up to 80 DEG C and is dried 10 hours in hot air drier, then the film of drying is warming up into 500 DEG C in atmosphere, and calcining 1 is small
When prepare the average pore size with five-layer structure be 5nm lead meta-columbute milipore filter.Insulation by anisotropic membrane at 100 DEG C
High voltage polarization is carried out in silicone oil environment, polarized electric field voltage is 1.5kV/mm, and polarization obtains ultrasound antipollution in situ after 1 hour
Film, piezoelectric film ultrasonic resonance frequency is 310-330kHz.The piezoelectricity seperation film is carried out into filtration experiment in glucan aqueous solution,
Piezoelectricity seperation film produces ultrasonic vibration under electric field action, has embodied good antifouling property, stabilized flux lifting 15-17
Times.
Embodiment five：Zinc oxide piezoelectric seperation film and its preparation with porous metals titanium as supporter
On the basis of average pore size prepared by example IV is for the lead meta-columbute milipore filter of 5nm, by 2g zinc oxide (particle diameters
5nm) ceramic powder is dispersed in 1000g deionized waters, adds 1.5g polyethyleneimines as dispersant, and 2g ethylene glycol is used as increasing
Thick dose, be uniformly dispersed the preparation liquid for preparing that quality solid content is 2%, is the lead meta-columbute milipore filter of 5nm in average pore size
Upper coating 30s.By wet film be warming up to 60 DEG C in hot air drier dry 10 hours, then will dry film in atmosphere temperature rising extremely
300 DEG C, calcining prepares the zinc oxide nano filter membrane that the average pore size with six layer structure is 1nm for 1 hour.Anisotropic membrane is existed
High voltage polarization is carried out in 80 DEG C of SOI oil environment, polarized electric field voltage is 1kV/mm, and polarization obtains ultrasound in situ after 2 hours
Pollution-resistant membrane, piezoelectric film ultrasonic resonance frequency is 390-410kHz.The piezoelectricity seperation film is carried out in Aqueous Solutions of Polyethylene Glycol
Filtration experiment, piezoelectricity seperation film produces ultrasonic vibration under electric field action, has embodied good antifouling property, stabilized flux
19-20 times of lifting.
Embodiment six：Lead titanates piezoelectricity seperation film and its preparation with nickel foam as supporter
2g lead titanate powders (particle diameter 2-3um) is dry-pressing formed on circular shaped foam nickel supporter, and nickel foam is a diameter of
30mm, thickness is 5mm, and average pore size is 15um.Film is warming up to 600 DEG C in atmosphere, calcining is prepared with two for 2 hours
The average pore size of Rotating fields is the microfiltration membranes of 1000nm.Anisotropic membrane is carried out into high voltage polarization, pole in 140 DEG C of air ambient
Change voltage of electric field is 2.1kV/mm, and polarization obtains ultrasound pollution-resistant membrane in situ after 1 hour, piezoelectric film ultrasonic resonance frequency is 390-
410kHz.The piezoelectricity seperation film is carried out into filtration experiment in the particle aqueous solution, piezoelectricity seperation film produces super under electric field action
Acoustic vibration, has embodied good antifouling property, and stabilized flux lifts 2-5 times.
Embodiment seven：Zinc oxide piezoelectric seperation film and its preparation with porous carbon as supporter
15g PZT powders (particle diameter 500nm) is dispersed in 100g water, 1.2g ammoniacal liquor is added as dispersant, point
Dissipate the preparation liquid that uniform preparation quality solid content is 15%.By spraying process in porous carbon (average pore size 1um) surface spraying 5s
Lead zirconate titanate separating layer is prepared, wet film is warming up into 80 DEG C dries 12 hours in hot air drier, then the film that will be dried is in nitrogen
900 DEG C are warming up in gas atmosphere, the average pore size that calcining prepares double-layer structure for 2 hours is the microfiltration membranes of 300nm.By 2g oxygen
Change zinc powder body (particle diameter 100nm) to be dispersed in 100g water, add 1ml ammonium polyacrylates as dispersant, be uniformly dispersed preparation matter
Amount solid content is 2% preparation liquid, and coating 25s in the lead zirconate titanate film layer of 300nm by spraying process prepares the smaller oxygen in aperture
Change zinc layers, wet film is warming up into 80 DEG C is dried 12 hours in hot air drier, then the film dried is heated up in argon gas atmosphere
To 750 DEG C, the average pore size that calcining prepares three-decker for 2 hours is the milipore filter of 30nm.By anisotropic membrane at 140 DEG C
High voltage polarization is carried out in air ambient, polarized electric field voltage is 1.6kV/mm, and polarization obtains ultrasound antipollution in situ after 1 hour
Film, piezoelectric film ultrasonic resonance frequency is 20-50kHz.The piezoelectricity seperation film is carried out into filtering in nano particle dusty gas real
Test, piezoelectricity seperation film produces ultrasonic vibration under electric field action, embodied good antifouling property, stabilized flux lifting
0.5-2 times.
Embodiment eight：Lead zirconate titanate piezoelectric seperation film and its preparation with foamed aluminium as supporter
By 5g PZT powders (particle diameter 2-3um) by dry pressing foamed aluminium (average pore size 16um, it is a diameter of
30mm, thickness is 5mm) it is compressing, argon gas atmosphere protection under be warming up to 1200 DEG C calcine 4 hours, prepare average hole
Footpath is the double-decker microfiltration membranes of 1000nm, prepares sketch as shown in Figure 1.Carried out during anisotropic membrane is insulated into silicone oil at 150 DEG C
High voltage polarization, polarized electric field voltage is 1kV/mm, and polarization obtains ultrasound pollution-resistant membrane in situ after 0.5 hour, piezoelectric film ultrasound is altogether
Vibration frequency is 70-90kHz.The piezoelectricity seperation film is carried out into filtration experiment in the particle aqueous solution, piezoelectricity seperation film is made in electric field
With lower generation ultrasonic vibration, good antifouling property is embodied, stabilized flux lifts 10-12 times.
Embodiment nine：Barium titanate piezoelectricity seperation film and its preparation with 316L type porous stainless steels as supporter
20g barium carbonate powders (particle diameter 500nm) is dispersed in 100g water, 1.2g ammoniacal liquor is added as dispersant, dispersion
It is uniform to prepare the preparation liquid that quality solid content is 20%, barium titanate is prepared in 316L type stainless steel surfaces by wet-milling spraying process
Layer, spray time is 25s；Wet film is dried be warming up to after 12h 80 DEG C and dried 12 hours in hot air drier, then will dried
Composite membrane under argon gas protection, is warming up to 700 DEG C in tube furnace, and the average pore size that calcining prepares double-layer structure in 2 hours is
The composite membrane of 200nm.Composite membrane is carried out into high voltage polarization in 140 DEG C of air ambient, polarized electric field voltage is 2.1kV/mm,
Polarization obtains ultrasound pollution-resistant membrane in situ after 1 hour, piezoelectric film ultrasonic resonance frequency is 130-150kHz.By the piezoelectricity seperation film
Filtration experiment is carried out in profit system, piezoelectricity seperation film produces ultrasonic vibration under electric field action, embodied good resisting
Pollutant performance, stabilized flux lifts 7-9 times.
Embodiment ten：Lead zirconate titanate piezoelectric seperation film and its preparation with foam copper as supporter
By 5g PZT powders (particle diameter 2-3um) by dry pressing foam copper (average pore size 15um, it is a diameter of
30mm, thickness is 5mm) it is compressing, argon gas atmosphere protection under be warming up to 1200 DEG C calcine 4 hours, prepare average hole
Footpath is the double-decker microfiltration membranes of 1000nm.High voltage polarization, polarized electric field electricity are carried out during anisotropic membrane is insulated into silicone oil at 150 DEG C
It is 1kV/mm to press, and polarization obtains ultrasound pollution-resistant membrane in situ after 0.5 hour, and piezoelectric film ultrasonic resonance frequency is 230-250kHz.
The piezoelectricity seperation film is carried out into filtration experiment in particle aqueous suspension, piezoelectricity seperation film produces ultrasound to shake under electric field action
It is dynamic, good antifouling property has been embodied, stabilized flux lifts 8-10 times.
Claims (10)
1. a kind of unsymmetric structure with piezoelectric as separating layer ultrasound pollution-resistant membrane in situ, it is characterised in that supporter is many
Hole conductive material, average pore size is 1-20um；Separating layer is porous piezoceramics, and average pore size is 1-1000nm.
2. unsymmetric structure according to claim 1 ultrasound pollution-resistant membrane in situ, it is characterised in that described porous, electrically conductive
Material is the one kind in porous carbon, porous metals titanium, nickel foam, foam copper, foamed aluminium, stainless steel or alloy；Supporter is porous
Conductive material is sheet or tubular structure.
3. unsymmetric structure according to claim 1 ultrasound pollution-resistant membrane in situ, it is characterised in that described porous piezoelectric
The material of ceramics is in barium titanate, lead titanates, lead zirconate titanate, zinc oxide, metaniobate, manganese niobium lead acid, lead zinc niobate or quartz
One kind or its mixture；The number of plies of separating layer is 1-5 layers；The resonant frequency of unsymmetric structure ultrasound pollution-resistant membrane in situ is
20-500kHz。
4. a kind of method for preparing unsymmetric structure as claimed in claim 1 ultrasound pollution-resistant membrane in situ, it is concretely comprised the following steps：
A, porous piezoelectric film is prepared on supporter porous conductive material surface, be warming up to 300-1200 DEG C, calcined 1-4 hour and be molded, made
Standby porous piezoelectric film；B or repeat step A1-4 times；C, the porous piezoelectric film of preparation is polarized under high voltage electric field, made
Porous piezoceramics separating layer possesses piezoelectric property, and unsymmetric structure ultrasound pollution-resistant membrane in situ is obtained.
5. method according to claim 4, it is characterised in that the calcination environment in step A is air atmosphere, argon gas atmosphere,
One kind in helium atmosphere or nitrogen atmosphere.
6. method according to claim 4, it is characterised in that prepare porous piezoelectric on supporter porous conductive material surface
The preparation method of film is the one kind in cement-dipping method, dry pressing or wet-milling spray mo(u)lding method.
7. method according to claim 6, it is characterised in that described cement-dipping method be piezoelectric ceramics is dispersed in it is water-soluble
Finely dispersed preparation liquid is prepared in liquid and supporting body surface is coated in, wherein soaking paste preparation liquid quality solid content is 2-20%；
Wet film coating time is 30-180s.
8. method according to claim 6, it is characterised in that described wet-milling spraying process is to be dispersed in piezoelectric ceramics
Finely dispersed preparation liquid is prepared in the aqueous solution and supporting body surface is sprayed on, wherein preparation liquid quality solid content is 2-20%；
Spray time is 5-25s.
9. method according to claim 4, it is characterised in that polarized in step C environment for insulation white oil, insulation silicone oil or
Person's air；Polarized electric field intensity is 1-3kV/mm；Poling temperature is 80-150 DEG C, polarization time 0.5-2h.
10. a kind of unsymmetric structure as claimed in claim 1 ultrasound pollution-resistant membrane in situ is in separation of solid and liquid, gas solid separation or liquid
Application in liquid separation.
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| CN107952370A (en) * | 2017-11-22 | 2018-04-24 | 北京科技大学 | Piezoelectric transducer for cylindrical membrane component automatically cleaning technology and preparation method thereof |
| KR101971797B1 (en) * | 2017-10-27 | 2019-04-23 | 한국과학기술연구원 | Membrane for water treatment and manufacturing method for the same |
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