CN108554206A - A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube - Google Patents
A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube Download PDFInfo
- Publication number
- CN108554206A CN108554206A CN201810343211.3A CN201810343211A CN108554206A CN 108554206 A CN108554206 A CN 108554206A CN 201810343211 A CN201810343211 A CN 201810343211A CN 108554206 A CN108554206 A CN 108554206A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- filter membrane
- polymer
- porous
- composite filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 234
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 201
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 201
- 239000012528 membrane Substances 0.000 title claims abstract description 131
- 239000002131 composite material Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 230000005684 electric field Effects 0.000 claims abstract description 30
- 239000012530 fluid Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 230000004907 flux Effects 0.000 claims abstract description 12
- 238000001020 plasma etching Methods 0.000 claims abstract description 11
- 239000004815 dispersion polymer Substances 0.000 claims abstract description 8
- 239000011159 matrix material Substances 0.000 claims abstract description 7
- -1 carbon nano-tube compound Chemical class 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- 239000006185 dispersion Substances 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 229920006393 polyether sulfone Polymers 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 239000004695 Polyether sulfone Substances 0.000 claims description 8
- 238000005530 etching Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- IMIMVUJTMYKZAB-UHFFFAOYSA-N CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.N.N Chemical compound CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.CC(C)C(N)=O.N.N IMIMVUJTMYKZAB-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000011017 operating method Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 description 20
- 229920000767 polyaniline Polymers 0.000 description 16
- 238000000034 method Methods 0.000 description 11
- 108091006146 Channels Proteins 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 6
- 235000011167 hydrochloric acid Nutrition 0.000 description 5
- 230000003321 amplification Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002090 nanochannel Substances 0.000 description 4
- 238000003199 nucleic acid amplification method Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000002048 multi walled nanotube Substances 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 108090000862 Ion Channels Proteins 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 1
- CHBCHAGCVIMDKI-UHFFFAOYSA-N [F].C=C Chemical group [F].C=C CHBCHAGCVIMDKI-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001599 direct drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000329 molecular dynamics simulation Methods 0.000 description 1
- 210000000337 motor cortex Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000004804 winding Methods 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
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/35—Use of magnetic or electrical fields
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/26—Electrical properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention belongs to Material Fields, disclose a kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube, the filter membrane is made of carbon nanotube and polymer, using polymer as film matrix, carbon nanotube aligns in film matrix, and the filter membrane is using carbon nanotube endoporus as fluid transport channel；The preparation method based on the high-throughput composite filter membrane of porous in carbon nanotube, it is characterised in that：Include the following steps：A) scattered carbon nanotube polymer dispersion liquid is taken to apply vertical electric field, in conjunction with heating, drying, the carbon nano-tube compound film after being dried by upper bottom crown；B) composite membrane after drying is subjected to plasma etching, obtains the high-throughput composite filter membrane based on porous in carbon nanotube.The filter membrane is due to being utilized porous in carbon nanotube, compared with Conventional nano filter membrane, flow velocity faster, flux it is high, be less prone to fouling membrane, electric conductivity is excellent, is conducive to promote.
Description
Technical field
The invention belongs to Material Field, it is related to a kind of high-throughput composite filter membrane based on porous in carbon nanotube and preparation
Method.
Background technology
Carbon nanotube is concerned with its excellent machinery, heat transfer, conduction and mass-transfer performance, and especially its endoporus is unique
Nano environment：The intimate atomically flat of inner wall becomes a friction free nanochannel.Either Molecular Dynamics Model
Simulation or the flowing research of actual carbon nano pipe array confirms, when liquid over carbon nanotubes endoporus, flow rate ratio
Other nanochannels want the fast 3-4 order of magnitude under the same terms.The flow at high speed characteristic of carbon nanotube endoporus makes it be expected to become
Next-generation novel film materials, therefore have in UF membrane field using carbon nanotube endoporus as the composite membrane of transmission channel good
Application prospect.
Traditional carbon nanotube composite filter membrane is made in the method for blending, winding accumulation mutually between carbon nanotube,
Random orientation, i.e., carbon nanotube is disorderly arranged, is duct by polymer itself, carbon nanometer when fluid flows through the film
The hole between gap (outer wall of carbon nanotube), carbon nanotube and polymer between pipe can not utilize the interior of carbon nanotube
Hole high speed transport property.
Through retrieval, the prior art is 201010246969.9 there are relevant application case, such as Chinese Patent Application No., open
Date is that the application case of 2010.11.24 discloses a kind of preparation method of carbon nano tube-polymer composite nanofiltration membrane, is operated
Step is：(1) porous support membrane is directly immersed in the oil-phase solution containing reaction monomers first, is impregnated 5~40 minutes, taken out
And the excessive solution in surface is discharged；(2) it is then immersed in the aqueous phase solution containing another reaction monomers and carboxylic carbon nano-tube
In, it reacts 5~40 minutes；(3) it is immersed again in the aforementioned oil-phase solution containing reaction monomers after taking out, reacts 5~40 minutes, pass through
Interfacial polymerization, in the aromatic polymer Motor cortex of one layer of load carbon nanotube of porous support membrane Surface Creation；(4) by above-mentioned step
Rapid obtained composite membrane spontaneously dries in air, then thermally treated, rinsing is to get to carbon nano tube-polymer composite nanofiltration
Film；In the aqueous phase solution, reaction monomers are triethanolamine, triisopropanolamine, o-phenylenediamine, m-phenylene diamine (MPD), divinyl three
The mixture of one or more of amine or triethylene tetramine.However the stream of the carbon nanotube composite nanometer filtering film of this application preparation
Body channel is the nano pore of the nanoaperture and polymer itself between carbon nanotube and polymer, and non-carbonic nanotube
Endoporus, fluid flow rate are limited.
If Chinese Patent Application No. is CN201410581837.X, the application case of publication date 2015.01.28 discloses one
The method that kind prepares vertical ordered carbon nanotube/polyaniline composite film, which is characterized in that include the following steps：Prepare mixing water
Carbon nanotube after acidification is configured to carbon nanotube aqueous dispersions, is reconfigured polyaniline nano fiber by dispersion liquid step
Then aqueous dispersions mix carbon nanotube aqueous dispersions and polyaniline nano fiber aqueous dispersions, ultrasonic 4h, mechanical agitation
30min obtains mix moisture dispersion liquid；It filters and electric field synergistic prepares carbon nano-tube/poly aniline composite membrane step, by mix moisture
Dispersion liquid pours into suction filtration-electric field arrangement, applies the voltage perpendicular to filter paper, which is 100~250V, adjusts suction filtration power and is
180W applies mix moisture dispersion liquid the synergistic effect of electric field and suction filtration, voltage is continued to for 24 hours after suction filtration, then will
Filter paper takes out, and obtains carbon nano-tube/poly aniline composite membrane after natural drying, wherein in mix moisture dispersion liquid carbon nanotube with it is poly-
The mass ratio of aniline nano-fiber is 5：1.However the carbon nano-tube/poly aniline composite membrane of this application is used as capacitance, according to
The preparation method of this application can not prepare filter membrane.
The prior art is by preparing vertical carbon nanotube array there is also the research using porous in carbon nanotube
Composite membrane, it is to synthesize vertical carbon nanotube array with chemical vapour deposition technique (CVD), then pass through polymer-filled, monolithic
1cm2Vertical carbon nanotube array cost be up to 900 yuan, cost is excessively high, and vertical carbon nanotube array sizes are only capable of accomplishing
Several centimetres, it is difficult to which large area synthesizes.
Defect based on the prior art, there is an urgent need for invent it is a kind of it is low-cost, high-throughput, conduct electricity very well based on carbon
The high-throughput composite filter membrane of nanometer pipe orifice.
Invention content
1. to solve the problems, such as
Use in the prior art blending method prepare carbon nanotube filter membrane channel for carbon nanotube and polymer between, gather
Close the nanoaperture of object itself, the defect that flux is smaller, conductive effect is bad, the present invention is intended to provide it is a kind of it is high-throughput, lead
The high-throughput composite filter membrane based on carbon nanotube endoporus of good electrical property.
2. technical solution
To solve the above-mentioned problems, the technical solution adopted in the present invention is as follows：
The present invention provides a kind of high-throughput composite filter membranes based on porous in carbon nanotube, it is characterised in that：It is described
Filter membrane is made of carbon nanotube and polymer, and using polymer as film matrix, carbon nanotube aligns in film matrix, the filter
Film is mainly using carbon nanotube endoporus as fluid transport channel.
As further improvement of the present invention, the flux of the filter membrane is 68.92LMH, and aperture is 3~4nm.
It is described based on the high-throughput composite filter membrane of porous in carbon nanotube as further improvement of the present invention
Preparation method includes the following steps：
A) it takes scattered carbon nano tube-polymer dispersion liquid to apply vertical electric field by upper bottom crown, is dried in conjunction with heating
It is dry, the carbon nano-tube compound film after being dried；In the step, take scattered carbon pipe-polymer solution bottomless in shallow mouth
In glass collar, vertical electric field is applied to the mixed liquor by upper bottom crown, specific operation process is：It is first powered a period of time, then
Heating, drying, heating, drying process are powered simultaneously.
B) carbon nano-tube compound film after drying is taken out, carries out plasma etching, obtain being based on carbon nanotube endoporus
The high-throughput composite filter membrane of property.
As further improvement of the present invention, in the step a) in carbon nano tube-polymer dispersion liquid, carbon nanotube
It accounts for polymer quality percentage and is no more than 1.0%.
As further improvement of the present invention, the polymer is polyether sulfone or Kynoar.
As further improvement of the present invention, in the step a) in carbon nano tube-polymer dispersion liquid, carbon nanotube
It is 0.4%~1.0% to account for polymer quality percentage.
As further improvement of the present invention, it is 0.4%~0.8% that carbon nanotube, which accounts for polymer quality percentage,.
Further include following operating procedure before the step a) as further improvement of the present invention：
1) purification step of carbon nanotube：Carbon nanotube is placed in three-necked flask, concentrated hydrochloric acid, constant temperature oil bath heating is added
Stirring, suction filtration are washed to neutrality, are dried for standby.
2) preparation process of polymer solution：It using nitrogen nitrogen dimethylacetylamide as solvent, dissolves a polymer in solvent, makes
Standby process constant temperature stirring.
3) preparation of carbon nano tube-polymer dispersion liquid：The carbon nanotube of purifying is taken to be added in polymer solution, ultrasound point
It dissipates, obtains the dispersion liquid of carbon nano tube-polymer.
As further improvement of the present invention, the vertical electric field strength be 300~600V/mm, frequency be 100~
800Hz, application electric field time are 2~12h.
As further improvement of the present invention, in the step 1), carbon nanotube (quality)：Concentrated hydrochloric acid (volume)=2：
1；The length of carbon nanotube is 50~100 μm, and outer diameter is 10~30nm；The oil bath temperature is 60~80 DEG C；The step
2) in, the mass fraction that the polymer accounts for solvent is 2%~5%, and mixing time is：12~for 24 hours；Temperature is 50~70 DEG C；
In the step 3), the ultrasonic disperse time is 10~15min, and program is：Ultrasonic 40s, stops 20s, is recycled with this.
As further improvement of the present invention, in the step a), the temperature of heating, drying is 80 DEG C；The step b)
In, when plasma etching, power is 50~100W, and pressure 0.1Torr, oxygen flow is 20~40sccm, positive and negative
It performs etching, etch period is 10~30min.
3. advantageous effect
Compared with the prior art, beneficial effects of the present invention are：
(1) the high-throughput composite filter membrane based on porous in carbon nanotube of the invention, by carbon nanotube and polyether sulfone or
Kynoar forms, good under the electric field using carbon nanotube (CNT) using polyether sulfone or Kynoar as film substrate
The property of response and arrangement regulates and controls directionality arrangement and polymeric material of the carbon nanotube in film matrix by additional vertical electric field
The final synthesis of fine and close filling of material.It is using carbon nanotube endoporus as fluid transport channel, with receiving for filter membrane compared with prior art
Rice grain pattern road is compared, and 3 orders of magnitude or more can be improved in fenestra flow velocity, and filter membrane body resistivity can reduce by 706.5 times, therefore compared to existing
Having the composite filter membrane of technology, not only fluid transport rate faster, and has superior electric conductivity, is conducive to promote.
(2) the high-throughput composite filter membrane based on porous in carbon nanotube of the invention, according to multi-wall carbon nano-tube bore
Statistical result, the internal diameter of carbon pipe orifice are 4.45nm, and the fenestra aperture 3.41nm that this value is measured with BET is very close to showing carbon
Pipe orifice is fenestra channel, and composite filter membrane of the invention is proved that the property of carbon nanotube endoporus is utilized；And in the prior art
Nanoaperture, the nanoaperture of polymer itself of the fluid channel of carbon nanotube filter membrane between carbon nanotube and polymer,
That is nanochannel, therefore be a kind of important breakthrough compared with the existing technology, further expand answering for carbon nanotube composite filter membrane
Use range.
(3) the high-throughput composite filter membrane based on porous in carbon nanotube of the invention, carbon nanotube and polymeric material
It measures percentage and is no more than 1.0%, composite filter membrane in the range has superior fluid flux and electric conductivity, carbon nanometer
Pipe is with polymer quality high percentage when 1.0%, and during the composite filter membrane of preparation, carbon nanotube is easier to reunite, existing
Current field condition be difficult to be allowed to arrange, filter membrane body resistivity based on carbon nanotube endoporus declines unobvious, and can not be preferable
Ensure the directionality of carbon nanotube.
(4) preparation method based on the high-throughput composite filter membrane of porous in carbon nanotube of the invention, takes scattered
Carbon pipe-polymer solution applies vertical electric field in the bottomless glass collar of shallow mouth, by upper bottom crown to the mixed liquor, and combines
Heating, drying processing, forms compacted zone under this condition, ensures to only form carbon nanotube endoporus on filter membrane；And the prior art is to use
Phase inversion, the i.e. mode of glass plate knifing obtain ultrafiltration membrane, are received with the method for interfacial polymerization on the basis of ultrafiltration membrane
Filter membrane, the nanometer of the nano pore and polymer itself of existing ultrafiltration membrane, nanofiltration membrane pores between carbon nanotube and polymer
Duct, and non-carbonic nanotube endoporus；Therefore the product that preparation method of the present invention is prepared has superior flux and electric conductivity
Can, it is conducive to promote.
(5) preparation method based on the high-throughput composite filter membrane of porous in carbon nanotube of the invention, in ultrasonic procedure
Program is set, i.e. ultrasound 40s stops 20s, on the one hand prevents continuous ultrasound solution overheat from having an impact to polymer intensity itself, separately
On the one hand preventing the mode that the excessively high nano material of temperature is easy to reunite that ultrasound procedures is taken to set to be unfavorable for disperseing not only makes
Carbon nanotube and the property of polymer keep stablizing, while can guarantee to obtain preferable dispersion effect.
(6) preparation method based on the high-throughput composite filter membrane of porous in carbon nanotube of the invention, using carbon nanometer
Pipe and polyether sulfone or Kynoar are to prepare material, and external electrical field is realized the vertical orientation of carbon nanotube, prepares and received with carbon
Mitron endoporus is the filter membrane of transfer passages, and entire preparation method is simple, of low cost, is conducive to promote.
Description of the drawings
Fig. 1 be prepare apply electric field during carbon nanotube composite filter membrane after section scanning electron microscope (SEM) photograph, in figure, a is to put
Big multiple is the cross-section morphology under 10,000 times；B is that amplification factor is under 50,000 times, the shape appearance figure that a picture frames constituency is further amplified；
Fig. 2 is the surface topography map of the carbon nanotube composite filter membrane that is prepared under scanning electron microscope after plasma etching；
Fig. 3 is carbon nanotube composite filter membrane (0.5%CNT) manufactured in the present embodiment and carbon nanotube simple blend filter membrane
(0.5%CNT) body resistivity comparison diagram；
Fig. 4 is experiment multi-wall carbon nano-tube bore statistical chart under transmission electron microscope；
Fig. 5 is that full-automatic specific surface area analysis tester (BET) analyzes filter membrane fenestra pore-size distribution prepared by the present invention
Figure；
Fig. 6 is that the carbon nanotube composite filter membrane flux that under different condition prepared by embodiment 1 measures comparison diagram；
Fig. 7 is the comparison collection of illustrative plates of carbon nanotube composite filter membrane and traditional flow model calculated value prepared by embodiment 1；
Fig. 8 is the scanning electron microscope (SEM) photograph that embodiment 2 prepares that carbon nanotube composite filter membrane applies section after electric field in the process, figure
In, a is the whole pattern of the filter membrane section under scanning electron microscope；B is that the filter membrane section part region (frame constituency) is further amplified
Shape appearance figure；
Fig. 9 is carbon nanotube composite filter membrane (0.8%CNT) and carbon nanotube simple blend filter membrane prepared by embodiment 2
(0.8%CNT) body resistivity comparison diagram；
Figure 10 is the comparison collection of illustrative plates of carbon nanotube composite filter membrane and traditional flow model calculated value prepared by embodiment 3；
Figure 11 is the comparison collection of illustrative plates of traditional flow model calculated value of carbon nanotube composite filter membrane prepared by comparative example B；
Figure 12 is carbon nanotube composite filter membrane (1%CNT) and carbon nanotube simple blend filter membrane prepared by this comparative example C
(1%CNT) body resistivity comparison diagram.
Specific implementation mode
The present invention is further described below with reference to specific embodiment.
Embodiment 1
The preparation method of the carbon nanotube high throughput composite filter membrane of the present embodiment, includes the following steps：
1) purifying of carbon nanotube：500mg carbon nanotubes are placed in three-necked flask, 250mL concentrated hydrochloric acids, 70 DEG C of perseverances are added
Warm oil bath heating stirs 12h, and suction filtration is washed to neutrality, is dried for standby at 80 DEG C；In this step, length of carbon nanotube is 50 μ
M, outer diameter 10nm.
2) preparation of polymer solution：20mL nitrogen nitrogen dimethylacetylamides and 0.6g polyether sulfones are added in 100mL beakers,
Constant temperature stirs for 24 hours at 70 DEG C.
3) preparation of the dispersion liquid of carbon nano tube-polymer：Take the carbon nanotube 3mg that step 1) purifies that step 2) is added
The dispersion liquid of carbon nano tube-polymer is prepared in polymer solution, ultrasonic disperse 15min, ultrasonic 40s stop 20s.The dispersion liquid
In, the polymer quality percentage that accounts for of carbon nanotube is 0.5%.
4) preparation of carbon nanotube composite filter membrane：Take scattered carbon pipe-polymer solution in the bottomless glass collar of shallow mouth
In, vertical electric field is applied to the mixed liquor by upper bottom crown, frequency 800HZ, electric field strength 467.6V/mm are first powered
0.5h is again heated to 80 DEG C of drying, and is powered simultaneously, and total conduction time is 2h, and through plasma etching, etching condition is：
Power is 100W, pressure 0.1Torr, oxygen flow 20sccm, and positive and negative performs etching, etch period 15min, most
It can be obtained the composite filter membrane based on carbon nanotube endoporus eventually.
The filter membrane has good electric conductivity, its flux is 68.92LMH after measured, and aperture is 3~4nm, pattern and tool
Body performance is as shown in Fig. 1~Fig. 7.
Fig. 1 be prepare apply electric field during carbon nanotube composite filter membrane after section scanning electron microscope (SEM) photograph, in figure, a is to put
Big multiple is the cross-section morphology under 10,000 times；B is that amplification factor is under 50,000 times, the shape appearance figure that a picture frames constituency is further amplified；By
Fig. 1 is it is found that carbon nanotube when fluid flows through the filter membrane, can be transported along the arrangement of section direction from carbon nanotube endoporus.
Fig. 2 is the surface topography map of the carbon nanotube composite filter membrane that is prepared under scanning electron microscope after plasma etching,
The figure amplification factor is 100,000 times, and as shown in Figure 2, there are one a white point, these small particles to represent carbon nanotube for film surface
Head is further verified carbon nanotube and is vertically aligned with film surface.
Fig. 3 is carbon nanotube composite filter membrane (0.5%CNT) manufactured in the present embodiment and carbon nanotube simple blend filter membrane
(0.5%CNT) body resistivity comparison diagram；Wherein, it is 0.5% that 0.5%CNT, which represents carbon nanotube and accounts for polymer quality percentage,；
By comparing result it is found that using the carbon nanotube simple blend filter membrane of direct drying mode, the present embodiment system compared with prior art
Standby carbon nanotube composite filter membrane body resistivity has dropped 204.2 times, shows that the good orientation of carbon pipe also significantly improves filter
The electric conductivity of film.
Fig. 4 is experiment multi-wall carbon nano-tube bore statistical chart under transmission electron microscope；Fig. 5 surveys for full-automatic specific surface area analysis
The filter membrane fenestra pore-size distribution analysis chart that examination instrument (BET) prepares the present invention；As shown in Figure 4, carbon nanotube internal diameter is 4.45nm,
The fenestra aperture 3.41nm that BET is measured in the value and figure is very close to showing that carbon pipe orifice is fenestra channel.
Fig. 6 is that the carbon nanotube composite filter membrane flux that under different condition prepared by embodiment 1 measures comparison diagram；Fig. 7 is to implement
The comparison collection of illustrative plates of carbon nanotube composite filter membrane prepared by example 1 and traditional flow model calculated value.
As can be seen from FIG. 6：1) only applying vertical electric field and after carrying out plasma etching, carbon nanotube composite filter membrane compared with
High flux；2) do not add vertical electric field, directly dry, i.e. carbon pipe is disorderly arranged, is not discharged still under 7bar test pressures.
As can be seen from FIG. 7, when other conditions are consistent, fluid flows through carbon nanotube composite filter membrane prepared by the present invention, stream
Speed is higher by 4 orders of magnitude of conventional model calculated value, and use in the prior art simple blend mode prepare the flow velocity of filter membrane with
Conventional model calculated value is suitable, root it is documented that：Fluid flows through 3.7 times that polycarbonate membrane is only conventional model calculated value,
Therefore the fluid transport channel of the present invention, carbon nanotube endoporus, compared with the nanochannel of the filter membrane of the prior art, fenestra flow velocity
3 orders of magnitude or more can be improved.
Embodiment 2
The preparation method of the carbon nanotube high throughput composite filter membrane of the present embodiment, includes the following steps：
1) purifying of carbon nanotube：500mg carbon nanotubes are placed in three-necked flask, 250mL concentrated hydrochloric acids, 60 DEG C of perseverances are added
Warm oil bath heating stirs 12h, and suction filtration is washed to neutrality, is dried for standby at 80 DEG C；In this step, length of carbon nanotube is 100 μ
M, outer diameter 30nm.
2) preparation of polymer solution：20mL nitrogen nitrogen dimethylacetylamides are added in 100mL beakers and 0.6g gathers inclined fluorine
Ethylene, constant temperature stirs for 24 hours at 70 DEG C.
3) preparation of the dispersion liquid of carbon nano tube-polymer：Take the carbon nanotube 4.8mg that step 1) purifies that step 2) is added
Polymer solution in prepare the dispersion liquid of carbon nano tube-polymer, ultrasonic disperse 12min, ultrasonic 40s stop 20s.The dispersion
In liquid, the polymer quality percentage that accounts for of carbon nanotube is 0.8%.
4) preparation of carbon nanotube composite filter membrane：Take scattered carbon pipe-polymer solution in the bottomless glass collar of shallow mouth
In, vertical electric field is applied to the mixed liquor by upper bottom crown, frequency 100HZ, electric field strength 300V/mm are first powered
0.5h is again heated to 80 DEG C of drying, and total conduction time is 12h, and through plasma etching, etching condition is：Power is 50W,
Pressure is 0.1Torr, oxygen flow 40sccm, and positive and negative performs etching, and etch period 10min finally can be obtained
Composite filter membrane based on carbon nanotube endoporus.
Fig. 8 is the scanning electron microscope (SEM) photograph that embodiment 2 prepares that carbon nanotube composite filter membrane applies section after electric field in the process, figure
In, a is the whole pattern of the filter membrane section under scanning electron microscope；B is that the filter membrane section part region (a picture frames constituency) is further
The shape appearance figure of amplification；As shown in Figure 8, in entire filter membrane section, carbon pipe is arranged each along section direction, when fluid flows through the film,
It can be transported from carbon nanotube endoporus.
Fig. 9 is carbon nanotube composite filter membrane (0.8%CNT) and carbon nanotube simple blend filter membrane prepared by embodiment 2
(0.8%CNT) body resistivity comparison diagram compares carbon nanotube simple blend filter membrane, carbon manufactured in the present embodiment as shown in Figure 9
Nanotube composite filter membrane body resistivity has dropped 706.5 times, shows the good orientation of carbon pipe, thus also improves the electric conductivity of film
Energy.
Embodiment 3
The preparation method of the carbon nanotube high throughput composite filter membrane of the present embodiment, includes the following steps：
1) purifying of carbon nanotube：500mg carbon nanotubes are placed in three-necked flask, 250mL concentrated hydrochloric acids, 80 DEG C of perseverances are added
Warm oil bath heating stirs 12h, and suction filtration is washed to neutrality, is dried for standby at 80 DEG C；In this step, length of carbon nanotube is 80 μ
M, outer diameter 20nm.
2) preparation of polymer solution：20mL nitrogen nitrogen dimethylacetylamides and 0.6g polyether sulfones are added in 100mL beakers,
Constant temperature stirs for 24 hours at 70 DEG C.
3) preparation of the dispersion liquid of carbon nano tube-polymer：Take the carbon nanotube 2.4mg that step 1) purifies that step 2) is added
Polymer solution in prepare the dispersion liquid of carbon nano tube-polymer, ultrasonic disperse 10min, ultrasonic 40s stop 20s.The dispersion
In liquid, the polymer quality percentage that accounts for of carbon nanotube is 0.4%.
4) preparation of carbon nanotube composite filter membrane：Take scattered carbon pipe-polymer solution in the bottomless glass collar of shallow mouth
In, vertical electric field is applied to the mixed liquor by upper bottom crown, frequency 500HZ, electric field strength 600V/mm are first powered
0.5h is again heated to 80 DEG C of drying, and total conduction time is 3h, and through plasma etching, etching condition is：Power is 80W, pressure
Power is 0.1Torr, oxygen flow 30sccm, and positive and negative performs etching, and etch period 30min finally can be obtained base
In the composite filter membrane of carbon nanotube endoporus.
Figure 10 is the comparison collection of illustrative plates of carbon nanotube composite filter membrane and traditional flow model calculated value prepared by embodiment 3；By
For figure it is found that when other conditions are consistent, fluid flows through filter membrane channel prepared by the present invention, the nanometer with filter membrane compared with prior art
Channel is compared, and 3 orders of magnitude can be improved in fenestra flow velocity.
Comparative example A
Using carbon nanotube and polyaniline, carries out filtering the mode with electric field, same property of the present invention can not be prepared
Product.
Chinese Patent Application No. be CN201410581837.X application cases disclosed in it is a kind of prepare vertical ordered carbon nanotube/
In the method for polyaniline composite film, preparation process includes：
1) mix moisture dispersion liquid step is prepared, the carbon nanotube after acidification is configured to carbon nanotube aqueous dispersions,
Polyaniline nano fiber aqueous dispersions are prepared again, then mix carbon nanotube aqueous dispersions and polyaniline nano fiber aqueous dispersions
It closes, ultrasonic 4h, mechanical agitation 30min obtain mix moisture dispersion liquid；
2) it filters and electric field synergistic prepares carbon nano-tube/poly aniline composite membrane step, mix moisture dispersion liquid is poured into suction filtration-
Electric field arrangement applies the voltage perpendicular to filter paper, which is 100~250V, and it is 180W to adjust and filter power, to mix moisture
Dispersion liquid applies the synergistic effect of electric field and suction filtration, continues to voltage for 24 hours after suction filtration, then takes out filter paper, dry in the air naturally
Carbon nano-tube/poly aniline composite membrane is obtained after dry, wherein the matter of carbon nanotube and polyaniline nano fiber in mix moisture dispersion liquid
Amount is than being 5：1.
Through analysis, carbon nano-tube/poly aniline composite membrane prepared by this application is used as capacitance, and being not used as filter membrane makes
With, the reason is as follows that：1) carbon nanotube is directly to be layered on the patented product, if being used as filter membrane, carbon nanotube can be with dampening
Stream washes away, and can not utilize the flow at high speed performance of its endoporus；2) bad mechanical strength of polyaniline, filter membrane is in use, be required for one
Fixed operating pressure, polyaniline are easy to fall off, contaminated filter water.
Comparative example B
The present embodiment is substantially same as Example 1, the difference is that：Carbon nanotube accounts for polyether sulfone/Kynoar
Mass percent is 0.2%；Final to be prepared into the composite filter membrane based on carbon nanotube endoporus, Figure 11 is prepared by comparative example B
The comparison collection of illustrative plates of traditional flow model calculated value of carbon nanotube composite filter membrane.
As a result known to：When other conditions are consistent, 3 orders of magnitude are higher by compared to traditional flow model calculated value；But it is real
Border flux is only 6.24LMH, 1/10th of 0.5%CNT/PES filter membrane fluxes prepared less than the present invention, practical application by
Limit.
Comparative example C
This comparative example C is substantially same as Example 1, the difference is that：Carbon nanotube accounts for polyether sulfone/Kynoar
Mass percent is 1.0%.
Figure 12 is carbon nanotube composite filter membrane (1%CNT) and carbon nanotube simple blend filter membrane prepared by this comparative example C
(1%CNT) body resistivity comparison diagram, as shown in Figure 12：1) after carbon nanotube mass score is promoted, carbon nanotube is easier group
Poly-, existing current field condition is difficult to be allowed to arrange, therefore the filter membrane body resistivity based on carbon nanotube endoporus has dropped less than 5
Times, decline effect and be not obvious, can not ensure the directionality of carbon nanotube；2) (1% when fluid flows through the filter membrane of the mass fraction
CNT), it is difficult to enter into carbon nanotube endoporus, carbon nanotube endoporus flow at high speed characteristic can not be utilized.
Schematically the invention and embodiments thereof are described above, description is not limiting, attached drawing
Shown in also be the invention one of embodiment, actual structure is not limited to this.So if this field
Those of ordinary skill enlightened by it, in the case where not departing from this creation objective, without creatively designing and the technology
The similar frame mode of scheme and embodiment, should all belong to the protection domain of this patent.
Claims (10)
1. a kind of high-throughput composite filter membrane based on porous in carbon nanotube, it is characterised in that：The filter membrane is by carbon nanotube
It is formed with polymer, using polymer as film matrix, carbon nanotube aligns in film matrix, and the filter membrane is mainly with carbon nanometer
Pipe orifice is fluid transport channel.
2. the high-throughput composite filter membrane according to claim 1 based on porous in carbon nanotube, it is characterised in that：It is described
The flux of filter membrane is 68.92LMH, and aperture is 3~4nm.
3. the preparation method as claimed in claim 1 or 2 based on the high-throughput composite filter membrane of porous in carbon nanotube, feature
It is：Include the following steps：
A) it takes scattered carbon nano tube-polymer dispersion liquid to apply vertical electric field by upper bottom crown to obtain in conjunction with heating, drying
Carbon nano-tube compound film after to drying；
B) carbon nano-tube compound film after drying is taken out, carries out plasma etching, obtained based on porous in carbon nanotube
High-throughput composite filter membrane.
4. the preparation method according to claim 3 based on the high-throughput composite filter membrane of porous in carbon nanotube, special
Sign is：In the step a) in carbon nano tube-polymer dispersion liquid, carbon nanotube accounts for polymer quality percentage and is no more than
1.0%.
5. the high-throughput composite filter membrane according to claim 1 or 4 based on porous in carbon nanotube, it is characterised in that：
The polymer is polyether sulfone or Kynoar.
6. the preparation method according to claim 4 based on the high-throughput composite filter membrane of porous in carbon nanotube, special
Sign is：In the step a) in carbon nano tube-polymer dispersion liquid, it is 0.4% that carbon nanotube, which accounts for polymer quality percentage,
~1.0%.
7. the preparation method based on the high-throughput composite filter membrane of porous in carbon nanotube according to claim 4 or 6,
It is characterized in that：Further include following operating procedure before the step a)；
1) purification step of carbon nanotube：Carbon nanotube is placed in three-necked flask, concentrated hydrochloric acid is added, constant temperature oil bath heating is stirred
It mixes, suction filtration is washed to neutrality, is dried for standby.
2) preparation process of polymer solution：It using nitrogen nitrogen dimethylacetylamide as solvent, dissolves a polymer in solvent, prepared
Cheng Hengwen is stirred.
3) preparation of the dispersion liquid of carbon nano tube-polymer：The carbon nanotube of purifying is taken to be added in polymer solution, ultrasound point
It dissipates, obtains the dispersion liquid of carbon nano tube-polymer.
8. the preparation method based on the high-throughput composite filter membrane of porous in carbon nanotube according to claim 4 or 6,
It is characterized in that：The vertical electric field strength be 300~600V/mm, frequency be 100~800Hz, apply the electric field time be 2~
12h。
9. the preparation method according to claim 7 based on the high-throughput composite filter membrane of porous in carbon nanotube, special
Sign is：In the step 1), carbon nanotube (quality)：Concentrated hydrochloric acid (volume)=2：1；The length of carbon nanotube be 50~
100 μm, outer diameter is 10~30nm；The oil bath temperature is 60~80 DEG C；In the step 2), the polymer accounts for the matter of solvent
It is 2%~5% to measure score, and mixing time is：12~for 24 hours；Temperature is 50~70 DEG C；In the step 3), the ultrasonic disperse time
For 10~15min, program is：Ultrasonic 40s, stops 20s, is recycled with this.
10. the preparation method according to claim 3 based on the high-throughput composite filter membrane of porous in carbon nanotube, special
Sign is：In the step a), the temperature of heating, drying is 80 DEG C；In the step b), when plasma etching, power is
50~100W, pressure 0.1Torr, oxygen flow are 20~40sccm, and positive and negative performs etching, etch period is 10~
30min。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810343211.3A CN108554206A (en) | 2018-04-17 | 2018-04-17 | A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810343211.3A CN108554206A (en) | 2018-04-17 | 2018-04-17 | A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108554206A true CN108554206A (en) | 2018-09-21 |
Family
ID=63535487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810343211.3A Pending CN108554206A (en) | 2018-04-17 | 2018-04-17 | A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108554206A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821418A (en) * | 2019-03-29 | 2019-05-31 | 天津工业大学 | It is a kind of with aligned carbon nanotube basement membrane, utilize its interfacial polymerization nanofiltration membrane and preparation method thereof |
| CN110917906A (en) * | 2019-12-11 | 2020-03-27 | 南京大学 | Ferroelectric nanofiltration membrane material, preparation method and application |
| CN111298666A (en) * | 2020-03-16 | 2020-06-19 | 中国人民解放军火箭军工程设计研究院 | Hollow fiber forward osmosis composite membrane containing oriented carbon nanotubes and preparation method thereof |
| CN111298664A (en) * | 2020-03-16 | 2020-06-19 | 中国人民解放军火箭军工程设计研究院 | Hollow fiber gas separation composite membrane and preparation method thereof |
| CN111318180A (en) * | 2020-03-16 | 2020-06-23 | 中国人民解放军火箭军工程设计研究院 | Preparation method of film material containing oriented carbon nanotubes |
| CN112295405A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | High-flux high-pollution-resistance polyethylene ultrafiltration membrane and preparation method thereof |
| CN112812567A (en) * | 2021-01-28 | 2021-05-18 | 中南大学 | Preparation method of carbon nano tube/polydimethylsiloxane conductive composite material |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101296743A (en) * | 2005-08-24 | 2008-10-29 | 加利福尼亚大学董事会 | Membranes for nanometer-scale mass fast transport |
| CN101947417A (en) * | 2010-08-25 | 2011-01-19 | 上海理工大学 | Carbon nano tube-based nanofiltration membrane device and preparation method thereof |
| CN101983758A (en) * | 2010-10-21 | 2011-03-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Polymer/inorganic nanometer composite separation membrane and preparation method thereof |
| JP2011240278A (en) * | 2010-05-19 | 2011-12-01 | Panasonic Corp | Method for manufacturing filter |
| EP3057687A1 (en) * | 2013-12-16 | 2016-08-24 | SABIC Global Technologies B.V. | Ultraviolet and plasma-treated polymeric membranes |
| CN106102885A (en) * | 2013-12-16 | 2016-11-09 | 沙特基础工业全球技术公司 | Plasma-treated polymeric film |
-
2018
- 2018-04-17 CN CN201810343211.3A patent/CN108554206A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101296743A (en) * | 2005-08-24 | 2008-10-29 | 加利福尼亚大学董事会 | Membranes for nanometer-scale mass fast transport |
| JP2011240278A (en) * | 2010-05-19 | 2011-12-01 | Panasonic Corp | Method for manufacturing filter |
| CN101947417A (en) * | 2010-08-25 | 2011-01-19 | 上海理工大学 | Carbon nano tube-based nanofiltration membrane device and preparation method thereof |
| CN101983758A (en) * | 2010-10-21 | 2011-03-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Polymer/inorganic nanometer composite separation membrane and preparation method thereof |
| EP3057687A1 (en) * | 2013-12-16 | 2016-08-24 | SABIC Global Technologies B.V. | Ultraviolet and plasma-treated polymeric membranes |
| CN106102885A (en) * | 2013-12-16 | 2016-11-09 | 沙特基础工业全球技术公司 | Plasma-treated polymeric film |
Non-Patent Citations (1)
| Title |
|---|
| 藏雨编著: "《气体分离膜材料科学》", 31 January 2017, 哈尔滨工业大学出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109821418A (en) * | 2019-03-29 | 2019-05-31 | 天津工业大学 | It is a kind of with aligned carbon nanotube basement membrane, utilize its interfacial polymerization nanofiltration membrane and preparation method thereof |
| CN112295405A (en) * | 2019-07-30 | 2021-02-02 | 上海恩捷新材料科技有限公司 | High-flux high-pollution-resistance polyethylene ultrafiltration membrane and preparation method thereof |
| CN112295405B (en) * | 2019-07-30 | 2022-06-10 | 上海恩捷新材料科技有限公司 | High-flux high-pollution-resistance polyethylene ultrafiltration membrane and preparation method thereof |
| CN110917906A (en) * | 2019-12-11 | 2020-03-27 | 南京大学 | Ferroelectric nanofiltration membrane material, preparation method and application |
| CN111298666A (en) * | 2020-03-16 | 2020-06-19 | 中国人民解放军火箭军工程设计研究院 | Hollow fiber forward osmosis composite membrane containing oriented carbon nanotubes and preparation method thereof |
| CN111298664A (en) * | 2020-03-16 | 2020-06-19 | 中国人民解放军火箭军工程设计研究院 | Hollow fiber gas separation composite membrane and preparation method thereof |
| CN111318180A (en) * | 2020-03-16 | 2020-06-23 | 中国人民解放军火箭军工程设计研究院 | Preparation method of film material containing oriented carbon nanotubes |
| CN112812567A (en) * | 2021-01-28 | 2021-05-18 | 中南大学 | Preparation method of carbon nano tube/polydimethylsiloxane conductive composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108554206A (en) | A kind of high-throughput composite filter membrane and preparation method based on porous in carbon nanotube | |
| Islam et al. | A high flux polyvinyl acetate-coated electrospun nylon 6/SiO2 composite microfiltration membrane for the separation of oil-in-water emulsion with improved antifouling performance | |
| Zeng et al. | Preparation and characterization of a novel PVDF ultrafiltration membrane by blending with TiO2-HNTs nanocomposites | |
| Wang et al. | Preparation of polyethersulfone/carbon nanotube substrate for high-performance forward osmosis membrane | |
| CN104772048B (en) | Inorganic-organic hybrid film that a kind of inorganic filler is combined with dopamine and its production and use | |
| Shaban et al. | Titanium dioxide nanotubes embedded mixed matrix PES membranes characterization and membrane performance | |
| Liu et al. | Superhydrophobic poly (vinylidene fluoride) membranes with controllable structure and tunable wettability prepared by one-step electrospinning | |
| Nour et al. | CNT/PDMS composite membranes for H2 and CH4 gas separation | |
| Ghazanfari et al. | Preparation and characterization of poly (vinyl chloride)(PVC) based membrane for wastewater treatment | |
| WO2022000608A1 (en) | Aerogel composite membrane, preparation method therefor and use thereof | |
| Mao et al. | Anti-fouling and easy-cleaning PVDF membranes blended with hydrophilic thermo-responsive nanofibers for efficient biological wastewater treatment | |
| Zhang et al. | Treatment of wastewater containing oil using phosphorylated silica nanotubes (PSNTs)/polyvinylidene fluoride (PVDF) composite membrane | |
| Pirzada et al. | Hybrid carbon silica nanofibers through sol–gel electrospinning | |
| CN108854604A (en) | A kind of polymeric membrane for separation, preparation method and application | |
| Vatanpour et al. | A comprehensive review on the applications of boron nitride nanomaterials in membrane fabrication and modification | |
| CN109925891B (en) | Small-aperture high-flux carbon nanotube low-pressure membrane and preparation method thereof | |
| Zahirifar et al. | Influence of hexagonal boron nitride nanosheets as the additives on the characteristics and performance of PVDF for air gap membrane distillation | |
| Ebrahimi et al. | Fabrication of hydrophilic special sandwich structure of PAN/GO/SiO2 electrospun membrane decorated with SiO2 nanoparticles for oil/water separation | |
| CN106693726A (en) | Formula for preparing polyvinylidene fluoride and carbon nanotube composite film and preparation method of formula | |
| Wang et al. | Enhanced antifouling performance of hybrid PVDF ultrafiltration membrane with the dual-mode SiO2-g-PDMS nanoparticles | |
| Liu et al. | Facile preparation of cross-linked porous poly (vinyl alcohol) nanofibers by electrospinning | |
| Gui et al. | g-C3N4 nanofibers network reinforced polyamide nanofiltration membrane for fast desalination | |
| CN107158953A (en) | A kind of preparation method of membrane distillation nano wire hydrophobic membrane | |
| Zhang et al. | Single-walled carbon nanotubes grafted with dextran as additive to improve separation performance of polymer membranes | |
| CN106345309A (en) | PVDF organic membrane modifying method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180921 |