CN110327789A - A kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof - Google Patents
A kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof Download PDFInfo
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- CN110327789A CN110327789A CN201910602872.8A CN201910602872A CN110327789A CN 110327789 A CN110327789 A CN 110327789A CN 201910602872 A CN201910602872 A CN 201910602872A CN 110327789 A CN110327789 A CN 110327789A
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- 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
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- 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
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- 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
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Abstract
The invention belongs to technical field of membrane, a kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof is provided.1-dimention nano fabric nonwoven cloth using electrostatic spinning process preparation is supporting layer, is crosslinked upper carbon nanotube as separating layer in supporting layer, constructs the conductive film for having the networked pore structures that monodimension nanometer material is interwoven.The membrane aperture for the composite membrane being related to is controllable from micro-filtration to ultrafiltration range, and film form includes that plate membrane, hollow-fibre membrane, rolled film are controllable.The composite membrane major advantage and beneficial effect being related to are: preparation step is simple, has preferable permeability and mechanical strength, good hydrophily and electric conductivity, is easy to large-scale production and application.
Description
Technical field
The present invention relates to a kind of carbon nanotube/nano fiber conductive composite films and preparation method thereof, belong to membrane technology neck
Domain.
Background technique
Membrane separation technique is widely used in water process neck as a kind of energy-efficient and simple and convenient phase detachment technique
Advanced treatment of wastewater, household drinking water purification and resource recycling in domain etc..However, there are dampenings for existing seperation film
The problems such as conflicting relationship, fouling membrane between permeability and separating capacity are serious, film has a single function seriously constrains film point
Further development and application from technology.
Research finds that the seperation film prepared based on carbon nanotube shows the webbed membrane structure of monodimension nanometer material intertexture
With the fenestra road being mutually communicated, have the advantages that high porosity, low hole curvature and high osmosis.And since carbon nanotube has
Outstanding electric conductivity assists (electrostatic repulsion, electrosorption enhanced and electrochemical oxidation etc.)-film to filter coupling technique by electricity,
Can effective decelerating membrane pollution, alleviate the contradictory relation between film permeability and separating capacity, meanwhile, electric auxiliary process is hopeful to assign
The new function of carbon nanotube separation film is given, the present problems faced of membrane separation technique can be effectively relieved.Research is received based on carbon at present
There are mainly three types of the seperation films of mitron: the first, the pure nano-carbon tube film of simple carbon nano-tube material assembling；Second, carbon is received
Mitron is uniformly mixed the mixed substrate membrane containing nano-grade molecular sieve of preparation with other material of preparing (high molecular material, ceramic membrane materials etc.)；The third, carbon
Nanotube is as separating layer, coated in the composite membrane prepared on supporting layer matrix.However the existing separation based on carbon nanotube
All there are some problems in film, affect the performance and application of seperation film.Such as: that there is preparation costs is high for pure nano-carbon tube film,
Bad mechanical strength is difficult to the problem of putting into application；Carbon nanotube is coated tight by other membrane materials in mixed-matrix carbon nano-tube film
Weight, masks the advantage of carbon nano-tube material itself；The permeance property of carbon nano-tube compound film is supported the limitation of layer matrix,
Structural advantage of the carbon nanotube as monodimension nanometer material can not be played.
Summary of the invention
Currently invention addresses the huge researchs and market prospects that are had based on carbon nanotube separation film, for existing carbon nanometer
Pipe separates disadvantage existing for membrane preparation technology, provides one kind simply, efficiently, the carbon nanotube/nano for being easy to large-scale production is fine
Tie up composite separating film.The present invention is supporting layer by using the non-woven fabrics that 1-dimention nano fiber is constituted, and is crosslinked upper carbon in supporting layer
Nanotube makes entire composite membrane remain the networked pore structures that monodimension nanometer material is interwoven as separating layer.
Technical solution of the present invention:
One kind being based on carbon nanotube/nano fiber composite seperation film, is divided into supporting layer and functional layer two parts, electrostatic spinning
The nanofiber of preparation is as supporting layer, and for carbon nanotube as separating layer, carbon nanotube is covered on nanofiber surface, carbon nanometer
Pipe by crosslinking agent 1 and crosslinking agent 2, fix jointly by crosslinking；Wherein carbon nanotube and nanofiber are one-dimensional linear material, and two
Kind of linear material constructs three-dimensional netted pore structure seperation film, and by linear material intermesh winding enhance supporting layer with separate
It interacts between layer, constitutes stable membrane structure.
Support layer material described in scheme can be synthetic polymer macromolecule, natural polymer, inorganic matter alkoxide, ceramics
Presoma etc. includes but is not limited to this, and the material for being suitable for electrostatic spinning can be used to prepare nanofiber supporting layer.
Crosslinking agent 1 and crosslinking agent 2: polyacrylamide and succinic acid, polyvinyl alcohol and glutaraldehyde, polyvinyl alcohol and penta 2
Acid, phenolic resin and ethanedioic acid.
Film form includes plate membrane, hollow-fibre membrane, three kinds of rolled film.
A kind of preparation method based on carbon nanotube/nano fiber composite seperation film, steps are as follows:
The first step, the preparation of nanofiber supporting layer
(1) spinning material as supporting layer is dissolved in corresponding solvent, be configured to mass fraction 10%-20% it
Between spinning solution, carry out electrostatic spinning；By spinning solution by micro-sampling pump slowly injection, drop under electrostatic field, to
Reception device migration is drawn into nanofiber, regulates and controls electrostatic spinning voltage density 1kV/cm, spinning distance is in 10cm-20cm model
It encloses, the spinning time is regulated and controled in 4-20h according to concentration, relevant nanometer filament support layer is obtained from reception device；
Wherein, different according to film form, concrete operations are as follows:
Plate membrane: electrostatic spinning is received using idler wheel collecting nanofibers device or plate collecting nanofibers device and prepares nanometer
Fiber directly removes hot-forming flat support layer from collector surface wait collect to finish；
Hollow-fibre membrane: using the continuous filament collector of dynamic, in electrostatic spinning filamentation process, control is continuous thin
After silk collector passes through reception nanofiber region with fixed rate, filament collector is sent to heating room, heat-resisting according to material
Property thermal-stable shrink nanofiber；Then filament collector is immersed into 0.1mol/L pickle or copper salt solution 5-60min, it
After detach filament collector, obtain doughnut supporting layer；
Rolled film: using conductive rolling center pipe network as collecting nanofibers device, finishing wait collect, by center pipe network with
Nanofiber is hot-forming together, is then fixed non-woven membrane by gluing, then cools to room temperature to obtain rolled film support
Layer；
Second step, electrostatic spraying prepare carbon nanotube functional layer
Carbon nanotube after nitration mixture is acidified is dispersed in water, and is configured to the dispersion liquid of 5-10mg/mL, and nitration mixture is volume ratio
For the 95-98wt.% concentrated sulfuric acid and 65-68wt.% concentrated nitric acid of 3:1；Then in regulation voltage density 1kV/cm, spinning distance exists
Electrostatic spraying is carried out to nanofiber supporting layer within the scope of 10-20cm；
Third step, the crosslinking of carbon nanotube/nano composite fiber membrane
Molding composite membrane will be prepared to remove, be immersed in the mixed liquor of crosslinking agent 1 and crosslinking agent 2, and 2M hydrochloric acid is added
Adjust pH to 2；Deionized water is cleaned after taking-up, dry solidification under the conditions of 60 DEG C.
Beneficial effects of the present invention:
(1) seperation film based on the building of full monodimension nanometer material, the advantage with netted perforation pore structure, membrane porosity
Height, hole tortuosity are low, effective porosity is high, these advantages enhance membrane permeability, and the present invention is than in the market the same as point of aperture size
2-10 times is higher by from membrane flux.
(2) monodimension nanometer material based on high draw ratio assembles building, and seperation film of the invention shows outstanding soft
Toughness and mechanical strength.
(3) separating layer and support bed boundary by two kinds of one-dimensional linear nano materials intermesh winding enhance supporting layer with
It interacts between separating layer, plays the role of stablizing whole membrane structure
(4) carbon nanotube separation layer is prepared for by electrostatic painting process, separating layer has 80% or more porosity, has
Conducive to resistance to mass tranfer is reduced, membrane permeability is improved.
(5) characteristic for remaining separating layer carbon nanotube conducting is conducive to couple with other techniques.
(6) using the fixed carbon nanotube of crosslinking agent, it ensure that the stability of separating layer.
(7) method is flexibly controllable, can prepare the seperation film of variform and be easy to large-scale production and application.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture of carbon nanotube/nano composite fiber membrane supporting layer.
Fig. 2 is the scanning electron microscopic picture of carbon nanotube/nano composite fiber membrane separating layer.
Specific embodiment
The embodiment of the present invention is illustrated with reference to the accompanying drawing, but the present invention is not limited solely to following embodiment.
Embodiment 1: preparation carbon nanotube/PAN nanofiber composite flat membrane
The first step, electrospun nanofibers substrate
High molecular polymer polyacrylonitrile (PAN) as substrate is dissolved in n,N dimethylformamide (DMF), is prepared
At spinning solution of the mass fraction between 15%, regulate and control voltage density 1kV/cm or so, spinning distance is in 10-20cm range, root
According to the concentration regulation spinning time in 10h, relevant nanometer fibrous substrate is obtained from reception device, heat is carried out under the conditions of 150 DEG C
Pressure, obtains plate nanofiber supporting layer.
Second step, electrostatic spraying prepare carbon nanotube functional layer
The carbon nanotube of 60-100nm caliber is dispersed in water after nitration mixture is acidified, and is configured to the dispersion liquid of 5mg/mL, so
Afterwards in regulation voltage density 1kV/cm or so, spinning distance carries out electrostatic spraying to nanofiber substrate within the scope of 10-20cm
6h。
Third step, the crosslinking of carbon nanotube/PAN nano-fiber composite film
Molding composite membrane will be prepared to remove, impregnating 1h in mass concentration is polyacrylamide (0.2%) and ethanedioic acid
(1%) in mixed liquor, and 2M salt acid for adjusting pH is added to acidity.Deionized water is cleaned after taking-up, dry solid under the conditions of 60 DEG C
Change.
As a result: the carbon nanotube of preparation/PAN nanofiber composite flat membrane supporting layer and separating layer show netted pass through
Through-hole structure, supporting layer aperture is in 1-2 μ m, and compound membrane aperture is in 300nm or so.And because of PAN better heat stability, just
Nanofiber is shunk in higher temperature hot pressing, so having most based on carbon nanotube/nano composite fiber membrane made of PAN material
Excellent mechanical strength and stability.
Embodiment 2: preparation carbon nanotube/PAN nanofiber composite hollow fiber membrane
The first step, electrospun nanofibers substrate
High molecular polymer PAN as substrate is dissolved in DMF, spinning of the mass fraction between 15% is configured to
Liquid, regulation voltage density 1kV/cm or so, spinning distance is in 10cm range, using stainless steel filament collector as reception device, root
According to the concentration regulation spinning time in 6h, relevant nanometer fiber doughnut supporting layer is obtained from reception device.
Second step, electrostatic spraying prepare carbon nanotube functional layer
The carbon nanotube of 60-100nm caliber is dispersed in water after nitration mixture is acidified, and is configured to the dispersion liquid of 5-10mg/mL,
Then in regulation voltage density 1kV/cm or so, spinning distance carries out electrostatic to nanofiber substrate within the scope of 10-20cm
Apply 6h.
Third step, the crosslinking of carbon nanotube/PAN nano-fiber composite film
Molding composite membrane and collector will be prepared to remove together, impregnating 1h in mass concentration is polyvinyl alcohol (0.2%)
In the mixed liquor of glutaric acid (1%), and 2M salt acid for adjusting pH is added to acidity.Deionized water is cleaned after taking-up, 60 DEG C of conditions
Lower dry solidification.Then film and collector are placed in baking oven, 250 DEG C of pre-oxidation treatments together.After pre-oxidation, by film and collector
It is placed in the copper-bath of 1M together and impregnates 10min, hollow-fibre membrane is extracted out from filament collector, deionized water cleaning
It is dried to obtain carbon nanotube/PAN nanofiber composite hollow fiber membrane.
As a result: the carbon nanotube of preparation/PAN nanofiber composite hollow fiber membrane supporting layer and separating layer show net
Shape penetrates through pore structure, and supporting layer aperture is in 1-2 μ m, and compound membrane aperture is in 300nm or so.
Embodiment 3: preparation carbon nanotube/PVDF nanofiber composite flat membrane
The first step, electrospun nanofibers substrate
High molecular polymer Kynoar (PVDF) as substrate is dissolved in the mixed solution (volume of DMF and acetone
Than in 9:1), to be configured to spinning solution of the mass fraction between 18%, regulation voltage density 1kV/cm or so, spinning distance exists
10cm range regulates and controls the spinning time in 10h according to concentration, carries out hot pressing under the conditions of 80 DEG C, obtains from reception device corresponding
Plate nano fibrous membrane substrate.
Second step, electrostatic spraying prepare carbon nanotube functional layer
10-20nm caliber carbon nanotube after nitration mixture is acidified is dispersed in water, and is configured to the dispersion liquid of 5-10mg/mL,
Then in regulation voltage density 1kV/cm or so, spinning distance carries out electrostatic to nanofiber substrate within the scope of 10-20cm
Apply 6h.
Third step, the crosslinking of carbon nanotube/PVDF nano-fiber composite film
Molding composite membrane will be prepared to remove, impregnate 1h in the ethanol solution that mass concentration is phenolic resin (0.2%),
And ethanedioic acid is added and adjusts pH to acidity.Ethyl alcohol cleans after taking-up, dry solidification under the conditions of 60 DEG C.
As a result: the carbon nanotube of preparation/PVDF nanofiber composite flat membrane supporting layer and separating layer show netted
Pore structure is penetrated through, supporting layer aperture is in 400-600nm range, and compound membrane aperture is in 70nm or so.
Embodiment 4: preparation carbon nanotube/Al2O3Nanofiber composite flat membrane
The first step, electrospun nanofibers substrate
Formic acid and acetic acid are added in high purity water according to the mass ratio of 1:1, a certain amount of Al powder, heating stirring is then added
It is completely dissolved to Al powder, then filters removal residue with glass fibre membrane, be configured to Al gel of the mass fraction 10% or so,
Then it adds a certain amount of polyvinylpyrrolidone and increases solution viscosity, regulation voltage density 1kV/cm or so, spinning distance
In 10cm range, the spinning time is regulated and controled in 10h according to concentration, relevant nanometer tunica fibrosa substrate is obtained from reception device.Then
800 DEG C of substrate calcinings are removed, keeping the temperature two hours obtains Al2O3Nano fibrous membrane substrate.
Second step, electrostatic spraying prepare carbon nanotube functional layer
60-100nm caliber carbon nanotube after nitration mixture is acidified is dispersed in water, and is configured to the dispersion liquid of 5-10mg/mL,
Then in regulation voltage density 1kV/cm or so, by calcined Al2O3Nano fibrous membrane substrate is fixed on the reception device, spins
Flight lead carries out electrostatic spraying 6h to nanofiber substrate within the scope of 10-20cm.
Third step, the crosslinking of carbon nanotube/nano composite fiber membrane
Molding composite membrane will be prepared to remove, impregnate 1h in the ethanol solution that mass concentration is phenolic resin (0.2%),
And ethanedioic acid is added and adjusts pH to acidity.Ethyl alcohol cleans after taking-up, dry solidification under the conditions of 60 DEG C.
As a result: carbon nanotube/Al of preparation2O3Nanofiber composite hollow fiber membrane supporting layer and separating layer show
Netted perforation pore structure, supporting layer aperture is in 300-500nm range, and compound membrane aperture is in 100nm or so.
Embodiment 5: preparation carbon nanotube/compound rolled film of PAN nanofiber
The first step, electrospun nanofibers substrate
Macromolecule PAN as substrate is dissolved in DMF, spinning solution of the mass fraction between 15% is configured to, is regulated and controled
Voltage density 1kV/cm or so, spinning distance regulate and control the spinning time in 10h, with stainless-steel roll in 10-20cm range, according to concentration
Formula pipe network is that non-woven membrane is fixed, then cooled to room temperature, obtained by gluing and hot pressing after spinning by reception device
To corresponding rolling nanofiber supporting layer.
Second step, electrostatic spraying prepare carbon nanotube functional layer
The carbon nanotube of 60-100nm caliber is dispersed in water after nitration mixture is acidified, and is configured to the dispersion liquid of 5mg/mL, so
Afterwards in regulation voltage density 1kV/cm or so, spinning distance carries out electrostatic spraying to nanofiber substrate within the scope of 10-20cm
6h。
Third step, the crosslinking of carbon nanotube/PAN nano-fiber composite film
Molding composite membrane will be prepared to remove, impregnating 1h in mass concentration is polyacrylamide (0.2%) and ethanedioic acid
(1%) in mixed liquor, and 2M salt acid for adjusting pH is added to acidity.Deionized water is cleaned after taking-up, dry solid under the conditions of 60 DEG C
Change.
As a result: the carbon nanotube of preparation/compound rolled film of PAN nanofiber shows netted perforation pore structure, composite membrane
Aperture is in 300nm or so.
Claims (4)
1. one kind is based on carbon nanotube/nano fiber composite seperation film, which is characterized in that carbon nanotube/nano fiber should be based on
Composite separating film is divided into supporting layer and functional layer two parts, and the nanofiber of electrostatic spinning preparation is as supporting layer, carbon nanotube
As separating layer, carbon nanotube is covered on nanofiber surface, and crosslinking is solid jointly by crosslinking agent 1 and crosslinking agent 2 for carbon nanotube
It is fixed；Wherein carbon nanotube and nanofiber are one-dimensional linear material, and two kinds of linear materials construct three-dimensional netted pore structure separation
Film, and intermeshed by linear material and interacted between winding enhancing supporting layer and separating layer, constitute stable membrane structure.
2. according to claim 1 be based on carbon nanotube/nano fiber composite seperation film, which is characterized in that the friendship
Join agent 1 and crosslinking agent 2: polyacrylamide and succinic acid, polyvinyl alcohol and glutaraldehyde, polyvinyl alcohol and glutaric acid, phenolic resin
With ethanedioic acid.
3. according to claim 1 or 2 be based on carbon nanotube/nano fiber composite seperation film, which is characterized in that described
Form based on carbon nanotube/nano fiber composite seperation film includes plate membrane, hollow-fibre membrane, three kinds of rolled film.
4. a kind of preparation method based on carbon nanotube/nano fiber composite seperation film, which is characterized in that steps are as follows:
The first step, the preparation of nanofiber supporting layer
(1) spinning material as supporting layer is dissolved in corresponding solvent, is configured to mass fraction between 10%-20%
Spinning solution carries out electrostatic spinning；Spinning solution is pumped into slowly injection by micro-sampling, drop is under electrostatic field, to reception
Device migration is drawn into nanofiber, regulates and controls electrostatic spinning voltage density 1kV/cm, spinning distance is in 10cm-20cm range, root
According to the concentration regulation spinning time in 4-20h, relevant nanometer filament support layer is obtained from reception device；
Wherein, different according to film form, concrete operations are as follows:
Plate membrane: electrostatic spinning is received using idler wheel collecting nanofibers device or plate collecting nanofibers device and prepares Nanowire
Dimension, directly removes hot-forming flat support layer from collector surface wait collect to finish；
Hollow-fibre membrane: it using the continuous filament collector of dynamic, in electrostatic spinning filamentation process, controls continuous filament and receives
Storage with fixed rate by receiving nanofiber region after, filament collector is sent to heating room, according to material thermal resistance plus
Nanofiber is shunk in thermostabilization；Then filament collector is immersed into 0.1mol/L pickle or copper salt solution 5-60min, taken out later
From filament collector, doughnut supporting layer is obtained；
Rolled film: it using conductive rolling center pipe network as collecting nanofibers device, is finished wait collect, by center pipe network and nanometer
Fiber is hot-forming together, is then fixed non-woven membrane by gluing, then cools to room temperature to obtain rolled film supporting layer；
Second step, electrostatic spraying prepare carbon nanotube functional layer
Carbon nanotube after nitration mixture is acidified is dispersed in water, and is configured to the dispersion liquid of 5-10mg/mL, and nitration mixture is that volume ratio is 3:
The 1 95-98wt.% concentrated sulfuric acid and 65-68wt.% concentrated nitric acid；Then in regulation voltage density 1kV/cm, spinning distance is in 10-
Electrostatic spraying is carried out to nanofiber supporting layer within the scope of 20cm；
Third step, the crosslinking of carbon nanotube/nano composite fiber membrane
Molding composite membrane will be prepared to remove, be immersed in the mixed liquor of crosslinking agent 1 and crosslinking agent 2, and the adjusting of 2M hydrochloric acid is added
PH to 2；Deionized water is cleaned after taking-up, dry solidification under the conditions of 60 DEG C.
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