CN108939945A - A kind of compound carbon film of stable ceramic base and preparation method thereof - Google Patents
A kind of compound carbon film of stable ceramic base and preparation method thereof Download PDFInfo
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- CN108939945A CN108939945A CN201810800787.8A CN201810800787A CN108939945A CN 108939945 A CN108939945 A CN 108939945A CN 201810800787 A CN201810800787 A CN 201810800787A CN 108939945 A CN108939945 A CN 108939945A
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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
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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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
- B01D69/06—Flat membranes
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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
- B01D69/08—Hollow fibre membranes
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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
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to technical field of membrane, a kind of compound carbon film of stable ceramic base and preparation method thereof is provided.Using aperture 100-2000nm porous ceramic film as supporting layer, be crosslinked by vacuum filtration carbon nano tube dispersion liquid, polyvinyl alcohol crosslinked, succinic acid, dry and heat treatment process, in ceramic membrane surface formation carbon nanotube separation layer.The aperture for the compound carbon film being related to is controllable from micro-filtration to ultrafiltration range.Preparation step of the invention is simple；With preferable stability, mechanical strength, excellent conductive performance and permeance property；Preparation cost is low；Convenient for the preparation of the compound carbon film of various forms ceramic base.
Description
Technical field
The invention belongs to technical field of membrane, it is related to a kind of compound carbon film of stable ceramic base and preparation method thereof.
Background technique
With water quality deterioration and shortage of water resources, membrane technology has obtained further popularization in field of water pollution control and has answered
With people also proposed requirement higher and higher to seperation film, for example require membrane material: thermal stability is good, at higher temperatures may be used
To use；Chemical stability is good, acid and alkali-resistance, chlorine-resistant；Biological stability is good, and antimicrobial erosiveness is strong etc..And current
The above requirement for membrane stability is not able to satisfy to widely applied organic polymer films.Carbon film is as a kind of inorganic material
Seperation film, thermal stability and chemical stability are preferable, and good electric conductivity and biggish specific surface area are the tax of carbonaceous seperation film
Given the functionality such as additional electrowetting, electric repulsions, antipollution, high-adsorption-capacity, with good application prospect with the valence of research
Value.
Existing research (Journal of Porous Materials, 2009,16 (2): 197-203；Nature
Communications, 2013,4:2220) use the organic materials such as coal, high molecular polymer, biomass to pass through high temperature cabonization mistake
Journey prepares carbon film using nano-carbon material assembling process.The carbon film matter that high temperature cabonization process is prepared is crisp, and pyrocarbon
Change process the high requirements on the equipment, and energy consumption is very big, the carbon film of this kind of method preparation is at high cost, and mechanical strength and stability are poor.
And the carbon film that nanomaterial assembly mode is prepared causes to separate because connecting between carbon nanomaterial without stronger active force
Film is easy to be dispersed in water again under sluicing, and stability has very big problem.
Therefore, seeking a kind of carbon film that can not needed high temperature cabonization and have good stability becomes the emphasis of research.
Summary of the invention
It is poor present invention is generally directed to film forming stability existing for current carbon film preparation process and some processes need high temperature
Carbonization, the higher problem of cost energy consumption provide a kind of based on ceramic membrane supporting layer, it is only necessary to it is heat-treated in 250-300 DEG C of range, by
Carbon nanotube after crosslinking stablizes compound carbon film as separating layer.Extra crosslinking agent is removed by controlling heat treatment time,
The use for reducing crosslinking agent is influenced caused by membrane permeability, enhances the bond strength between the carbon-coating and supporting layer of compound carbon film
(attached drawing 3,4).
Technical solution of the present invention:
A kind of compound carbon film of stable ceramic base, is divided into supporting layer and separating layer two parts, aperture is 100-2000nm's
Ceramic membrane is supported on support layer surface as separating layer, separating layer as supporting layer, carbon nanotube layer；Carbon nanotube after acidification
By polyvinyl alcohol and the common crosslinked action of succinic acid, guarantee the stability of composite membrane carbon-coating；Heat treatment process removes extra
Crosslinking agent, while enhancing the bond strength between the carbon-coating and supporting layer of compound carbon film.
It is single wall, double-walled or the multi-walled carbon nanotube of 2~100nm that the carbon nanotube, which selects diameter,.
The aperture of the compound carbon film of the ceramic base is by carbon nanotube diameter, polyvinyl alcohol concentration and heat treatment time tune
Control.
The cross-linked stable agent is polyvinyl alcohol and succinic acid quasi polymer.
A kind of preparation method of the compound carbon film of stable ceramic base, steps are as follows:
The first step, supporter pretreatment
After supporter is ultrasonically treated 10min in ethanol, cleans to neutrality and be dried for standby using deionized water；
Second step, the preparation of carbon nano tube dispersion liquid
According to the demand in aperture, after the carbon nanotube that caliber is 2~100nm is acidified by sulfuric acid and nitric acid collective effect
Carbon nano tube dispersion liquid even to be distributed in water, that preparation concentration is 0.5~5mg/mL, is acidified both the concentrated sulfuric acid and concentrated nitric acid used
Volume ratio be 3:1；
Third step, the molding of the compound carbon film of ceramic base
Firstly, forming different thickness as needed on the carbon nanotube vacuum filtration to ceramic membrane supporting layer of different tube diameters
Then the carbon nanotube separation layer of degree filters the poly-vinyl alcohol solution that mass concentration is 0.2%~1%, after to be soaked in quality dense
Degree is 1h in 1% succinic acid solution；Deionized water is cleaned after taking-up, dry solidification under the conditions of 60 DEG C, finally at 250-300 DEG C
Under the conditions of heat treatment 1-4h obtain the compound carbon film of stable ceramic base.
Beneficial effects of the present invention: preparation step of the invention is simple；With preferable stability, mechanical strength, good
Electric conductivity and permeance property；Preparation cost is low；Convenient for the preparation of the compound carbon film of various forms ceramic base.
Detailed description of the invention
Fig. 1 is the scanning electron microscopic picture of the compound carbon film ceramic support of ceramic base.
Fig. 2 is the scanning electron microscopic picture of the compound carbon film carbon nanotube separation layer of ceramic base.
Fig. 3 is heat treatment front and back, ceramic base composite carbon membrane permeability figure of changing.
Fig. 4 is heat treatment front and back, the compound carbon film scratch experiment comparative result figure of ceramic base.
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.
The compound carbon film of ceramic base in the preparation of embodiment 1 ultrafiltration aperture.
It uses the porous ceramic film that aperture is 400nm as supporter, prepares aperture in 20-100nm wide-ultra filter opening diameter
The compound carbon film of ceramic base, steps are as follows:
The first step, the pretreatment of supporter earthenware slab film
After handling 10min with EtOH Sonicate as the earthenware slab film of supporter, cleaned using deionized water to neutrality
And it is dried for standby；
Second step, the preparation of carbon nano tube dispersion liquid
According to the demand in aperture, caliber is evenly spread to for carbon nanotube after the acidification of 40~60nm and prepares concentration in water
For the dispersion liquid of 0.5mg/mL；
Third step, the molding of the compound carbon film of ceramic base
Firstly, then filtering the poly- second that mass concentration is 0.2-1% on carbon nanotube vacuum filtration to porous ceramic film
Enolate solution, after be soaked in mass concentration be 1% succinic acid solution in 1h.Deionized water is cleaned after taking-up, under the conditions of 60 degree
Dry solidification is finally heat-treated 1h under the conditions of 250 DEG C and obtains the compound carbon film of stable ceramic base.
As a result: being measured according to aperture tester, the aperture of the compound carbon film of obtained ceramic base belongs to ultrafiltration in 70nm or so
Film, membrane flux 698L*m-2bar-1h-1.Stereoscan photograph shows that carbon nanotube is staggered to form reticular structure, and uniform fold exists
In ceramic membrane substrate.
Embodiment 2 prepares the compound carbon film of ceramic base in micro-filtration aperture.
It uses the porous ceramic film that aperture is 400nm as supporter, prepares ceramic base of the aperture within the scope of 100-300nm
Compound carbon film, steps are as follows:
The first step, the pretreatment of supporter earthenware slab film
After handling 10min with EtOH Sonicate as the earthenware slab film of supporter, cleaned using deionized water to neutrality
And it is dried for standby；
Second step, the preparation of carbon nano tube dispersion liquid
According to the demand in aperture, caliber is evenly spread to for carbon nanotube after the acidification of 40~60nm and prepares concentration in water
For the dispersion liquid of 0.5mg/mL；
Third step, the molding of the compound carbon film of ceramic base
Firstly, then filtering the polyethylene that mass concentration is 0.2% on carbon nanotube vacuum filtration to porous ceramic film
Alcoholic solution, after be soaked in mass concentration be 1% succinic acid solution in 1h.Deionized water is cleaned after taking-up, is done under the conditions of 60 degree
Dry solidification is finally heat-treated 4h under the conditions of 300 DEG C and obtains the compound carbon film of stable ceramic base.
As a result: being measured according to aperture tester, the aperture of the compound carbon film of obtained ceramic base belongs to micro- in 140nm or so
Filter membrane, membrane flux 1057L*m-2bar-1h-1.Stereoscan photograph shows that carbon nanotube is staggered to form reticular structure, uniformly covers
It covers in ceramic membrane substrate.
Embodiment 3 prepares the compound carbon film of ceramic base doughnut in micro-filtration aperture.
It uses the porous ceramics hollow-fibre membrane that aperture is 1 μm as supporter, prepares aperture within the scope of 100-1000nm
The compound carbon film of ceramic base doughnut, steps are as follows:
The first step, the pretreatment of supporter ceramic hollow fibrous membrane
By as the ceramic hollow fibrous membrane of supporter with EtOH Sonicate handle 10min after, using deionized water clean to
Neutrality is simultaneously dried for standby；
Second step, the preparation of carbon nano tube dispersion liquid
According to the demand in aperture, carbon nanotube after acidification that caliber is 60~100nm is evenly spread in water prepare it is dense
Degree is the dispersion liquid of 0.5mg/mL；
Third step, the molding of the compound carbon film of ceramic base
Firstly, then filtering mass concentration is 0.2% by carbon nanotube vacuum filtration to porous ceramics hollow-fibre membrane
Poly-vinyl alcohol solution, after be soaked in mass concentration be 1% succinic acid solution in 1h.Deionized water is cleaned after taking-up, and 60 degree
Under the conditions of dry solidification, finally under the conditions of 300 DEG C be heat-treated 4h obtain the stable compound carbon film of ceramic base doughnut.
As a result: being measured according to aperture tester, the aperture of the obtained compound carbon film of ceramic base doughnut is on the left side 260nm
The right side belongs to microfiltration membranes, membrane flux 3100L*m-2bar-1h-1.Stereoscan photograph shows that carbon nanotube is staggered to form netted knot
Structure, uniform fold is in ceramic membrane substrate.
Embodiment described above, only typical embodiment in the present invention, does not constitute improper limitations of the present invention, therefore
It is all according to obvious change described in scope of the present invention patent and other changes for not departing from essence of the invention,
It should include within protection scope of the present invention.
Claims (7)
1. a kind of compound carbon film of stable ceramic base, which is characterized in that the compound carbon film of stable ceramic base is divided into support
Layer and separating layer two parts, ceramic membrane of the aperture in 100-2000nm are used as supporting layer, and carbon nanotube layer is separated as separating layer
Layer is supported on support layer surface；Carbon nanotube after acidification passes through polyvinyl alcohol and the common crosslinked action of succinic acid, guarantees compound
The stability of film carbon-coating.
2. the compound carbon film of stable ceramic base according to claim 1, which is characterized in that the carbon nanotube is selected straight
Diameter is single wall, double-walled or the multi-walled carbon nanotube of 2~100nm.
3. the compound carbon film of stable ceramic base according to claim 1 or 2, which is characterized in that the cross-linked stable agent
For polyvinyl alcohol and succinic acid quasi polymer.
4. the compound carbon film of stable ceramic base according to claim 1 or 2, which is characterized in that the ceramic base is compound
The aperture of carbon film is regulated and controled by carbon nanotube diameter, polyvinyl alcohol concentration and heat treatment time.
5. the compound carbon film of stable ceramic base according to claim 3, which is characterized in that the compound carbon film of the ceramic base
Aperture by carbon nanotube diameter, polyvinyl alcohol concentration and heat treatment time regulate and control.
6. a kind of preparation method of the compound carbon film of stable ceramic base, which is characterized in that steps are as follows:
The first step, supporter pretreatment
After supporter is ultrasonically treated 10min in ethanol, cleans to neutrality and be dried for standby using deionized water；
Second step, the preparation of carbon nano tube dispersion liquid
According to the demand in aperture, uniformly divide after the carbon nanotube that caliber is 2~100nm is acidified by sulfuric acid and nitric acid collective effect
It is scattered in water, the carbon nano tube dispersion liquid that preparation concentration is 0.5~5mg/mL；
Third step, the molding of the compound carbon film of ceramic base
Firstly, forming different-thickness as needed on the carbon nanotube vacuum filtration to ceramic membrane supporting layer of different tube diameters
Then carbon nanotube separation layer filters the poly-vinyl alcohol solution that mass concentration is 0.2%~1%, after be soaked in mass concentration and be
1h in 1% succinic acid solution；Deionized water is cleaned after taking-up, dry solidification under the conditions of 60 DEG C, finally in 250-300 DEG C of condition
Lower heat treatment 1-4h obtains the compound carbon film of stable ceramic base.
7. preparation method according to claim 6, which is characterized in that be acidified the volume of both concentrated sulfuric acid and concentrated nitric acid used
Than for 3:1.
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| CN201810800787.8A CN108939945A (en) | 2018-07-20 | 2018-07-20 | A kind of compound carbon film of stable ceramic base and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327789A (en) * | 2019-07-05 | 2019-10-15 | 大连理工大学 | A kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof |
| CN111545078A (en) * | 2020-05-15 | 2020-08-18 | 洛阳中超新材料股份有限公司 | Flat ceramic membrane and preparation method thereof |
| WO2021003599A1 (en) * | 2019-07-05 | 2021-01-14 | 大连理工大学 | Carbon nanotube/nanofiber conductive composite membrane and manufacturing method therefor |
| CN113893708A (en) * | 2021-09-24 | 2022-01-07 | 南京南开伊沃环境研究院有限公司 | Preparation method of ceramic-based loaded carbon nanotube composite membrane |
| CN117164045A (en) * | 2023-07-21 | 2023-12-05 | 大连海事大学 | Convection type solar interface evaporator and preparation method and application thereof |
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| CN103418252A (en) * | 2013-07-20 | 2013-12-04 | 大连理工大学 | Ceramic base carbon nano tube inorganic composite membrane and preparation method thereof |
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| CN103418252A (en) * | 2013-07-20 | 2013-12-04 | 大连理工大学 | Ceramic base carbon nano tube inorganic composite membrane and preparation method thereof |
Non-Patent Citations (1)
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| YI, GANG: "Enhanced separation performance of carbon nanotube-polyvinyl alcohol composite membranes for emulsified oily wastewater treatment under electrical assistance", 《SEPARATION AND PURIFICATION TECHNOLOGY》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110327789A (en) * | 2019-07-05 | 2019-10-15 | 大连理工大学 | A kind of carbon nanotube/nano fiber conductive composite film and preparation method thereof |
| WO2021003599A1 (en) * | 2019-07-05 | 2021-01-14 | 大连理工大学 | Carbon nanotube/nanofiber conductive composite membrane and manufacturing method therefor |
| CN110327789B (en) * | 2019-07-05 | 2022-02-15 | 大连理工大学 | Carbon nano tube/nano fiber conductive composite film and preparation method thereof |
| CN111545078A (en) * | 2020-05-15 | 2020-08-18 | 洛阳中超新材料股份有限公司 | Flat ceramic membrane and preparation method thereof |
| CN113893708A (en) * | 2021-09-24 | 2022-01-07 | 南京南开伊沃环境研究院有限公司 | Preparation method of ceramic-based loaded carbon nanotube composite membrane |
| CN117164045A (en) * | 2023-07-21 | 2023-12-05 | 大连海事大学 | Convection type solar interface evaporator and preparation method and application thereof |
| CN117164045B (en) * | 2023-07-21 | 2024-04-30 | 大连海事大学 | Convection type solar interface evaporator and preparation method and application thereof |
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Application publication date: 20181207 |