CN113046927A - PTFE/CNT composite nanofiber membrane and preparation method thereof - Google Patents
PTFE/CNT composite nanofiber membrane and preparation method thereof Download PDFInfo
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- CN113046927A CN113046927A CN202110476652.2A CN202110476652A CN113046927A CN 113046927 A CN113046927 A CN 113046927A CN 202110476652 A CN202110476652 A CN 202110476652A CN 113046927 A CN113046927 A CN 113046927A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
- D04H1/4291—Olefin series
Abstract
The invention discloses a PTFE/CNT composite nanofiber membrane and a preparation method thereof. Because PTFE is difficult to dissolve in all solvents, the invention adopts PTFE suspension dispersion liquid, which is beneficial to environmental protection, and the added CNT promotes the functionalization and high performance of the prepared film, so that the film has great application potential in the fields of film distillation, oil-water separation, electromagnetic wave absorption, electromagnetic shielding and the like.
Description
Technical Field
The invention relates to the technical field of composite nanofiber membranes, in particular to a PTFE/CNT composite nanofiber membrane and a preparation method thereof.
Background
Polytetrafluoroethylene (PTFE) is a non-polar linear crystalline polymer with many unique physical and chemical properties, such as good electrical insulation and thermal stability, excellent aging resistance, minimal water absorption, excellent resistance to ultraviolet radiation, and excellent chemical inertness. Therefore, the coating is widely applied to the fields of electronics and electricity, corrosion prevention and wear reduction, machinery, petrochemical industry, textile and aerospace.
At present, commercial PTFE membranes are mostly prepared by mechanical stretching and a forming process method of a pore-forming agent, the energy consumption is large in the preparation process, the environment is polluted, and the obtained PTFE membranes have large pore diameter difference and low porosity. Moreover, PTFE itself is poorly soluble in various solvents, and the melt strength in the molten state is very high, so that PTFE films cannot be directly prepared by solution spinning and melt spinning.
In addition, most of the prepared PTFE nano fiber membranes at present are pure PTFE nano fiber membranes, the mechanical property, the dielectric property and other properties of the PTFE nano fiber membranes are difficult to meet the application in some fields, and in order to overcome the defects and widen the application field of the PTFE nano fiber membranes, the addition of functional nano fillers to enable the PTFE nano fiber membranes to have high performance and multiple functions is a difficult point and a hot point problem which needs to be solved in the field of the PTFE membranes at present.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a PTFE/CNT composite nanofiber membrane and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a PTFE/CNT composite nanofiber membrane comprises the following steps:
1) preparing a PEO solution: dissolving polyethylene oxide (PEO) in deionized water, and uniformly stirring to obtain a PEO solution;
2) preparing a PTFE/PEO mixed solution: adding the PTFE suspension into the PEO solution, and uniformly stirring to obtain a PTFE/PEO mixed solution;
3) preparing a PTFE/PEO/CNT spinning solution: adding the aqueous dispersion of the Carbon Nano Tubes (CNT) into the PTFE/PEO mixed solution, and uniformly stirring to obtain a PTFE/PEO/CNT mixed solution;
4) preparing a PTFE/CNT composite nanofiber membrane by electrostatic spinning: and (3) preparing a PTFE/PEO/CNT composite nanofiber membrane precursor from the PTFE/PEO/CNT mixed solution through electrostatic spinning, and performing heat treatment to finally obtain the PTFE/CNT composite nanofiber membrane.
Further, step 1) is to divide the weight average intoA quantum number of 105-107g/mol of the PEO powder with ultrahigh molecular weight is dissolved in water with the temperature of 35-45 ℃ and is evenly stirred to obtain a PEO solution.
The PEO content in the PEO solution is 8-12 wt.%, and the PTFE content in the PTFE suspension is 55-65 wt.%.
The mass ratio of the PTFE suspension to the PEO solution in step 2) was 88: 12.
The content of the CNT in the PTFE/PEO/CNT mixed solution is 0.5 wt.% to 1 wt.%.
The electrostatic spinning voltage in the step 4) is 14-16kV, the distance between the spinning nozzle and the counter electrode roller collector is 14-16cm, and the spinning flow rate is 0.8-1.2 ml/h.
The heat treatment in the step 4) is to firstly place the PTFE/PEO/CNT composite fiber membrane in a vacuum drying box (45 ℃) for drying for at least 12h, and then sinter the PTFE/PEO/CNT composite fiber membrane in a muffle furnace at the temperature of 330 ℃ and 400 ℃ to decompose and remove PEO, so as to obtain the PTFE/CNT composite nanofiber membrane.
The invention overcomes the defect of difficult processing of the traditional PTFE, adopts the electrostatic spinning technology, uses PTFE suspension dispersion liquid and combines water-soluble PEO as a spinning aid (sacrificial body) to prepare the PTFE nano-fiber film, and finally prepares the PTFE/CNT composite nano-fiber film with good mechanics, wettability, conductivity and dielectricity by introducing CNT on the PTFE nano-fiber. Since PTFE is difficult to dissolve in all solvents, the PTFE suspension dispersion liquid is adopted in the invention, which is beneficial to environmental protection, and the added CNT promotes the functionalization and high performance of the prepared film.
The invention also has the following advantages:
1. the surface structure, the mechanical property and the hydrophobic property of the PTFE composite nanofiber are optimized by introducing the CNT, so that the PTFE composite nanofiber has great application potential in the fields of membrane distillation, oil-water separation, electromagnetic wave absorption (dielectric), electromagnetic shielding (electric conduction) and the like.
2. The prepared PTFE/CNT composite nanofiber porous membrane has continuous fibers, uniform pore diameter and excellent thermal stability, mechanical property and hydrophobic property.
3. In the preparation process, water system polyethylene oxide (PEO) and water system PTFE suspension are used as raw materials, and an organic solvent is not used, so that the preparation method is safe and is beneficial to environmental protection. Therefore, the method has the advantages of simple operation, economy and environmental protection.
Drawings
Fig. 1 is a schematic diagram of a PTFE/CNT composite nanofiber membrane preparation process.
Fig. 2(a) is a scanning electron micrograph of a pure PTFE nanofiber membrane prepared by electrospinning according to example 3, and fig. 2(b) is a partially enlarged view of fig. 2 (a).
Fig. 3(a) is a scanning electron micrograph of a PTFE/CNT (99.5 wt.%: 0.5 wt.%) composite nanofiber membrane prepared by electrospinning according to example 3, and fig. 3(b) is a partial enlarged view of fig. 3 (a).
Fig. 4(a) is a scanning electron micrograph of a PTFE/CNT (99.0 wt.%: 1.0 wt.%) composite nanofiber membrane prepared by electrospinning according to example 3, and fig. 4(b) is a partial enlarged view of fig. 4 (a).
Fig. 5 is the water contact angle of the composite nanofiber membrane prepared in example 3, (a) a pure PTFE nanofiber membrane, (b) a PTFE/CNT (0.5 wt.%) composite nanofiber membrane, (c) PTFE/CNT (1.0 wt.%).
Fig. 6 is a stress-strain curve for pure PTFE nanofiber membrane, PTFE/CNT (0.5 wt.%) composite nanofiber membrane, PTFE/CNT (1.0 wt.%) composite nanofiber membrane prepared in example 3.
Detailed Description
Example 1
A preparation method of a PTFE/CNT composite nanofiber membrane comprises the following steps:
1) preparing a PEO solution: will have a weight average molecular weight of 105Dissolving g/mol of ultrahigh molecular weight PEO powder in water at 35 ℃, and uniformly stirring to obtain a PEO solution with the PEO content of 8 wt.%;
2) preparing a PTFE/PEO mixed solution: adding a PTFE suspension with PTFE content of 55 wt.% into the PEO solution, and uniformly stirring to obtain a PTFE/PEO mixed solution;
the mass ratio of the PTFE suspension to the PEO solution is 88: 12;
3) preparing a PTFE/PEO/CNT spinning solution: adding the aqueous dispersion of the CNT into the PTFE/PEO mixed solution, and uniformly stirring to obtain a PTFE/PEO/CNT mixed solution, wherein the content of the CNT in the PTFE/PEO/CNT mixed solution is 0.5 wt.%;
4) preparing a PTFE/CNT composite nanofiber membrane by electrostatic spinning: preparing a PTFE/PEO/CNT composite nanofiber membrane precursor by carrying out electrostatic spinning on the PTFE/PEO/CNT mixed solution, wherein the electrostatic spinning voltage is 14kV, the distance from a spinning nozzle to a counter electrode roller collector is 14cm, and the spinning flow rate is 0.8 ml/h;
and then, drying the PTFE/PEO/CNT composite fiber membrane precursor in a vacuum drying oven at 45 ℃ for 12h, and sintering in a muffle furnace at 330 ℃ to decompose and remove PEO, thereby finally obtaining the PTFE/CNT composite nanofiber membrane.
Example 2
A preparation method of a PTFE/CNT composite nanofiber membrane comprises the following steps:
1) preparing a PEO solution: will have a weight average molecular weight of 107Dissolving g/mol of ultrahigh molecular weight PEO powder in water at 45 ℃, and uniformly stirring to obtain a PEO solution with the PEO content of 12 wt.%;
2) preparing a PTFE/PEO mixed solution: adding a PTFE suspension with the PTFE content of 65 wt.% into the PEO solution, and uniformly stirring to obtain a PTFE/PEO mixed solution;
the mass ratio of the PTFE suspension to the PEO solution is 88: 12;
3) preparing a PTFE/PEO/CNT spinning solution: adding the aqueous dispersion of the CNT into the PTFE/PEO mixed solution, and uniformly stirring to obtain a PTFE/PEO/CNT mixed solution, wherein the content of the CNT in the PTFE/PEO/CNT mixed solution is 0.75 wt.%;
4) preparing a PTFE/CNT composite nanofiber membrane by electrostatic spinning: preparing a PTFE/PEO/CNT composite nanofiber membrane precursor by carrying out electrostatic spinning on the PTFE/PEO/CNT mixed solution, wherein the electrostatic spinning voltage is 6kV, the distance from a spinning nozzle to a counter electrode roller collector is 16cm, and the spinning flow rate is 1.2 ml/h;
and then, drying the PTFE/PEO/CNT composite fiber membrane in a vacuum drying oven at 45 ℃ for 12h, and then sintering in a muffle furnace at 400 ℃ to decompose and remove PEO, thereby finally obtaining the PTFE/CNT composite nanofiber membrane.
Example 3
A preparation method of a PTFE/CNT composite nanofiber membrane comprises the following steps:
1) preparing a PEO solution: will have a weight average molecular weight of 106Dissolving g/mol of ultrahigh molecular weight PEO powder in water at 40 ℃, and uniformly stirring to obtain a PEO solution with the PEO content of 10 wt.%;
2) preparing a PTFE/PEO mixed solution: adding a PTFE suspension with PTFE content of 60 wt.% into the PEO solution, and uniformly stirring to obtain a PTFE/PEO mixed solution;
the mass ratio of the PTFE suspension to the PEO solution is 88: 12;
3) preparing a PTFE/PEO/CNT spinning solution: adding the aqueous dispersion of the CNT into the PTFE/PEO mixed solution, and uniformly stirring to obtain a PTFE/PEO/CNT mixed solution, wherein the content of the CNT in the PTFE/PEO/CNT mixed solution is 0 wt.%, 0.5 wt.%, and 1 wt.%, respectively;
4) preparing a PTFE/CNT composite nanofiber membrane by electrostatic spinning: preparing a PTFE/PEO/CNT composite nanofiber membrane precursor by carrying out electrostatic spinning on the PTFE/PEO/CNT mixed solution, wherein the electrostatic spinning voltage is 15kV, the distance from a spinning nozzle to a counter electrode roller collector is 15cm, and the spinning flow rate is 1 ml/h;
and then, drying the PTFE/PEO/CNT composite fiber membrane in a vacuum drying oven at 45 ℃ for 12h, and then sintering in a muffle furnace at 380 ℃ to decompose and remove PEO, thereby finally obtaining the PTFE/CNT composite nanofiber membrane.
Table 1 shows tensile strength, elongation at break, young's modulus of the pure PTFE nanofiber membrane, PTFE/CNT (0.5 wt.%) composite nanofiber membrane, PTFE/CNT (1 wt.%) composite nanofiber membrane prepared in example 3.
TABLE 1
| Sample (I) | Tensile strength(MPa) | Elongation at Break (%) | Young's modulus (MPa) |
| PTFE | 2.50±0.13 | 123.0±0.13 | 2.03±0.11 |
| PTFE/CNT(0.5wt.％) | 4.03±0.26 | 320.1±0.14 | 1.25±0.08 |
| PTFE/CNT(1.0wt.％) | 5.92±0.42 | 330.4±0.12 | 1.79±0.12 |
As can be seen from table 1, the mechanical properties of the PTFE composite nanofiber were optimized by introducing CNT.
Claims (8)
1. A preparation method of a PTFE/CNT composite nanofiber membrane is characterized by comprising the following steps: the method comprises the following steps:
1) preparing a PEO solution: dissolving PEO in deionized water, and uniformly stirring to obtain a PEO solution;
2) preparing a PTFE/PEO mixed solution: adding the PTFE suspension into the PEO solution, and uniformly stirring to obtain a PTFE/PEO mixed solution;
3) preparing a PTFE/PEO/CNT spinning solution: adding the CNT aqueous dispersion into the PTFE/PEO mixed solution, and uniformly stirring to obtain a PTFE/PEO/CNT mixed solution;
4) preparing a PTFE/CNT composite nanofiber membrane by electrostatic spinning: and (3) preparing a PTFE/PEO/CNT composite nanofiber membrane precursor from the PTFE/PEO/CNT mixed solution through electrostatic spinning, and performing heat treatment to finally obtain the PTFE/CNT composite nanofiber membrane.
2. The method of claim 1, wherein the PTFE/CNT composite nanofiber membrane is prepared by: step 1) is to adjust the weight average molecular weight to 105-107g/mol of the PEO powder with ultrahigh molecular weight is dissolved in water with the temperature of 35-45 ℃ and is evenly stirred to obtain a PEO solution.
3. The method of claim 1, wherein the PTFE/CNT composite nanofiber membrane is prepared by: the PEO content in the PEO solution is 8-12 wt.%, and the PTFE content in the PTFE suspension is 55-65 wt.%.
4. The method of claim 1, wherein the PTFE/CNT composite nanofiber membrane is prepared by: the mass ratio of the PTFE suspension to the PEO solution in step 2) was 88: 12.
5. The method of claim 1, wherein the PTFE/CNT composite nanofiber membrane is prepared by: the content of the CNT in the PTFE/PEO/CNT mixed solution is 0.5 wt.% to 1 wt.%.
6. The method of claim 1, wherein the PTFE/CNT composite nanofiber membrane is prepared by: the electrostatic spinning voltage in the step 4) is 14-16kV, the distance between the spinning nozzle and the counter electrode roller collector is 14-16cm, and the spinning flow rate is 0.8-1.2 ml/h.
7. The method of claim 1, wherein the PTFE/CNT composite nanofiber membrane is prepared by: and 4) the heat treatment in the step 4) is to firstly place the PTFE/PEO/CNT composite fiber membrane in a vacuum drying oven for drying for at least 12h, and then sinter the PTFE/PEO/CNT composite fiber membrane in a muffle furnace at the temperature of 330-.
8. PTFE/CNT composite nanofiber membrane obtainable by the preparation process according to any one of claims 1 to 7.
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| CN113713638A (en) * | 2021-10-14 | 2021-11-30 | 山东海科创新研究院有限公司 | Double-layer high-strength super-hydrophobic separation membrane and preparation method and application thereof |
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| CN113713638A (en) * | 2021-10-14 | 2021-11-30 | 山东海科创新研究院有限公司 | Double-layer high-strength super-hydrophobic separation membrane and preparation method and application thereof |
| CN113713638B (en) * | 2021-10-14 | 2024-02-13 | 山东海科创新研究院有限公司 | Double-layer high-strength super-hydrophobic separation membrane and preparation method and application thereof |
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Application publication date: 20210629 |