CN109012221B - Method for preparing high-hydrophilicity PVDF (polyvinylidene fluoride) filter membrane by magnetron sputtering SiO2 nano particles and product thereof - Google Patents

Method for preparing high-hydrophilicity PVDF (polyvinylidene fluoride) filter membrane by magnetron sputtering SiO2 nano particles and product thereof Download PDF

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CN109012221B
CN109012221B CN201810990776.0A CN201810990776A CN109012221B CN 109012221 B CN109012221 B CN 109012221B CN 201810990776 A CN201810990776 A CN 201810990776A CN 109012221 B CN109012221 B CN 109012221B
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pvdf
filter membrane
sio
hydrophilicity
nano particles
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CN109012221A (en
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王飞鹏
穆朋
万春香
***
李剑
黄正勇
胡克林
王开正
赵琦
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Chongqing University
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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
    • B01D69/02—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
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physical Vapour Deposition (AREA)
  • Filtering Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The invention discloses a method for utilizing magnetic control sputteringSiO-emitting SiO2The invention discloses a method for preparing a high-hydrophilicity PVDF (polyvinylidene fluoride) filter membrane by using nano particles and a product thereof, and relates to a method for preparing the high-hydrophilicity PVDF filter membrane by using nano particles and a product thereof2The method for improving the hydrophilicity of the PVDF filter membrane by the nano particles comprises the steps of preparing the PVDF single nano fiber filter membrane by an electrostatic spinning method, and sputtering SiO on the surface of the PVDF filter membrane fiber by direct current sputtering2Nano particles, PVDF nano fiber filter membrane prepared by electrostatic spinning method has certain hydrophobicity, and SiO is sputtered by near one step2The nano particles introduce hydrophilic groups on the surface of the filter membrane so as to improve the hydrophilicity of the filter membrane. The hydrophilic filter membrane prepared by the invention is suitable for the fields of membrane distillation, sewage treatment, oil-water separation and the like, can enhance the anti-pollution capacity of the membrane, has good practicability, is simple to realize by adopting simple mechanical equipment, and has strong repeatability.

Description

Method for preparing high-hydrophilicity PVDF (polyvinylidene fluoride) filter membrane by magnetron sputtering SiO2 nano particles and product thereof
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a method for preparing SiO by magnetron sputtering2A method for preparing a high-hydrophilicity PVDF filter membrane by nano particles and a product prepared by the method.
Background
Polyvinylidene fluoride (PVDF) is favored by researchers of separation membranes for its excellent chemical stability, radiation resistance, stain resistance, heat resistance and easy film-forming properties. However, the PVDF membrane has low surface energy, strong hydrophobicity, easy membrane pollution, fast membrane flux reduction and limited application to a certain extent, so that the hydrophilicity of the PVDF membrane needs to be improved.
The preparation method of the fiber filter membrane mainly comprises a sol-gel method, a phase separation method, an etching method, a self-assembly method, chemical vapor deposition and the like, but the methods have the defects of complex preparation process, overhigh cost and the like. The electrostatic spinning method is the only method for preparing continuous and uniform nano fibers at present, and the fiber membrane prepared by the method has the properties of high porosity, large specific surface area, high uniformity and the like. In order to further enhance the hydrophilicity, the pollution resistance and the mechanical property of the filter membrane prepared by electrostatic spinning, the method for modifying the nanofiber by adding the inorganic nano material into the polymer nanofiber is one of the main methods for modifying the nanofiber. For example, patent No. CN201110068729.9 proposes a method for preparing hydrophilic nano TiO2Adding the sol into a casting solution containing PVDF, an organic solvent and an additive, and preparing the hydrophilic PVDF ultrafiltration membrane by using a phase conversion method. However, the nano particles have the problems of poor dispersibility, easy agglomeration and the like in the solution, and the prepared hydrophilic filter membrane has uneven surface nano particle distribution, which affects the membrane separation performance. Therefore, a method for preparing a PVDF membrane with uniformly distributed nanoparticles and high hydrophilicity is urgently needed.
Disclosure of Invention
In view of the above, the present invention provides a method for forming SiO by magnetron sputtering2The method for preparing the PVDF filter membrane with high hydrophilicity by the nano particles can effectively solve the problem of nano particle agglomeration when the inorganic nano/organic composite nanofiber membrane is prepared only by electrostatic spinning, and simultaneously improves the hydrophilicity of the filter membrane; the second purpose of the invention is to provide the PVDF filter membrane with high hydrophilicity prepared by the method.
In order to achieve the purpose, the invention provides the following technical scheme:
1. by magnetron sputtering of SiO2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles comprises the following steps:
1) preparing a PVDF nanofiber film by adopting an electrostatic spinning method;
2) after being fully dried, sputtering SiO on the surface of the PVDF nano fiber film by adopting a magnetron sputtering method2And (4) obtaining the high-hydrophilicity PVDF filter membrane by using nano particles.
Preferably, step 1) is specifically as follows: firstly, putting PVDF powder into a drying oven for full drying, then adding the dried PVDF powder into an organic solvent for ultrasonic oscillation, then stirring the solution by using a magnetic stirrer to enable the PVDF powder to be fully dissolved in the organic solvent, and finally standing and defoaming the mixed solution for electrostatic spinning.
Preferably, the organic solvent used is N, N-Dimethylformamide (DMF), N-N-dimethylacetamide (DMAc) or a mixed solution thereof with acetone.
More preferably, in the step 1), the drying is carried out at a temperature of 50-80 ℃ for 12-24 hours; the stirring temperature of the magnetic stirrer is set to be 30-60 ℃, and the rotating speed is 300-1000 r/min.
More preferably, in the step (1), PVDF in the organic solvent is added according to the mass fraction of 5-30%.
More preferably, in step 1), the electrospinning conditions are as follows: the spinning voltage is positive pressure 10-30 kV, the negative pressure (-1) — (-10) kV, the distance from the spray head to the flat plate filament collecting device is 10-30 cm, the temperature is 25-60 ℃, and the humidity is 30-70%.
More preferably, in the step 2), the drying is to place the PVDF nano-fiber membrane into a forced air drying oven for full drying, wherein the drying temperature is 50-80 ℃, and the drying time is 12-24 hours.
More preferably, the magnetron sputtering method is used for sputtering SiO2The nano particles are PVDF nano fiber film and SiO2The distance between the targets is 10-30 cm, the sputtering power is 30-120W, the reaction gas is high-purity argon, the flow is 50-300 sccm, the sputtering vacuum is 0-10 pa, and the sputtering time is 3-30 min.
2. The highly hydrophilic PVDF filter membrane prepared by the method.
The invention has the beneficial effects that: the invention discloses a method for preparing SiO by magnetron sputtering2The method for preparing the PVDF filter membrane with the nano particles comprises the steps of improving the hydrophilicity of the PVDF filter membrane by utilizing the magnetron sputtering of the SiO2 nano particles, preparing the PVDF nanofiber filter membrane by electrostatic spinning, and then utilizing a magnetron sputtering device and adopting a SiO2Target material, directly sputtering SiO on the surface of PVDF film2Nano meterThe hydrophobic groups are introduced on the surface of the filter membrane by the particles, so that the purposes of improving the hydrophilicity and the anti-pollution performance of the filter membrane are achieved. Compared with the prior art, the method can prepare the hydrophilic organic-inorganic composite nanofiber filter membrane with uniform nano dispersion and controllable content.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 shows the electrostatic spinning PVDF nano-fiber filter membrane and DC sputtering SiO observed by field emission scanning electron microscope2PVDF/SiO after 10min of treatment2Surface topography of composite nanofiber filtration membrane (a: PVDF nanofiber membrane; b: PVDF/SiO)2Composite nanofiber membranes);
FIG. 2 shows an electrospun PVDF nanofiber filter membrane and DC sputtered SiO measured by a Fourier infrared spectrometer2PVDF/SiO after various times2Infrared spectrum of the composite nanofiber filter membrane;
FIG. 3 shows an electrospun PVDF nanofiber membrane and DC sputtered SiO2PVDF/SiO after various times2And (5) measuring the contact angle of the water drops of the composite nanofiber filter membrane.
Detailed Description
The present invention is further described with reference to the following drawings and specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
Example 1
By magnetron sputtering of SiO2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles comprises the following steps:
1) firstly, putting PVDF powder into a drying oven, drying for 12-24 hours at the temperature of 50-80 ℃, then adding the dried PVDF powder into N, N-Dimethylformamide (DMF) according to the mass fraction of 5-30%, carrying out ultrasonic oscillation, stirring the solution at the temperature of 30-60 ℃ and the rotating speed of 300-1000 r/min by using a magnetic stirrer to fully dissolve the PVDF powder in the N, N-Dimethylformamide (DMF), and finally standing and defoaming the mixed solution for electrostatic spinning to obtain a PVDF nanofiber membrane; the spinning voltage is positive voltage of 10-30 kV, the negative voltage is (-1) — (-10) kV, the distance from a spray head to a flat plate filament collecting device is 10-30 cm, the temperature is 25-60 ℃, and the humidity is 30-70%;
2) putting the PVDF nano-fiber film into a forced air drying oven for full drying at the drying temperature of 50-80 ℃ for 12-24 h, and sputtering SiO on the surface of the PVDF nano-fiber film by a magnetron sputtering method after drying2Nanoparticles, control of PVDF nanofiber membranes and SiO2The distance between the targets is 10-30 cm, the sputtering power is 30-120W, the reaction gas is high-purity argon, the flow is 50-300 sccm, the sputtering vacuum is 0-10 pa, and the sputtering time is 3-30 min.
Preferably, PVDF powder is dried in a drying oven at the temperature of 60 ℃ for 24 hours for standby, then the PVDF powder and a DMF organic solvent (10 mass percent of PVDF) are weighed, mixed and placed on a magnetic stirrer at the temperature of 50 ℃ and the rotating speed of 500r/min for stirring for 3 hours, and the PVDF is fully dissolved and kept stand for defoaming; the prepared solution is used for electrostatic spinning, the spinning voltage is set to be positive pressure 18kV and negative pressure-2 kV, the distance from a spray head to a flat plate filament collecting device is 15cm, the temperature is 40 ℃, the humidity is 40%, and the spinning time is 3 h.
Preferably, the dried PVDF nano-fiber membrane is placed in a sample chamber of a magnetron sputtering device and is away from SiO215cm of target material, setting the direct current sputtering power to be 60W, the argon gas flow to be 200sccm, the sputtering vacuum to be 2Pa, and comparing SiO with different contents2The sputtering time is set to be 5min, 10min and 15min respectively for influencing the hydrophilic property of the PVDF film.
In this example, magnetron sputtering of SiO was used2The filter membrane obtained from the nanoparticles is characterized in physical and chemical properties by a JEOL JSM-7800F field emission scanning electron microscope, an ALPHA Brookfield Fourier infrared spectrometer and an SDC-100 optical contact angle measuring instrument.
The scanning electron microscope test result shown in FIG. 1 shows that the DC sputtering of SiO for 10min2After the nano particles are added, the surface of the PVDF nano fiber becomes rough, and uniformly distributed micro nano particles appear.
FIG. 2 shows an infrared spectrumTest results show that in the magnetron sputtering process, the PVDF film receives SiO with higher energy2The nano particles impact to break partial hydrogen bonds on the surface of the PVDF film and react with SiO2Acting at 2423cm-1A large number of hydroxyl groups with hydrophilic property are formed nearby, so that the hydrophilic property of the surface of the PVDF membrane is changed.
The water drop contact angle measurement result shown in FIG. 3 shows that the PVDF nanofiber membrane prepared by electrostatic spinning has a contact angle as high as 143 degrees, has hydrophobic property, and is sputtered with SiO for 5min2After the nanoparticles, the contact angle decreased to 96.8 °, and with the increase of the sputtering time, the contact angle further decreased, and when the sputtering time reached 15min, the contact angle decreased to 36.8 °. The method provided by the invention can effectively improve the hydrophilicity of the PVDF membrane.
In the present invention, N-dimethylformamide as an organic solvent may be replaced with N-N-dimethylacetamide (DMAc), and N, N-dimethylformamide or a mixed solution of N-N-dimethylacetamide and acetone may be used.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.

Claims (6)

1. By magnetron sputtering of SiO2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles is characterized by comprising the following steps: the method comprises the following steps:
1) the PVDF nanofiber film is prepared by adopting an electrostatic spinning method, which comprises the following steps: firstly, putting PVDF powder into a drying oven for full drying, then adding the dried PVDF powder into an organic solvent for ultrasonic oscillation, then stirring the solution by using a magnetic stirrer to enable the PVDF powder to be fully dissolved in the organic solvent, and finally standing and defoaming the mixed solution for electrostatic spinning; the adopted organic solvent is N, N-dimethylformamide, N-N-dimethylacetamide or a mixed solution of the N, N-dimethylformamide and the N-dimethylacetamide and acetone;
2) after being fully dried, the surface of the PVDF nano-fiber film adopts a magnetron sputtering methodSputtering of SiO2Nano particles to obtain a high-hydrophilicity PVDF filter membrane;
the magnetron sputtering method is used for sputtering SiO2The nano particles are PVDF nano fiber film and SiO2The distance between the targets is 10-30 cm, the sputtering power is 30-120W, the reaction gas is high-purity argon, the flow is 50-300 sccm, the sputtering vacuum is 0-10 pa, and the sputtering time is 3-30 min.
2. The method of claim 1 wherein said SiO is deposited by magnetron sputtering2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles is characterized by comprising the following steps: in the step 1), drying is carried out for 12-24 hours at the temperature of 50-80 ℃; the stirring temperature of the magnetic stirrer is set to be 30-60 ℃, and the rotating speed is 300-1000 r/min.
3. The method of claim 1 wherein said SiO is deposited by magnetron sputtering2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles is characterized by comprising the following steps: in the step 1), PVDF in the organic solvent is added according to the mass fraction of 5-30%.
4. The method of claim 1 wherein said SiO is deposited by magnetron sputtering2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles is characterized by comprising the following steps: in the step 1), the electrostatic spinning conditions are as follows: the spinning voltage is positive voltage of 10-30 kV, the negative voltage is-1-10 kV, the distance from a spray head to a flat plate filament collecting device is 10-30 cm, the temperature is 25-60 ℃, and the humidity is 30-70%.
5. The method of claim 1 wherein said SiO is sputtered by magnetron sputtering2The method for preparing the high-hydrophilicity PVDF filter membrane by the nano particles is characterized by comprising the following steps: in the step 2), the drying is to place the PVDF nano-fiber membrane into a forced air drying oven for full drying, wherein the drying temperature is 50-80 ℃, and the drying time is 12-24 hours.
6. A highly hydrophilic PVDF filter membrane produced by the method of any one of claims 1 to 5.
CN201810990776.0A 2018-08-28 2018-08-28 Method for preparing high-hydrophilicity PVDF (polyvinylidene fluoride) filter membrane by magnetron sputtering SiO2 nano particles and product thereof Active CN109012221B (en)

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