CN115418795B - Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic properties and preparation method thereof - Google Patents
Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic properties and preparation method thereof Download PDFInfo
- Publication number
- CN115418795B CN115418795B CN202211073114.XA CN202211073114A CN115418795B CN 115418795 B CN115418795 B CN 115418795B CN 202211073114 A CN202211073114 A CN 202211073114A CN 115418795 B CN115418795 B CN 115418795B
- Authority
- CN
- China
- Prior art keywords
- sided
- fiber membrane
- spinning
- ptfe
- tio
- 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.)
- Active
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 121
- 239000000835 fiber Substances 0.000 title claims abstract description 112
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 46
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000009987 spinning Methods 0.000 claims abstract description 75
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 63
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 60
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 60
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 26
- 239000007853 buffer solution Substances 0.000 claims abstract description 24
- 230000004048 modification Effects 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 58
- 238000010438 heat treatment Methods 0.000 claims description 42
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 21
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000000872 buffer Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 238000000926 separation method Methods 0.000 abstract description 37
- 239000002131 composite material Substances 0.000 abstract description 14
- 238000001035 drying Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract 1
- 229920001690 polydopamine Polymers 0.000 description 44
- 238000003756 stirring Methods 0.000 description 30
- 239000002105 nanoparticle Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- SFRDXVJWXWOTEW-UHFFFAOYSA-N 2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)CO SFRDXVJWXWOTEW-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000002121 nanofiber Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000005661 hydrophobic surface Effects 0.000 description 6
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 235000019198 oils Nutrition 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- MHXFWEJMQVIWDH-UHFFFAOYSA-N 1-amino-4-hydroxy-2-phenoxyanthracene-9,10-dione Chemical compound C1=C(O)C=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C1OC1=CC=CC=C1 MHXFWEJMQVIWDH-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 235000019476 oil-water mixture Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005594 polymer fiber Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2505/00—Industrial
- D10B2505/04—Filters
Abstract
The invention relates to a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic and a preparation method thereof, wherein the method comprises the following steps: (1) Preparation of polytetrafluoroethylene/polyvinyl alcohol/titanium dioxide (PTFE/PVA/TiO) by centrifugal spinning or electrostatic spinning method 2 ) A composite fiber membrane; (2) Preparation of micro-nano PTFE/PVA/TiO by centrifugal spinning or electrostatic spinning 2 Fibrous membrane of PTFE/PVA/TiO 2 Fully sintering the fiber membrane in a muffle furnace with uniform temperature rise, taking out, ultrasonically cleaning and drying to obtain PTFE/TiO 2 A fibrous membrane; (3) Hydrophobic micro-nano PTFE/TiO 2 The fiber membrane is subjected to single-sided modification in PDA buffer solution to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus micro-nano composite fiber membrane. The Janus type fiber membrane prepared by the method can be used for industrial oil-water separation and has the characteristics of good operability, simple process, high efficiency, environmental protection, high oil-water separation efficiency and the like.
Description
Technical Field
The invention relates to an oil-water separation film, in particular to a Janus type micro-nano composite fiber film with single-sided superhydrophobic and single-sided superhydrophilic surfaces and a preparation method thereof, and belongs to the technical field of new materials.
Background
In recent years, water resources have become limited, and due to this problem, reuse of water has become unavoidable. Thus, treating the reuse water in an efficient manner may reduce the impact on human health and the environment. One major environmental problem is the direct discharge of oily water and oily wastewater into the environment. Today, direct emission of oil-in-water contaminants generated by petroleum, automobiles, and refineries into an aqueous environment can affect human health and the aqueous environment. Used engine oil from automotive service stations contains high contaminants. Thus, the wastewater needs to be effectively treated before entering the ground, water body or sewer. The industrial oil-water separation methods mainly comprise air flotation, gravity separation, adsorption separation, condensation, flocculation and the like, but the methods can not effectively separate oil-water mixtures, are easy to cause energy consumption and secondary pollution, and are gradually replaced by some emerging separation technologies.
In order to maintain good ecological environment and human health and protect limited water resources, it is important to effectively separate oily sewage, and the traditional oil-water separation method has the disadvantages of long separation time, complex operation, incapability of continuous separation and incomplete separation. Although various special wettability materials with good oil-water separation function are currently available, most of the materials are mainly nondegradable or nondegradable high polymer materials, and the materials are easy to be polluted in the process of treating oily sewage due to the oleophilic property, so that a large amount of polluted garbage and waste materials which are difficult to treat are often generated after the materials are used, secondary pollution is easy to cause to the environment, and the comprehensive cost of post-treatment is high, so that the materials become one of important factors restricting the practical application of the oil-water separation materials. The membrane separation technology is an advanced novel separation technology, has the advantages of low energy consumption, low cost, high efficiency, no phase change, simple operation and the like, and in recent years, the strategic position in the fields of industry, municipal water treatment and the like is gradually highlighted, and is considered as a new generation of water treatment technology. However, with the continuous development of separation membrane technology, the requirements on the membrane materials in the aspects of intelligent response and accurate control are higher and higher, so that the development of novel separation membranes with special functions is of great significance.
Janus membranes, a separation membrane with liquid passage properties, are often characterized by differences in the chemical wetting properties of the two sides of the membrane. In recent years, materials having a Janus structure have been receiving increasing attention from researchers in the field of structural and functional design, and Janus membranes can remove certain liquids from specific areas and can effectively prevent liquid accumulation and contamination during related liquid transportation. With the technological progress, there is an increasing demand for composite materials, and the Janus structure can bring about dual-function effect or function synergistic effect compared with other single homogeneous materials, so that the composite materials are applied to a plurality of fields. However, the preparation method of the Janus material is complex, single in function and high in cost so far, so that the practical application of the material is hindered, the preparation process of the Jaun material is simplified, the cost is reduced, and more applications are still important in the research of the field.
Disclosure of Invention
The invention aims to provide a preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic, which is simple and easy to control, is suitable for composite finishing of various polymer fiber membranes, has the characteristics of single-sided superhydrophobic and single-sided superhydrophilic double-sided anisotropy, and has better oil-water separation performance.
The technical scheme adopted for solving the technical problems is as follows:
a preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following steps:
(1) Micro-nano polytetrafluoroethylene/polyvinyl alcohol/titanium dioxide (PTFE/PVA/TiO) prepared by adopting centrifugal spinning or electrostatic spinning method 2 ) A fibrous membrane;
the spinning solution is prepared from nano TiO 2 The PVA aqueous solution of the particles and the PTFE emulsion are mixed to prepare the spinning solution, wherein the mass fraction of PVA in the spinning solution is 5-9wt% and the mass fraction of nano TiO is 2 1wt% of particles and 27-33wt% of PTFE;
(2) PTFE/PVA/TiO prepared in the step (1) is mixed with 2 The PVA component is fully sintered and removed by the fiber membrane in a muffle furnace with uniform temperature rise, and the fiber membrane is taken out, ultrasonically cleaned and dried to obtain the hydrophobic micro-nano PTFE/TiO 2 A fibrous membrane;
the sintering temperature is 384+/-10 ℃, and the heat preservation time is 20-60 min;
(3) PTFE/TiO prepared in the step (2) is treated 2 Carrying out single-sided modification on the fiber membrane in a PDA buffer solution to prepare a single-sided superhydrophobic single-sided superhydrophilic Janus micro-nano composite fiber membrane;
the PDA buffer is an aqueous solution containing dopamine hydrochloride (HCL-PDA) and tris (hydroxymethyl) aminomethane, and the pH is adjusted to 7-8 by hydrochloric acid.
The invention is different from the single-sided super-hydrophobic or hydrophilic finishing of the fiber membrane, and is characterized in that the hydrophilic fiber membrane is sintered to obtain super-hydrophobic, and then is subjected to hydrophilic modification, so that the fiber membrane has higher oil-water separation effect.
The invention takes the economic and environment-friendly polyvinyl alcohol (PVA) and Polytetrafluoroethylene (PTFE) emulsion as raw materials, and adds a small amount of nano-particles TiO 2 The PVA particles can be uniformly dispersed in water, and the problems of insufficient swelling and wall hanging of the PVA particles in the dissolving process can be solved. Hydrophilic PTFE/PVA/TiO prepared by centrifugal spinning or electrostatic spinning 2 The fiber membrane is prepared into a Janus micro-nano fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic through sintering and PDA modification, and the Janus micro-nano fiber membrane is applied to oil-water separation, so that the oil-water separation efficiency can be improved to 98.7%, and the problem of oil-water pollution in the environment can be effectively solved.
The invention prepares the asymmetric wettability micro-nano composite fiber membrane by using a hot pressing method and an adhesive method, and prepares the hydrophilic PTFE/PVA/TiO by using a centrifugal spinning or electrostatic spinning technology 2 The fiber membrane is sintered at 384 ℃ in a muffle furnace to be changed into a super-hydrophobic membrane, and then PDA single-sided modification (pH=7-8) treatment is carried out to lead the PTFE/TiO to be prepared 2 The fiber membrane has single-sided hydrophilicity, and the single-sided superhydrophobic single-sided superhydrophilic Janus micro-nano fiber membrane is prepared. The Janus type fiber membrane prepared by the method can be used for industrial oil-water separation and has the characteristics of simple raw materials, good operability, simple process, high efficiency, environmental protection, high oil-water separation efficiency and the like.
Preferably, in step (1), the PTFE emulsion has a PTFE solids content of 50 to 60%.
Preferably, in the step (1),
during centrifugal spinning, the mass fraction of PVA in the spinning solution is 6-9wt%;
during electrostatic spinning, the mass fraction of PVA in the spinning solution is 5-8wt%.
Preferably, in the step (2), the constant temperature rising method of sintering is: in the air environment, when the temperature is between 0 and 370 ℃, the temperature rising rate is 5 ℃/min; the temperature is 370-384 ℃, and the heating rate is 1 ℃/min; the temperature is 384 ℃, and the heat preservation time is 30min; at 384-27 ℃, the cooling rate is 25 ℃/min.
Preferably, in the PDA buffer solution in the step (3), the mass concentration of the dopamine hydrochloride solution is 5-20g/L, and the mass concentration of the tris (hydroxymethyl) aminomethane is 10-30%.
Preferably, the spinning conditions of the centrifugal spinning are: the diameter of the spinning hole is 0.2-0.6mm, and the spinning rotating speed is 2000-10000rpm/min;
the spinning conditions of the electrostatic spinning are as follows: the diameter of the spinning hole is 0.24 plus or minus 0.05mm, the injection speed of the spinning solution is 0.01-0.6mm/min, the spinning voltage is 10-20KV, and the receiving distance is 10-20cm.
Preferably, the control of the receiving rod is 12 cm.+ -.2 cm from the spinneret during centrifugal spinning.
The Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic is prepared by the preparation method.
The single-sided superhydrophobic single-sided superhydrophilic Janus type PTFE/TiO prepared by the invention 2 The micro-nano composite fiber membrane is prepared by sintering and single-sided modification, so that stable super-hydrophobic characteristics of a fibril membrane are maintained, a composite fiber membrane with hydrophilic and hydrophobic double-sided anisotropy is prepared, and the single-sided super-hydrophobic single-sided super-hydrophilic Jaun composite fiber membrane prepared by the method has good separation effect when being used for oil-water separation, and has the following characteristics:
(1) The preparation method is simple in preparation process, efficient, environment-friendly, simple and convenient to operate and good in controllability;
(2) The invention adds a small amount of nano-particle TiO 2 Not only can help PVA particles to be uniformly dispersed in water and improve the insufficient swelling and wall hanging phenomena of the PVA particles, but also can accelerate the dissolution of the PVA particles in water and enhance the fiber membrane preparedPerformance;
(3) The invention utilizes the high-temperature sintering and PDA single-sided modification method to lead the PTFE/PVA/TiO with hydrophilicity 2 Removing hydrophilic component PVA in the fiber membrane to obtain superhydrophobicity, modifying the fiber membrane by using PDA buffer solution to make one side of the fiber membrane hydrophilic, and obtaining the composite fiber membrane with excellent asymmetric wettability;
(4) The Jauns type micro-nano composite fiber membrane prepared by the invention has good stability and large porosity, and the highest oil-water separation efficiency can reach 98.7%.
Drawings
FIG. 1 is a photograph of the hydrophobic surface of a Janus micro-nanofiber membrane prepared in example 1 with water and oil droplets (1, 2-dibromoethane) dropped thereon;
FIG. 2 is a droplet contact angle of a hydrophobic surface of Janus composite fiber membranes prepared in various examples;
FIG. 3 shows the oil-water separation rate of the Janus composite fiber membrane prepared in each example for oil-water separation application test;
FIG. 4 is a scanning electron microscope image of Janus micro-nanofiber membrane prepared in example 3;
FIG. 5 is a Transmission Electron Microscope (TEM) obtained in example 1;
FIG. 6 is TiO 2 The mass fraction of the nano particles is 0,0.4,0.6,0.8,1,1.2,1.4 and 1.6wt% of the spinning solution.
Detailed Description
The technical scheme of the invention is further specifically described by the following specific examples. It should be understood that the practice of the invention is not limited to the following examples, but is intended to be within the scope of the invention in any form and/or modification thereof.
In the present invention, unless otherwise specified, all parts and percentages are by weight, and the equipment, materials, etc. used are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
In the following examples, the molecular weight of PVA is 10000g/mol, and the solid content of PTFE in PTFE emulsion is 60%;
muffle furnace, OTF-1200X, hefei Ke Jing materials Co., ltd.
The PDA buffer solution comprises dopamine hydrochloride, tris and deionized water. The preparation method comprises the following steps: taking a 150ml beaker, adding 120ml deionized water into the beaker, adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 5-20g/L, the mass concentration of the trimethylol aminomethane is 10-30%, the reaction temperature is 25 ℃, and simultaneously, dropwise adding the solution into the solution by using 37% concentrated hydrochloric acid, stirring and adjusting the pH=7-8.
The single-sided modification reaction time of the fiber membrane in PDA buffer is 6-12 hours.
Example 1
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) 13wt% of PVA and 13wt% of TiO are prepared 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 1h, slowly heating to 95 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution completely, injecting the spinning solution into an injector, and then spinning on an electrostatic spinning machine, wherein the spinning voltage is 15KV, the receiving distance is 20cm, and the injection speed is 0.09mm/min;
(2) Spin PTFE/PVA/TiO 2 Placing the fiber membrane into a muffle furnace with constant temperature rise for full sintering,
the constant-speed temperature rising method for sintering comprises the following steps: setting the temperature at 0-370 deg.C, and setting the heating rate at 5 deg.C/min. Setting the temperature at 370-381 deg.C, and setting the heating rate at 1 deg.C/min.
Setting the temperature at 381 deg.C, and setting the heat preservation time at 30min.
Setting the temperature at 381-27 deg.C, setting the cooling rate at 25 deg.C/min.
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 16g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
The hydrophobic micro-nano PTFE/TiO obtained by sintering the step (2) 2 The fiber membrane is subjected to single-sided modification in the PDA buffer solution for 12 hours, namely one side of the fiber membrane floats on the surface of the buffer solution, PDA molecules are oxidized and self-gathered on the surface of the fiber, and the modified surface has good hydrophilicity after modification.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
To examine different contents of TiO 2 Influence of nano particles on performance of nano composite fiber membrane, and TiO is prepared by adopting the method 2 The mass fraction of the nano particles is 0,0.4,0.6,0.8,1,1.2,1.4 and 1.6wt% of the spinning solution, and other conditions are unchanged. And detecting the water contact angle of the prepared nano composite fiber membrane, testing the surface contact angle of the nano composite fiber membrane by using a video contact angle tester, designing 3 mu L of deionized water to drop on the surface of the fiber membrane, randomly selecting five points for testing each sample, and calculating the average value of test data.
The experimental results in FIG. 6 show that the water contact angles are 143.6 °, 145 °, 146.1 °, 147.7 °, 152.7 °, 152 °, 152.3 °, 152.2 °, respectively, and from this result, 1wt% TiO is known 2 The hydrophobicity is optimal under the condition of the addition amount.
The wettability of porous surfaces is described by the Cassie-Baxter equation:
cosθc＝σ1cosθ1–σ2＝σ1(cosθ1+1)–1，
since the angle of the droplet to the air is 180 °, σ2=1 to σ1. The model shows that when the contact angle on the same smooth solid is greater than 90 °, the contact angle increases by decreasing the contact area between the solid and the liquid (i.e., increasing the contact area of the liquid with air). Using a micropillar array, nanoparticles are added to increase the roughness on the nanometer scale. This results in an increase in roughness and an increase in superhydrophobic property.
In the test process, when preparing spinning solution, different contents of TiO 2 The nano particles are originally used for improving the roughness of the composite fiber membrane so as to improve the hydrophobicity, and unexpectedly, when the spinning solution is prepared, the PVA nano particles are easy to generate flocculation when heated unevenly during heating and dissolution, and the TiO is easy to generate flocculation 2 The addition of nanoparticles allows the dope to be heated more uniformly, which can also help in the dissolution of PVA. As can be seen from the observation of the dissolution change, the composition contains TiO at a concentration of about 1wt% 2 The addition of the nanoparticles has an optimal effect on the dissolution of PVA.
Example 2
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) Preparing PVA with 15wt% and TiO 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 0.5h, slowly heating to 98 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution after complete stirring, stirring on the heating magnetic stirrer at 55 ℃ for 1h, and carrying out centrifugal spinning, wherein the diameter of a spinning head is 0.4mm, and the spinning rotating speed is 8000rpm/min; the method comprises the steps of carrying out a first treatment on the surface of the
(2) Spin PTFE/PVA/TiO 2 The fiber membrane is put into a muffle furnace to be fully sintered at 0-384 ℃, and the heating rate is set to be 5 ℃/min when the set temperature is 0-370 ℃. Setting the temperature at 370-384 deg.C, and setting the heating rate at 1 deg.C/min. Setting the temperature at 384 ℃ and setting the heat preservation time to be 30min. Setting the temperature at 384-27 ℃ and setting the cooling rate at 25 ℃/min.
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 16g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
The hydrophobic micro-nano PTFE/TiO obtained by sintering the step (2) 2 The fiber membrane is subjected to single-sided modification in the PDA buffer solution for 12 hours, namely one side of the fiber membrane floats on the surface of the buffer solution, PDA molecules are oxidized and self-gathered on the surface of the fiber, and the modified surface has good hydrophilicity after modification.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
Example 3
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) Preparation of PVA with mass fraction of 14wt% and TiO 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 1h, slowly heating to 95 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution completely, injecting the spinning solution into an injector, and then spinning on an electrostatic spinning machine at a spinning voltage of 16KV, wherein the receiving distance is 20cm, and the injection speed is 0.10mm/min;
(2) Spin PTFE/PVA/TiO 2 The fiber membrane is put into a muffle furnace to be fully sintered at 0-381 ℃, and the heating rate is set to be 5 ℃/min when the set temperature is 0-370 ℃. Setting the temperature at 370-381 deg.C, and setting the heating rate at 1 deg.C/min. Setting the temperature at 381 deg.C, and setting the heat preservation time at 30min. Setting the temperature at 381-27 deg.C, setting the cooling rate at 25 deg.C/min. The method comprises the steps of carrying out a first treatment on the surface of the
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 17g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
Sintering (2) to obtainHydrophobic micro-nano PTFE/TiO of (C) 2 The fiber membrane is subjected to single-sided modification in the PDA buffer solution for 12 hours, namely one side of the fiber membrane floats on the surface of the buffer solution, PDA molecules are oxidized and self-gathered on the surface of the fiber, and the modified surface has good hydrophilicity after modification.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
Example 4
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) Preparing PVA with 15wt% and TiO 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 1h, slowly heating to 95 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution completely, injecting the spinning solution into an injector, and then spinning on an electrostatic spinning machine at a spinning voltage of 17KV, a receiving distance of 20cm and a push injection speed of 0.12mm/min;
(2) Spin PTFE/PVA/TiO 2 The fiber membrane is put into a muffle furnace to be fully sintered at 0-381 ℃, and the heating rate is set to be 5 ℃/min when the set temperature is 0-370 ℃. Setting the temperature at 370-381 deg.C, and setting the heating rate at 1 deg.C/min. Setting the temperature at 381 deg.C, and setting the heat preservation time at 30min. Setting the temperature at 381-27 deg.C, setting the cooling rate at 25 deg.C/min. The method comprises the steps of carrying out a first treatment on the surface of the
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 18g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
The hydrophobic micro-nano PTFE/TiO obtained by sintering the step (2) 2 Fibrous membraneAnd the PDA molecules are oxidized and self-aggregated on the surface of the fiber, and the modified surface has better hydrophilicity.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
Example 5
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) Preparation of PVA with mass fraction of 16wt% and TiO 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 0.5h, slowly heating to 98 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with a solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution after complete stirring, stirring on the heating magnetic stirrer at 55 ℃ for 1h, and carrying out centrifugal spinning, wherein the diameter of a spinning head is 0.5mm, and the spinning rotating speed is 9000rpm/min; the method comprises the steps of carrying out a first treatment on the surface of the
(2) Spin PTFE/PVA/TiO 2 The fiber membrane is put into a muffle furnace to be fully sintered at 0-384 ℃, and the heating rate is set to be 5 ℃/min when the set temperature is 0-370 ℃. Setting the temperature at 370-384 deg.C, and setting the heating rate at 1 deg.C/min. Setting the temperature at 384 ℃ and setting the heat preservation time to be 30min. Setting the temperature at 384-27 ℃ and setting the cooling rate at 25 ℃/min.
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 19g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
The hydrophobic micro-nano PTFE/TiO obtained by sintering the step (2) 2 The fiber membrane is modified for 12 hours on one side in PDA buffer solution, namely the fiber membraneOne surface floats on the surface of the buffer solution, PDA molecules are oxidized and self-gathered on the surface of the fiber, and the modified surface has better hydrophilicity after modification.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
Example 6
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) Preparation of PVA with mass fraction of 17wt% and TiO 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 0.5h, slowly heating to 98 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution after complete stirring, stirring on the heating magnetic stirrer at 55 ℃ for 1h, and carrying out centrifugal spinning, wherein the diameter of a spinning head is 0.4mm, and the spinning rotating speed is 8000rpm/min; the method comprises the steps of carrying out a first treatment on the surface of the
(2) Spin PTFE/PVA/TiO 2 The fiber membrane is put into a muffle furnace to be fully sintered at 0-384 ℃, and the heating rate is set to be 5 ℃/min when the set temperature is 0-370 ℃. Setting the temperature at 370-384 deg.C, and setting the heating rate at 1 deg.C/min. Setting the temperature at 384 ℃ and setting the heat preservation time to be 30min. Setting the temperature at 384-27 ℃ and setting the cooling rate at 25 ℃/min.
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 20g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
The hydrophobic micro-nano PTFE/TiO obtained by sintering the step (2) 2 The fiber membrane is modified for 12 hours on one side in PDA buffer solution, namely one side of the fiber membrane floats on the surface of the buffer solution, and PDA molecules pass through oxygenThe modified surface has better hydrophilicity after being modified on the surface of the fiber.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
Example 7
A preparation method of a Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic comprises the following specific steps:
(1) Preparation of PVA with mass fraction of 17wt% and TiO 2 PVA/TiO with mass fraction of nano particles of 1wt% 2 Stirring the solution on a heating magnetic stirrer at 25 ℃ for 0.5h, slowly heating to 98 ℃ until PVA is completely dissolved, cooling to room temperature, adding a PTFE emulsion with solid content of 60% to ensure that the PTFE accounts for 30% of the spinning solution, stirring on the heating magnetic stirrer at 25 ℃ for 12h, stirring the spinning solution after complete stirring, stirring on the heating magnetic stirrer at 55 ℃ for 1h, and carrying out centrifugal spinning, wherein the diameter of a spinning head is 0.6mm, and the spinning rotating speed is 8600rpm/min; the method comprises the steps of carrying out a first treatment on the surface of the
(2) Spin PTFE/PVA/TiO 2 The fiber membrane is put into a muffle furnace to be fully sintered at 0-384 ℃, and the heating rate is set to be 5 ℃/min when the set temperature is 0-370 ℃. Setting the temperature at 370-384 deg.C, and setting the heating rate at 1 deg.C/min. Setting the temperature at 384 ℃ and setting the heat preservation time to be 30min. Setting the temperature at 384-27 ℃ and setting the cooling rate at 25 ℃/min.
(3) Preparing a PDA buffer solution: taking a 150ml beaker, adding 120ml deionized water into the beaker, and adding dopamine hydrochloride and trimethylol methane, wherein the mass concentration of the dopamine hydrochloride is 20g/L, the mass concentration of the trimethylol aminomethane is 20wt%, the reaction temperature is 25 ℃, meanwhile, the pH=7-8 is regulated by hydrochloric acid, and the solution preparation reaction time is 6 hours.
The hydrophobic micro-nano PTFE/TiO obtained by sintering the step (2) 2 The fiber membrane is single-sided modified in PDA buffer for 12 hours, namely one side of the fiber membrane floats on the surface of the buffer, PDA molecules are oxidized and self-gathered on the surface of the fiber, and the modified surface is modifiedHas better hydrophilicity.
(4) And carrying out ultrasonic cleaning on the Janus type micro-nano composite fiber membrane obtained through single-sided modification of the PDA solution to remove superfluous polydopamine on the surface, and drying in an oven at 60 ℃ to prepare the single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane.
The performance test result of the Janus micro-nano fiber film prepared by the invention is as follows:
1. as can be seen from fig. 1, when water droplets and oil droplets (1, 2-dibromoethane) were dropped on the hydrophobic surface of the Janus micro-nanofiber membrane prepared in example 1, it was observed that the fiber membrane had good hydrophobicity and lipophilicity. In order to more intuitively observe the states of the water phase and the oil phase on the Janus composite fiber membrane, the Janus fiber membranes prepared in examples 1-6 are tested for water-oil contact angle under a liquid drop morphological analyzer, the liquid drops are contacted with fabrics for 60 seconds, the test data are tested, the average value is obtained after the liquid drops are tested for 5 times at different positions of the same sample, and the liquid drop contact angle of the water repellent surface of the Janus composite fiber membrane is measured as shown in figure 2.
As can be seen from FIG. 2, the water contact angle of the hydrophobic surface of the Janus type micro-nano composite fiber membrane prepared by the method is higher than 150 degrees, wherein the water contact angle of the hydrophobic surface of the Janus type micro-nano composite fiber membrane prepared by the method in the embodiment 4 is highest and reaches 155 degrees, and the water contact angle of the oil phase on the hydrophobic surface of the fiber membrane in each embodiment is 0 degree, which indicates that the Janus type micro-nano composite fiber membrane prepared by the method has higher hydrophobicity and good lipophilicity.
2. The Janus type micro-nano composite fiber membrane prepared in the embodiment is used for carrying out an oil-water separation application test on an oil-water mixed solution of 1, 2-dibromoethane and deionized water (water/1, 2-dibromoethane mixed solution: 1, 2-dibromoethane is dyed by disperse red FB, deionized water is dyed by methylene blue, the two are mixed to be used as an oil-water mixed solution), water separation equipment is a sand core suction filtration device, a filter bowl is arranged above, the oil-water mixed solution is added from above, a sand core filtration head is arranged in the middle of the oil-water mixed solution, the prepared Janus fiber membrane is placed between the filter bowl and the filtration head, the fixation is carried out by a fixing clamp, and separation liquid is collected after separation is finished. The oil-water separation rate is shown in figure 3, and the separation efficiency of the composite fiber membrane prepared by the method is above 98%, wherein the highest oil-water separation rate of examples 1 and 2 is 98.7%, which shows that the composite fiber membrane has good oil-water separation effect.
3. As can be seen from fig. 4, a Scanning Electron Microscope (SEM) image shows that the Janus type micro-nano composite fiber film prepared in example 3 has a fiber morphology with a uniform diameter. As can be seen from FIG. 5, the Transmission Electron Microscope (TEM) of the Janus micro-nano composite fiber film prepared in example 1 shows nano TiO loaded on single fibers 2 The particles are more uniformly arranged in the fiber and on the surface.
In this specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, so that the same or similar parts between the embodiments are referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic provided by the invention and the preparation method thereof are described in detail. The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to facilitate an understanding of the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (7)
1. The preparation method of the Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic is characterized by comprising the following steps:
(1) Micro-nano polytetrafluoroethylene/polyvinyl alcohol/titanium dioxide (PTFE/PVA/TiO) prepared by adopting centrifugal spinning or electrostatic spinning method 2 ) A fibrous membrane;
the spinning solution is prepared from nano TiO 2 The PVA water solution of the particles and the PTFE emulsion are mixed to prepare PThe PTFE in the TFE emulsion has a solid content of 50-60%;
in the spinning solution, the mass fraction of PVA is 5-9wt% and nano TiO 2 1wt% of particles and 27-33wt% of PTFE;
(2) PTFE/PVA/TiO prepared in the step (1) is mixed with 2 The PVA component is fully sintered and removed by the fiber membrane in a muffle furnace with uniform temperature rise, and the fiber membrane is taken out, ultrasonically cleaned and dried to obtain the hydrophobic micro-nano PTFE/TiO 2 A fibrous membrane;
the sintering temperature is 384+/-10 ℃, and the heat preservation time is 20-60 min;
(3) PTFE/TiO prepared in the step (2) is treated 2 Carrying out single-sided modification on the fiber membrane in a PDA buffer solution to prepare a single-sided superhydrophobic single-sided superhydrophilic Janus micro-nano composite fiber membrane;
the PDA buffer is an aqueous solution containing dopamine hydrochloride (HCL-PDA) and tris (hydroxymethyl) aminomethane, and the pH is adjusted to 7-8 by hydrochloric acid.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the step of (a),
during centrifugal spinning, the mass fraction of PVA in the spinning solution is 6-9wt%;
during electrostatic spinning, the mass fraction of PVA in the spinning solution is 5-8wt%.
3. The method of manufacturing according to claim 1, characterized in that: in the step (2), the constant-speed temperature rising method for sintering is as follows: in the air environment, when the temperature is between 0 and 370 ℃, the temperature rising rate is 5 ℃/min; the temperature is 370-384 ℃, and the heating rate is 1 ℃/min; the temperature is 384 ℃, and the heat preservation time is 30min; at 384-27 ℃, the cooling rate is 25 ℃/min.
4. The method of manufacturing according to claim 1, characterized in that: in the PDA buffer solution in the step (3), the mass concentration of the dopamine hydrochloride solution is 5-20g/L, and the mass concentration of the tris (hydroxymethyl) aminomethane is 10-30%.
5. The method of manufacturing according to claim 1, characterized in that: the spinning conditions of centrifugal spinning are: the diameter of the spinning hole is 0.2-0.6mm, and the spinning rotating speed is 2000-10000rpm/min;
the spinning conditions of the electrostatic spinning are as follows: the diameter of the spinning hole is 0.24 plus or minus 0.05mm, the injection speed of the spinning solution is 0.01-0.6mm/min, the spinning voltage is 10-20KV, and the receiving distance is 10-20cm.
6. The method of manufacturing according to claim 1, characterized in that: the distance between the receiving rod and the spinning head is controlled to be 12cm plus or minus 2cm during centrifugal spinning.
7. A single-sided superhydrophobic single-sided superhydrophilic Janus type micro-nano composite fiber membrane obtained by the preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211073114.XA CN115418795B (en) | 2022-09-02 | 2022-09-02 | Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic properties and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211073114.XA CN115418795B (en) | 2022-09-02 | 2022-09-02 | Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic properties and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115418795A CN115418795A (en) | 2022-12-02 |
| CN115418795B true CN115418795B (en) | 2024-01-12 |
Family
ID=84203091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211073114.XA Active CN115418795B (en) | 2022-09-02 | 2022-09-02 | Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic properties and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115418795B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102111A (en) * | 2023-03-27 | 2023-05-12 | 长春理工大学 | Photocatalysis-water evaporation dual-function solar evaporation film |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100114808A (en) * | 2009-04-16 | 2010-10-26 | 주식회사 파라 | Method for asymmetric microporous hollow fiber membrane |
| EP2484432A1 (en) * | 2011-02-03 | 2012-08-08 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Microfiltration membrane |
| CN106115689A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of nanometer wall thickness Carbon foam |
| CN106283386A (en) * | 2016-10-24 | 2017-01-04 | 天津工业大学 | A kind of nanofiber pluralgel ultrafilter membrane and preparation method thereof |
| CN106637502A (en) * | 2016-12-21 | 2017-05-10 | 北京化工大学 | Method for preparing graphene/silica nanocomposite fiber through coaxial electrostatic spinning |
| CN108286127A (en) * | 2018-02-02 | 2018-07-17 | 南京工业大学 | A kind of preparation method of hydrophobic oleophobic nano fibrous membrane |
| CN111384241A (en) * | 2018-12-28 | 2020-07-07 | 东泰高科装备科技有限公司 | Flexible solar cell and preparation method thereof |
| CN215551580U (en) * | 2021-01-22 | 2022-01-18 | 苏州市织布鸟纺织品有限公司 | Breathable polyester fabric |
-
2022
- 2022-09-02 CN CN202211073114.XA patent/CN115418795B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100114808A (en) * | 2009-04-16 | 2010-10-26 | 주식회사 파라 | Method for asymmetric microporous hollow fiber membrane |
| EP2484432A1 (en) * | 2011-02-03 | 2012-08-08 | Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung GmbH | Microfiltration membrane |
| CN106115689A (en) * | 2016-06-27 | 2016-11-16 | 梅庆波 | A kind of preparation method of nanometer wall thickness Carbon foam |
| CN106283386A (en) * | 2016-10-24 | 2017-01-04 | 天津工业大学 | A kind of nanofiber pluralgel ultrafilter membrane and preparation method thereof |
| CN106637502A (en) * | 2016-12-21 | 2017-05-10 | 北京化工大学 | Method for preparing graphene/silica nanocomposite fiber through coaxial electrostatic spinning |
| CN108286127A (en) * | 2018-02-02 | 2018-07-17 | 南京工业大学 | A kind of preparation method of hydrophobic oleophobic nano fibrous membrane |
| CN111384241A (en) * | 2018-12-28 | 2020-07-07 | 东泰高科装备科技有限公司 | Flexible solar cell and preparation method thereof |
| CN215551580U (en) * | 2021-01-22 | 2022-01-18 | 苏州市织布鸟纺织品有限公司 | Breathable polyester fabric |
Non-Patent Citations (1)
| Title |
|---|
| 中国材料研究学会组织编写.高性能分离膜材料.中国铁道出版社,2017,第96-97页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115418795A (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110039863B (en) | Single-side super-hydrophobic and single-side hydrophilic Janus type micro-nano composite fiber membrane and preparation method thereof | |
| Sun et al. | Robust preparation of flexibly super-hydrophobic carbon fiber membrane by electrospinning for efficient oil-water separation in harsh environments | |
| Wang et al. | Electrospun polyvinylidene fluoride-based fibrous nanocomposite membranes reinforced by cellulose nanocrystals for efficient separation of water-in-oil emulsions | |
| CN106731012B (en) | A kind of super preparation for infiltrating titanium dioxide nano-rod perforated membrane and its application in lotion separation | |
| CN115418795B (en) | Janus type micro-nano composite fiber membrane with single-sided superhydrophobic and single-sided superhydrophilic properties and preparation method thereof | |
| CN109316981A (en) | A kind of preparation method of the super hydrophilic polymer film with demulsification function | |
| Cao et al. | Construction of Polytetrafluoroethylene nanofiber membrane via continuous electrospinning/electrospraying strategy for oil-water separation and demulsification | |
| CN110368718B (en) | Three-dimensional printed super-hydrophilic and underwater super-oleophobic net film and preparation method thereof | |
| CN114749039B (en) | Super-hydrophilic and underwater super-oleophobic carbon nanofiber membrane and preparation method thereof | |
| CN111001190B (en) | Preparation method and application of emulsion separation membrane with controllable wettability | |
| CN106178599B (en) | A kind of automatically cleaning polybenzoxazine super-hydrophobic super-oleophylic fiber web material and its preparation and the application in water-oil separating | |
| CN110368717B (en) | Polylactic acid non-woven filter cloth material for oil/water separation and preparation method thereof | |
| CN107081075A (en) | A kind of preparation method and applications of selective water-oil separating Dynamic Membrane | |
| CN108744992A (en) | A kind of preparation method of plate membrane for sludge condensation | |
| Mou et al. | Fabrication of stable super‐hydrophilic/underwater super‐oleophobic poly (arylene ether nitrile) nanofibrous composite membranes via the one‐step co‐deposition of dopamine and 3‐aminopropyltriethoxysilane for efficient oil‐in‐water emulsion separation | |
| Shen et al. | Hydrophilic SPE/MPTES-PAN electrospun membrane prepared via click chemistry for high efficiency oil–water separation | |
| CN112755805B (en) | Underwater super-oleophobic two-dimensional nanoscale mica sheet oil-water separation membrane and preparation method and application thereof | |
| Shen et al. | Antifouling hydrophilic electrostatic spinning PAN membrane based on click chemistry with high efficiency oil-water separation | |
| Chingakham et al. | Hydrophobic nano-bamboo fiber-reinforced acrylonitrile butadiene styrene electrospun membrane for the filtration of crude biodiesel | |
| CN108079798B (en) | Preparation method of super-hydrophilic organic membrane based on nano hydrotalcite-like compound | |
| CN116288931A (en) | Single-sided superhydrophobic single-sided superhydrophilic three-dimensional micro-nano composite fiber membrane and preparation method thereof | |
| CN114247312B (en) | Composite fiber membrane with asymmetric wettability, preparation method thereof and application thereof in oil-water separation | |
| Chang et al. | Facile fabrication of electrospun silica nanofibrous membrane with hydrophobic, oleophilic and breathable performances | |
| Wang et al. | Bicontinuous porous membranes with micro-nano composite structure using a facile atomization-assisted nonsolvent induced phase separation method | |
| CN112090295B (en) | Degradable oil-water separation membrane material and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |