CN105013351B - A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film - Google Patents
A kind of preparation method of polytetrafluoroethylene (PTFE) super-hydrophobic film Download PDFInfo
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- CN105013351B CN105013351B CN201410163044.6A CN201410163044A CN105013351B CN 105013351 B CN105013351 B CN 105013351B CN 201410163044 A CN201410163044 A CN 201410163044A CN 105013351 B CN105013351 B CN 105013351B
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- polytetrafluoroethylene
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- sintering
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 100
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 88
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000003075 superhydrophobic effect Effects 0.000 title abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 41
- 238000005245 sintering Methods 0.000 claims abstract description 38
- 238000001816 cooling Methods 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000009987 spinning Methods 0.000 claims abstract description 21
- 108010010803 Gelatin Proteins 0.000 claims abstract description 17
- 229920000159 gelatin Polymers 0.000 claims abstract description 17
- 239000008273 gelatin Substances 0.000 claims abstract description 17
- 235000019322 gelatine Nutrition 0.000 claims abstract description 17
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000004321 preservation Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000003570 air Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 230000003466 anti-cipated effect Effects 0.000 claims description 2
- 239000012510 hollow fiber Substances 0.000 claims description 2
- 239000012456 homogeneous solution Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000001935 peptisation Methods 0.000 claims 1
- 230000005661 hydrophobic surface Effects 0.000 abstract description 4
- 239000002352 surface water Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 208000027418 Wounds and injury Diseases 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 238000001523 electrospinning Methods 0.000 description 7
- 239000000284 extract Substances 0.000 description 7
- 230000004907 flux Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000004804 winding Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000010041 electrostatic spinning Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides a kind of preparation methods of polytetrafluoroethylene (PTFE) super-hydrophobic film, including spinning solution is with liquid, system is fine, is sintered, it is characterised in that: ptfe emulsion is added after being configured to solution at fine carrier and solvent, is gelatin at fine carrier, solvent is water；Sintering is sintered using temperature programmed control zonal cooling；And specifically provide its processing step.The present invention, which has been made, has beading superfine fibre polytetrafluoroethylene film, forms the hydrophobic surface with multistage coarse structure together；Surface water contact angle >=150 °, porosity are up to 80% or more；And solving the problems, such as that fiber is givey in the sintering of polytetrafluoroethylene (PTFE) precursor film, fibre morphology and surface are intact, and intensity and toughness also improve a lot, and are able to bear certain vacuum pressure.
Description
Technical field
The present invention relates to a kind of preparation methods of separation membrane material for separation field, and in particular to a kind of hydrophobic membrane material
Preparation method.
Technical background
Hydrophobicity is the critical nature of polytetrafluoroethylene (PTFE) (PTFE) material, is that polytetrafluoroethylporous porous membrane is applied to membrane material
The main performance of material.Although polytetrafluoroethylene material has low-surface-energy, the water contact angle of smooth polytetrafluoroethylene (PTFE) plane
Between 98 to 112 °, hydrophobic performance is simultaneously bad.
Polytetrafluoroethylporous porous membrane preparation at present mostly uses bidirectional extending method.This method is to obtaining higher porosity
Film when, need to film carry out large scale stretching, can not Surface Structures controlled, and film thickness only more than ten microns with
Under, backing material is needed in use, and backing material itself often has one in heat resistance or chemical stability or hydrophobic performance
Foregone conclusion limit, thus limit the application of this biaxial stretching film.Stretch the shape for being often difficult to control film at high proportion simultaneously, therefore
Mainly based on plate membrane.Chinese patent CN1775847A, CN102007242A, CN101543734B, CN102151494A etc.
Patent is all based on the above stretch processes and carries out polytetrafluoroethylporous porous membrane preparation.
Support methods are to prepare the important method of polytetrafluoroethylene fibre, the patents such as CN101994161A and CN102282301A
The preparation of polytetrafluoroethylsuperfine superfine fiber is reported using electrostatic spinning technique.High temperature sintering is directed in these reports
The step of removing into fine carrier, but these sintering processes are concerned only with into the removal of fine template.Specifically: CN101994161A
Purpose be to prepare a kind of polytetrafluoroethylsuperfine superfine fiber, preparation method is to make carrier using polyvinyl alcohol, passes through Static Spinning
Silk method is weaved out polytetrafluoroethylene fibre precursor, post-processing approach be by polytetrafluoroethylene fibre precursor at 100~120 DEG C
It is 5~15 minutes dry, it is sintered 30~90 minutes at 280~350 DEG C；The purpose of sintering be in order to make polyvinyl alcohol decompose and
Removal.And a kind of improved method for being mainly to provide polytetrafluoroethylene (PTFE) pad of CN102282301A, its purpose is to improve electricity
The technological parameter (spinning fluid viscosity) of spinning pads precursor to obtain the polytetrafluoroethylene fibre of uniform diameter, is sintered at 400 DEG C
Polytetrafluoroethylene fibre pad is obtained, the ash content of carrier (fibre-forming polymer) is less than 5%.CN101994161A and CN102282301A
Etc. patents using electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber (pad), only account for how obtaining polytetrafluoroethylene (PTFE) ultra-fine
Fiber (pad), it may be said that have to conventional polytetrafluoroethylsuperfine superfine fiber (pad).
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of polytetrafluoroethylene film, by controlling containing at the poly- of fine carrier
The post-processing sintering condition of tetrafluoroethene precursor film, by the method precision of temperature programmed control control sintering condition and cooling condition with
Obtain the superfine fibre reticular membrane that fibre morphology remains intact and has beading structure, the special construction of this nanoscale with
Superfine fibre forms the hydrophobic surface with multistage coarse structure together.Thus there is ultra-hydrophobicity.
The purpose of the present invention is realized by following technical measures:
A kind of preparation method of polytetrafluoroethylene film, including spinning solution is with liquid, system is fine, is sintered, it is characterised in that: it is carried at fibre
Ptfe emulsion is added after being configured to solution in body and solvent, is gelatin at fine carrier, solvent is water；Sintering uses program control
Warm zonal cooling sintering, in the case where flowing atmosphere, with the rate of 3~10 DEG C/min from room temperature to 120 DEG C~200 DEG C, 120
DEG C~200 DEG C of 30~120min of heat preservation；360 DEG C~400 DEG C are warming up to from 120 DEG C~200 DEG C with the rate of 2~8 DEG C/min,
360 DEG C~400 DEG C 5~120min of heat preservation；Cooling treatment is carried out after sintering, the cooling in the case where flowing atmosphere, with 3~15 DEG C/
The rate of min is cooled to 150~200 DEG C from 360 DEG C~400 DEG C, then naturally cold in 150~200 DEG C of heat preservation 30~120min
But.By controlling the post-processing sintering condition containing the polytetrafluoroethylene (PTFE) precursor film at fine carrier, under stress, protected in carrier
Under shield effect, polytetrafluoroethylgranule granule starts reorientation arrangement, then decomposes in appropriate opportunity carrier, polytetrafluoroethylgranule granule
Further orientation is reset, and forms catenate superfine fibre reticular structure.Preparation side is carried out using the process control condition
The super-hydrophobic polytetrafluoroethylfiber fiber film with special construction can be made.If not under the conditions of process control of the invention, such as
It is sintered 30-90 minutes at be set forth in 280-350 DEG C of CN101994161A, then can not obtain with multilevel roughness, water contact
The super-hydrophobic polytetrafluoroethylfiber fiber film at 150 ° of angle or more, and film is without flexibility.If in addition not using process control (such as
CN102282301A is sintered at 400 DEG C and obtains polytetrafluoroethylene fibre pad, and the ash content of carrier (fibre-forming polymer) is less than 5%.)
The original form that then cannot keep fiber, causes fiber to collapse to flat.By controlling sintered cooling condition, further
Reduce the micro-fractures on fiber, forms seamless fiber surface, the intensity and toughness of reinforcing fiber.
The preparation method of above-mentioned polytetrafluoroethylene film includes preforming step before being sintered after system is fine, it is described it is preforming be by
Polytetrafluoroethylene (PTFE) precursor film is wrapped on branch hold mode, controls polytetrafluoroethylene (PTFE) film thickness by winding layer number and average pore size is big
It is small.The stress orientation that the winding of fiber is superimposed with conducive to sintering process.
The mass concentration of aqueous gelatin solution is 0.5%~30%, and gelatin and polytetrafluoroethylene (PTFE) dry weight ratio are 1: 1~50.
Specifically, a kind of preparation method of polytetrafluoroethylene film, comprising the following steps:
(1) preparation of spinning solution；Gelatin is dissolved in water and is made into the homogeneous solution that concentration is 0.5%~30% mass concentration, so
Ptfe emulsion is added in stirring afterwards, obtains uniform mixed liquor；Gelatin and polytetrafluoroethylene (PTFE) dry weight ratio are 1: 1~50；
(2) system is fine；Fiber is prepared to the spinning solution progress spinning prepared in (1) using the method for spinning or stretching to be gathered
Tetrafluoroethene precursor film；
(3) preforming: it is anticipated that use specification, by (2) it is obtained obtain polytetrafluoroethylene (PTFE) precursor film winding
On the branch hold mode of respective shapes, the film of the different shapes and specification such as flat, tubular type, hollow fiber form or rolling is formed, is led to
Cross winding layer number control film thickness；
(4) it is sintered；Preforming polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace together with branch hold mode even
Continue and is sintered under conditions of being passed through flowing atmosphere；Sintering is sintered using temperature programmed control zonal cooling, with the speed of 3~10 DEG C/min
Rate is from room temperature to 120 DEG C~200 DEG C, in 120 DEG C~200 DEG C 30~120min of heat preservation；With the rate of 2~8 DEG C/min from
120 DEG C~200 DEG C are warming up to 360 DEG C~400 DEG C, in 360 DEG C~400 DEG C 5~120min of heat preservation；
(5) cooling: in the case where flowing atmosphere, to be cooled to 150~200 from 360 DEG C~400 DEG C with the rate of 3~15 DEG C/min
DEG C, in 150~200 DEG C of 30~120min of heat preservation, then natural cooling.
Above-mentioned flowing atmosphere is that nitrogen, air or inert gas are at least one.
Beneficial effect
1. the unique polytetrafluoroethylene film of structure has been made in the present invention, with what is formed in a crisscross manner by beading fiber filament
Hole three-dimensional communication structure, is the hydrophobic surface that one of formation has multistage coarse structure, and beading fiber filament refers to polytetrafluoro
Mutually the fiber filament to be formed is cohered in point and/or face between ethylene particle；Hole is in labyrinth hole, and maximum diameter of hole is 1.0 μm, minimum aperture
Diameter is 0.01 μm, and average pore size is 0.1 μm~0.5 μm；Fiber filament is nanofiber, and average diameter is 500 ± 50nm.
2. the present invention is fabulous to solve the problems, such as that fiber is givey in the sintering of polytetrafluoroethylene (PTFE) precursor film, and obtains
There is beading superfine fibre reticular membrane, stick to each other is become from unordered stacking between fiber, fibre morphology and surface are intact,
Intensity and toughness also improve a lot, and are able to bear certain vacuum pressure (can under 0.7kPa vacuum degree still stably operable).
3. polytetrafluoroethylporous porous membrane obtained by the present invention has special super-hydrophobicity structure, obtained PTFE fiber
Surface forms a large amount of rough surfaces, surface water contact angle >=150 °, and porosity is up to 80% or more.
4, for the polytetrafluoroethylporous porous membrane obtained by the present invention without support, thickness is controllable, is applied to membrane distillation process, leads to
Amount > 20L/m2H, rejection is 99% or more.
5, the invention proposes before sintering winding process carry out it is preforming, can to the shape and thickness of final products film
It is controlled, while guaranteeing high porosity (80% or more), thickness needed for providing film and intensity.In contrast to obtain
High porosity and the stretch processes that stretch at high proportion, the obtained polytetrafluoroethylene film of the method for the present invention is without support, shape
Formula multiplicity, thickness are controllable.
6, polytetrafluoroethylene (PTFE) super-hydrophobic film preparation method provided by the invention makes carrier using sintering condition rate-determining steps
It is decomposed on appropriate opportunity, and polytetrafluoroethylgranule granule melting orientation is reset, and has obtained having beading superfine fibre reticular membrane, this
The special construction of kind nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus have super thin
Aqueous energy.
7, the invention avoids the uses of lubricant in biaxial tension etc., and there is no the removing problem of lubricant, technique letters
Single, without squeezing out, the Complicated Flows such as press mold pollute small.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of polytetrafluoroethylene film made from preparation method of the present invention；It can be seen from attached drawing
Observe: polytetrafluoroethylene film of the invention has the hole three-dimensional communication structure formed in a crisscross manner by beading fiber filament, hole
Gap is in labyrinth hole, and even pore distribution is connected to, and nanofiber form is uniform intact.
Specific embodiment
The present invention is specifically described below by embodiment, it is necessary to which indicated herein is that the present embodiment can only be used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
Embodiment 1
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 15%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into the support of diameter 5cm cylinder
On mould, 5 layers are wound, and is sent in tube furnace and leads to nitrogen, sintering process temperature programmed control, from room temperature to 140 DEG C of 7 DEG C of heating rates/
Min, 140 DEG C of heat preservation 80min are warming up to 373 DEG C from 140 DEG C, and heating rate is 8 DEG C/min is sintered after reaching sintering temperature
373 DEG C of Duan Wendu, keep the temperature 100min.
It is cooling: under the flowing atmosphere of nitrogen, to be cooled to 180 DEG C from 373 DEG C with the rate of 8 DEG C/min, kept the temperature at 180 DEG C
80min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 180 μm, cutting off can
Obtain flat porous membrane.173 ° of the film hydrophobic contact angle, porosity 88%, 0.25 μm of average pore size, tensile strength
497psi, elongation 365%, when for membrane distillation operation, flux 25L/m2H, rejection 99.6%.
Embodiment 2
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 8%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into the support of diameter 5cm cylinder
On mould, 5 layers are wound, and be sent to blowing air in tube furnace, sintering process temperature programmed control, from room temperature to 150 DEG C of 6 DEG C of heating rates/
Min keeps the temperature 70min at 150 DEG C, 390 DEG C is warming up to from 150 DEG C, heating rate is 6 DEG C/min is burnt after reaching sintering temperature
392 DEG C of section temperature of knot keeps the temperature 10min.
It is cooling: under the flowing atmosphere of air, to be cooled to 200 DEG C from 390 DEG C with the rate of 15 DEG C/min, protected at 200 DEG C
Warm 30min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 220um, cutting off can
Obtain flat porous membrane.165 ° of the film hydrophobic contact angle, porosity 88%, 0.5 μm of average pore size, tensile strength
450psi, elongation 320%, when for membrane distillation operation, flux 24L/m2H, rejection 99.6%.
Embodiment 3
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 6%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into the support of diameter 5cm cylinder
On mould, 5 layers are wound, and is sent in tube furnace and leads to nitrogen, sintering process temperature programmed control, from room temperature to 180 DEG C of 4 DEG C of heating rates/
Min, 180 DEG C of heat preservation 40min are warming up to 376 DEG C from 180 DEG C, and heating rate is 3 DEG C/min is sintered after reaching sintering temperature
376 DEG C of Duan Wendu, keep the temperature 80min.
It is cooling: under the flowing atmosphere of nitrogen, to be cooled to 190 DEG C from 376 DEG C with the rate of 5 DEG C/min, kept the temperature at 190 DEG C
40min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 195um, cutting off can
Obtain flat porous membrane.164 ° of the film hydrophobic contact angle, porosity 84%, 0.35 μm of average pore size, tensile strength
470psi, elongation 320%, when for membrane distillation operation, flux 25L/m2H, rejection 99.5%.
Embodiment 4
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 5%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into the support of diameter 5cm cylinder
On mould, 6 layers are wound, and is sent in tube furnace and leads to argon gas, sintering process temperature programmed control, from room temperature to 120 DEG C of 10 DEG C of heating rates/
Min, 120 DEG C of heat preservation 120min are warming up to 388 DEG C from 120 DEG C, and heating rate is 4 DEG C/min is burnt after reaching sintering temperature
388 DEG C of section temperature of knot keeps the temperature 26min.
It is cooling: under the flowing atmosphere of argon gas, to be cooled to 150 DEG C from 388 DEG C with the rate of 15 DEG C/min, protected at 150 DEG C
Warm 120min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the cylindric polytetrafluoroethylene film with a thickness of 220um, cut off
Flat porous membrane can be obtained.157 ° of the film hydrophobic contact angle, porosity 85%, 0.5 μm of average pore size, tensile strength
482psi, elongation 340%, when for membrane distillation operation, flux 28L/m2H, rejection 99.2%.
Embodiment 5
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 10%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.5cm cylinder branch
On hold mode, 5 layers are wound, and is sent in Muffle furnace and leads to nitrogen, sintering process temperature programmed control, from room temperature to 130 DEG C of heating rates 8
DEG C/min, 130 DEG C of heat preservation 100min, 385 DEG C are warming up to from 130 DEG C, heating rate is 7 DEG C/min, after reaching sintering temperature, i.e.,
385 DEG C of sintering stage temperature, keep the temperature 35min.
It is cooling: under the flowing atmosphere of nitrogen, to be cooled to 160 DEG C from 385 DEG C with the rate of 12 DEG C/min, protected at 160 DEG C
Warm 100min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the tubular membrane with a thickness of 177um.The film hydrophobic contact angle
173 °, porosity 86%, 0.12 μm of average pore size, tensile strength 470psi, elongation 345% is grasped for tubular membrane membrane distillation
When making, flux 35L/m2H, rejection 99.6%.
Embodiment 6
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 6%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.5cm cylinder branch
On hold mode, 5 layers are wound, and is sent in tube furnace and leads to argon gas, sintering process temperature programmed control, from room temperature to 160 DEG C of heating rates 5
DEG C/min, 160 DEG C of heat preservation 100min, 380 DEG C are warming up to from 160 DEG C, heating rate is 5 DEG C/min, after reaching sintering temperature, i.e.,
380 DEG C of sintering stage temperature, keep the temperature 60min.
It is cooling: under the flowing atmosphere of argon gas, to be cooled to 170 DEG C from 380 DEG C with the rate of 10 DEG C/min, protected at 170 DEG C
Warm 90min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the tubular membrane with a thickness of 218um.The film hydrophobic contact angle
167 °, porosity 85%, 0.25 μm of average pore size, tensile strength 480psi, elongation 335% is grasped for tubular membrane membrane distillation
When making, flux 39L/m2H, rejection 99.6%.
Embodiment 7
It is equal that the ptfe emulsion of solid content 60% is added drop-wise to stirring in the aqueous gelatin solution that mass fraction is 3%
It is even, it is made into spinning solution.Then polytetrafluoroethylene (PTFE) precursor film is made using electrospinning process.It is wound into diameter 0.1cm cylinder branch
On hold mode, 6 layers are wound, and be sent to blowing air in tube furnace, sintering process temperature programmed control, from room temperature to 200 DEG C of heating rates 3
DEG C/min, 200 DEG C of heat preservation 30min, 385 DEG C are warming up to from 200 DEG C, heating rate is 2 DEG C/min, after reaching sintering temperature, i.e.,
At 370 DEG C of sintering stage temperature, 120min is kept the temperature.
It is cooling: under the flowing atmosphere of air, to be cooled to 185 DEG C from 370 DEG C with the rate of 9 DEG C/min, kept the temperature at 185 DEG C
70min, then natural cooling.
It extracts cylinder branch hold mode after taking out after cooling out, obtains the hollow-fibre membrane with a thickness of 207um.The film hydrophobic contact angle
175 °, porosity 85%, 0.40 μm of average pore size, tensile strength 480psi, elongation 370% is steamed for hollow-fibre membrane
When evaporating operation, flux 40L/m2H, rejection 99.9%.
Claims (6)
1. a kind of preparation method of polytetrafluoroethylene film, including spinning solution is with liquid, system is fine, is sintered, it is characterised in that: at fine carrier
Ptfe emulsion is added after being configured to solution with solvent, is gelatin at fine carrier, solvent is water；Sintering uses temperature programmed control
Zonal cooling sintering, in the case where flowing atmosphere, with the rate of 3~10 DEG C/min from room temperature to 120 DEG C~200 DEG C, at 120 DEG C
~200 DEG C of 30~120min of heat preservation；360 DEG C~400 DEG C are warming up to from 120 DEG C~200 DEG C with the rate of 2~8 DEG C/min,
360 DEG C~400 DEG C 5~120min of heat preservation；Cooling treatment is carried out after sintering, the cooling in the case where flowing atmosphere, with 3~15 DEG C/
The rate of min is cooled to 150~200 DEG C from 360 DEG C~400 DEG C, then naturally cold in 150~200 DEG C of heat preservation 30~120min
But.
2. the preparation method of polytetrafluoroethylene film as described in claim 1 includes preforming step before being sintered after system is fine, described
Preforming is that polytetrafluoroethylene (PTFE) precursor film is wrapped on branch hold mode.
3. the mass concentration of the preparation method of polytetrafluoroethylene film as claimed in claim 1 or 2, institute's gelatin water solution is
0.5%~30%, gelatin and polytetrafluoroethylene (PTFE) dry weight ratio are 1:1~50.
4. the preparation method of polytetrafluoroethylene film as described in claim 1, comprising the following steps: (1) preparation of spinning solution；It will be bright
Peptization is made into the homogeneous solution that concentration is 0.5%~30% mass concentration in water, and then ptfe emulsion is added in stirring, obtains
Uniform mixed liquor；Gelatin and polytetrafluoroethylene (PTFE) dry weight ratio are in 1:1~50；(2) system is fine；Using the method pair of spinning or stretching
(1) the spinning solution progress spinning prepared in prepares fiber and obtains polytetrafluoroethylene (PTFE) precursor film；(3) preforming: it is anticipated that make
With specification, the polytetrafluoroethylene (PTFE) precursor film that obtains obtained in (2) is wrapped on the branch hold mode of respective shapes, forms plate
Formula, tubular type, hollow fiber form or rolling shape；(4) it is sintered；By preforming polytetrafluoroethylene (PTFE) precursor film obtained in (3) together with
Branch hold mode is put into high temperature furnace to be sintered under conditions of being continuously passed through flowing atmosphere；Sintering uses temperature programmed control zonal cooling
Sintering, with the rate of 3~10 DEG C/min from room temperature to 120 DEG C~200 DEG C, 120 DEG C~200 DEG C keep the temperature 30~
120min；360 DEG C~400 DEG C are warming up to from 120 DEG C~200 DEG C with the rate of 2~8 DEG C/min, keeps the temperature 5 at 360 DEG C~400 DEG C
~120min；(5) cooling: in the case where flowing atmosphere, to be cooled to 150~200 from 360 DEG C~400 DEG C with the rate of 3~15 DEG C/min
DEG C, in 150~200 DEG C of 30~120min of heat preservation, then natural cooling.
5. the preparation method of the polytetrafluoroethylene film as described in claim 1,2 or 4, the flowing atmosphere be nitrogen, air or
Inert gas is at least one.
6. the preparation method of polytetrafluoroethylene film as claimed in claim 3, the flowing atmosphere is nitrogen, air or indifferent gas
Body is at least one.
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| CN109395603A (en) * | 2017-08-18 | 2019-03-01 | 重庆润泽医药有限公司 | A kind of preparation method of macromolecule semi-permeable material |
| CN114318936B (en) * | 2022-01-17 | 2022-11-25 | 中国人民解放军国防科技大学 | Flexible repairable super-hydrophobic membrane and preparation method and application thereof |
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|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN101994161A (en) * | 2009-08-25 | 2011-03-30 | 东丽纤维研究所（中国）有限公司 | Method for preparing polytetrafluoroethylene superfine fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
| CN101994161A (en) * | 2009-08-25 | 2011-03-30 | 东丽纤维研究所（中国）有限公司 | Method for preparing polytetrafluoroethylene superfine fiber |
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| Title |
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| 热处理对PTFE牵伸性能的影响;郭占军等;《纺织学报》;20100630;第31卷(第6期);第21-24页 |
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