CN105013350A - Preparation method of super-hydrophobic polytetrafluoroethylene fiber film - Google Patents
Preparation method of super-hydrophobic polytetrafluoroethylene fiber film Download PDFInfo
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- CN105013350A CN105013350A CN201410163014.5A CN201410163014A CN105013350A CN 105013350 A CN105013350 A CN 105013350A CN 201410163014 A CN201410163014 A CN 201410163014A CN 105013350 A CN105013350 A CN 105013350A
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 88
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 79
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 52
- 239000000835 fiber Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000003075 superhydrophobic effect Effects 0.000 title description 5
- 238000005245 sintering Methods 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 75
- 238000009413 insulation Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000009987 spinning Methods 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 210000002950 fibroblast Anatomy 0.000 claims description 8
- 239000003570 air Substances 0.000 claims description 6
- 238000004804 winding Methods 0.000 claims description 5
- 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
- 230000000873 masking effect Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 230000005661 hydrophobic surface Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002352 surface water Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 description 24
- 208000027418 Wounds and injury Diseases 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 13
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000001523 electrospinning Methods 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 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
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 1
- 208000013201 Stress fracture Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 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
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 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 invention provides a preparation method of a polytetrafluoroethylene film. The preparation method comprises the steps of preparing fibers with a fiber forming carrier and sintering and is characterized by adopting multistep continuous sintering through program temperature control, and in flowing atmospheres, insulating at 90-120 DEG C for 30-120 minutes, increasing the temperature from 90-120 DEG C to 260-300 DEG C at a rate of 3-10 DEG C/min and insulating at 260-300 DEG C for 30-120 minutes; increasing the temperature from 260-300 DEG C to 370-390 DEG C at a rate of 2-8 DEG C/min and insulating at 370-390 DEG C for 5-120 minutes; carrying out cooling treatment after sintering: in the flowing atmospheres, reducing the temperature from 360-400 DEG C to 150-200 DEG C at a rate of 3-15 DEG C/min, insulating at 150-200 DEG C for 30-120 minutes and then carrying out natural cooling. The preparation method has the beneficial effects that the polytetrafluoroethylene film with bead-like superfine fibers is prepared and a hydrophobic surface with a multistage coarse structure is formed together; the surface water contact angle is not less than 150 degrees and the porosity is higher than 80%; the problem that fibers are easy to collapse during sintering of a polytetrafluoroethylene precursor film is solved; the fibers have intact morphologies and surfaces and greatly improved strength and tenacity and can bear higher vacuum pressure.
Description
Technical field
The present invention relates to a kind of preparation method of the diffusion barrier material for separating of field, be specifically related to a kind of preparation method of hydrophobic membrane material.
Technical background
Hydrophobicity is the critical nature of polytetrafluoroethylene (PTFE) (PTFE) material, is the main performance that polytetrafluoroethylporous porous membrane is applied to membrane material.Although polytetrafluoroethylmaterial material has low-surface-energy, the water contact angle of smooth polytetrafluoroethylene (PTFE) plane is between 98 to 112 °, and hydrophobic performance is not good.
Current polytetrafluoroethylporous porous membrane preparation adopts bidirectional extending method more.When this method will expect the film of higher porosity, need to carry out vast scale stretching to film, cannot control by Surface Structures, and thickness is only below tens microns, backing material is needed in using, and backing material itself often has certain limitation in heat resistance or chemical stability or hydrophobic performance, thus limit the application of this biaxial stretching film.Stretch at high proportion simultaneously and be often difficult to the shape of controlling diaphragm, therefore main based on Flat Membrane.The patents such as Chinese patent CN1775847A, CN102007242A, CN101543734B, CN102151494A all carry out polytetrafluoroethylporous porous membrane preparation based on above stretch processes.
The patents such as support methods prepares the important method of polytetrafluoroethylene fibre, CN101994161A and CN102282301A adopt the preparation of electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber to report.All relate to the step of high temperature sintering removing fibroblast carrier in these reports, but these sintering processes only pay close attention to the removal of fibroblast template.Specifically: the object of CN101994161A is a kind of polytetrafluoroethylsuperfine superfine fiber of preparation, its preparation method adopts polyvinyl alcohol to make carrier, to be weaved out polytetrafluoroethylene fibre precursor by electrospinning process, post-processing approach is by polytetrafluoroethylene fibre precursor at 100 ~ 120 DEG C dry 5 ~ 15 minutes, then sinters 30 ~ 90 minutes at 280 ~ 350 DEG C; The object of sintering removes to make polyvinyl alcohol decompose.And CN102282301A improving one's methods of a kind of polytetrafluoroethylene (PTFE) pad is mainly provided, its objective is that the technological parameter (spinning fluid viscosity) in order to improve electrospinning obtains the polytetrafluoroethylene fibre pad precursor of uniform diameter, at 400 DEG C, sintering obtains polytetrafluoroethylene fibre pad again, and the ash content of carrier (fibre-forming polymer) is less than 5%.The patents such as CN101994161A and CN102282301A adopt electrostatic spinning technique to polytetrafluoroethylsuperfine superfine fiber (pad), only consider and how to obtain polytetrafluoroethylsuperfine superfine fiber (pad), have to conventional polytetrafluoroethylsuperfine superfine fiber (pad).
Summary of the invention
The object of the present invention is to provide a kind of preparation method of poly tetrafluoroethylene, by controlling the post processing sintering condition of the polytetrafluoroethylene (PTFE) precursor film containing fibroblast carrier, by the method precise hard_drawn tuhes sintering condition of temperature programmed control and cooling condition to obtain fibre morphology and remain intact and to have the superfine fibre reticular membrane of beading structure, the special construction of this nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus there is ultra-hydrophobicity.
Object of the present invention is realized by following technical measures:
A kind of preparation method of poly tetrafluoroethylene, comprise fibroblast carrier system fibre sintering, it is characterized in that: sintering adopts temperature programmed control zonal cooling sintering, under flowing atmosphere, at 90 DEG C ~ 120 DEG C insulation 30 ~ 120min, 260 DEG C ~ 300 DEG C are warmed up to from 90 DEG C ~ 120 DEG C, at 260 DEG C ~ 300 DEG C insulation 30 ~ 120min with the speed of 3 ~ 10 DEG C/min; 370 DEG C ~ 390 DEG C are warmed up to from 260 DEG C ~ 300 DEG C, at 370 DEG C ~ 390 DEG C insulation 5 ~ 120min with the speed of 2 ~ 8 DEG C/min; Cooling processing after sintering, described cooling, under flowing atmosphere, is cooled to 150 ~ 200 DEG C with the speed of 3 ~ 15 DEG C/min from 360 DEG C ~ 400 DEG C, at 150 ~ 200 DEG C of insulation 30 ~ 120min, then naturally cools.
By controlling the post processing sintering condition of the polytetrafluoroethylene (PTFE) precursor film containing fibroblast carrier; under effect of stress; under carrier protective effect; polytetrafluoroethylgranule granule starts reorientation arrangement; subsequently in appropriate carrier decomposition on opportunity; the further orientation of polytetrafluoroethylgranule granule is reset, and forms catenate superfine fibre network structure.Programme-control condition described in employing is prepared the super-hydrophobic polytetrafluoroethylfiber fiber film that can obtain and have special construction.If not under programme-control condition of the present invention, as CN101994161A be set forth in 280-350 DEG C at sinter 30-90 minute, then cannot obtain have multilevel roughness, the super-hydrophobic polytetrafluoroethylfiber fiber film of water contact angle more than 150 °, and film does not have flexibility.If (obtain polytetrafluoroethylene fibre pad as CN102282301A sinters at 400 DEG C, the ash content of carrier (fibre-forming polymer) is less than 5% not adopt programme-control in addition.) then cannot keep original form of fiber, cause fiber to collapse to flat.By controlling the cooling condition after sintering, further reducing the micro-fractures on fiber, forming seamless fiber surface, the intensity of fortifying fibre and toughness.
Preferably, above-mentioned sintering adopts temperature programmed control zonal cooling sintering, under flowing atmosphere, with 2 ~ 15 DEG C/min from room temperature to 90 DEG C ~ 120 DEG C, at 100 DEG C ~ 120 DEG C insulation 50 ~ 100min, 280 DEG C ~ 300 DEG C are warmed up to from 100 DEG C ~ 120 DEG C, at 280 DEG C ~ 300 DEG C insulation 60 ~ 120min with the speed of 5 ~ 8 DEG C/min; 380 DEG C ~ 390 DEG C are warmed up to from 280 DEG C ~ 300 DEG C, at 380 DEG C ~ 390 DEG C insulation 30 ~ 80min with the speed of 4 ~ 7 DEG C/min.
The preparation method of above-mentioned poly tetrafluoroethylene, comprise preforming step before sintering after system is fine, described preformed is wrapped on supporting die by polytetrafluoroethylene (PTFE) precursor film, by winding layer numerical control polytetrafluoroethylene (PTFE) film thickness and mean pore size.The winding of fiber is superimposed with the stress orientation being beneficial to sintering process.
Particularly, a kind of preparation method of poly tetrafluoroethylene, comprises the following steps:
(1) preparation of spinning solution; Be made into water-soluble for water-soluble polymer the homogeneous solution that concentration is 0.5% ~ 30% mass concentration, then stir and add ptfe emulsion, obtain uniform mixed liquor; Fibroblast carrier and polytetrafluoroethylene (PTFE) dry weight ratio are 1: 1 ~ 50;
(2) system is fine; Adopt the method for spinning or stretching spinning solution to preparation in (1) to carry out spinning to prepare fiber and obtain polytetrafluoroethylene (PTFE) precursor film;
(3) preformed: according to the use specification of expection, the polytetrafluoroethylene (PTFE) precursor film that obtains obtained in (2) is wrapped on the supporting die of respective shapes, form the film of flat, the difformity such as tubular type, hollow fiber form or rolling and specification, thick by winding layer numerical control masking;
(4) sinter; The preformed polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace together with supporting die sinter under the condition passing into flowing atmosphere continuously; Sintering adopts temperature programmed control zonal cooling sintering, with the speed of 3 ~ 10 DEG C/min from room temperature to 120 DEG C ~ 200 DEG C, at 120 DEG C ~ 200 DEG C insulation 30 ~ 120min; 360 DEG C ~ 400 DEG C are warmed up to from 120 DEG C ~ 200 DEG C, at 360 DEG C ~ 400 DEG C insulation 5 ~ 120min with the speed of 2 ~ 8 DEG C/min;
(5) cool: under flowing atmosphere, be cooled to 150 ~ 200 DEG C with the speed of 3 ~ 15 DEG C/min from 360 DEG C ~ 400 DEG C, at 150 ~ 200 DEG C of insulation 30 ~ 120min, then naturally cool.
Above-mentioned flowing atmosphere is air, nitrogen or inert gas at least one.
Beneficial effect
1. the present invention has obtained the poly tetrafluoroethylene of structure uniqueness, have by the crisscross hole three-dimensional communication structure formed of beading filament, be the hydrophobic surface that one formation has multistage coarse structure, beading filament refers to that between polytetrafluoroethylgranule granule, the filament of formation is cohered in point and/or face mutually; Hole is hole, labyrinth, and maximum diameter of hole is 1.0 μm, and minimum-value aperture is 0.01 μm, and average pore size is 0.1 μm ~ 0.5 μm; Filament is nanofiber, and average diameter is 500 ± 50nm.
2. what the present invention was fabulous solves the givey problem of fiber in polytetrafluoroethylene (PTFE) precursor film sintering, and obtain and there is beading superfine fibre reticular membrane, between fiber from unordered stacking become inter-adhesive, fibre morphology and surface intact, intensity and toughness also improve a lot, and can bear high vacuum pressure (can under 0.8kPa vacuum still stably operable).
3. the polytetrafluoroethylporous porous membrane obtained by the present invention, has special super-hydrophobicity structure, and the PTFE fiber surface obtained forms a large amount of rough surface, surface water contact angle >=150 °, and porosity is up to more than 80%.
4, the polytetrafluoroethylporous porous membrane obtained by the present invention is without the need to supporting, and thickness is controlled, is applied to Membrane Materials process, flux > 20L/m
2h, rejection is more than 99%.
5, the present invention proposes the winding process before sintering and carry out preformed, can control the shape of final products film and thickness, while guarantee high porosity (more than 80%), provide the thickness needed for film and intensity.In contrast to the stretch processes stretched at high proportion for obtaining high porosity, the poly tetrafluoroethylene that the inventive method obtains is without the need to supporting, and various informative, thickness is controlled.
6, polytetrafluoroethylene (PTFE) super-hydrophobic film preparation method provided by the invention, adopt sintering condition rate-determining steps, carrier was decomposed on appropriate opportunity, and polytetrafluoroethylgranule granule melting orientation is reset, obtain and have beading superfine fibre reticular membrane, the special construction of this nanoscale forms the hydrophobic surface with multistage coarse structure together with superfine fibre.Thus there is ultra-hydrophobicity.
7, present invention, avoiding the use of lubricant in biaxial tension etc., there is not the removing problem of lubricant, technique is simple, and without the need to extruding, the Complicated Flows such as press mold, pollute little.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the poly tetrafluoroethylene that preparation method of the present invention obtains; Can observe from accompanying drawing: poly tetrafluoroethylene of the present invention has by the crisscross hole three-dimensional communication structure formed of beading filament, and hole is hole, labyrinth, even pore distribution is communicated with, and nanofiber form is homogeneous intact.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the present embodiment can only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 12%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in tube furnace, sintering process temperature programmed control, with 10 DEG C/min from room temperature to 110 DEG C, 110 DEG C of insulation 90min, be warming up to 290 DEG C with 7 DEG C/min programming rate from 110 DEG C, 290 DEG C of insulation 100min, are warmed up to 380 DEG C from 290 DEG C, programming rate is 6 DEG C/min, insulation 60min.
Cooling: under the flowing atmosphere of nitrogen, be cooled to 180 DEG C with the speed of 8 DEG C/min from 373 DEG C, at 180 DEG C of insulation 80min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain the cylindric poly tetrafluoroethylene that thickness is 185 μm, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 175 °, porosity 88%, average pore size 0.45 μm, hot strength 585psi, percentage elongation 388%, when operating for Membrane Materials, flux 42L/m
2h, rejection 99.7%.
Embodiment 2
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyacrylic acid aqueous solution of 9%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in tube furnace, sintering process temperature programmed control, with 2 DEG C/min from room temperature to 90 DEG C, 90 DEG C of insulation 120min, be warming up to 260 DEG C with 10 DEG C/min programming rate from 90 DEG C, 260 DEG C of insulation 120min, are warmed up to 375 DEG C from 260 DEG C, programming rate is 8 DEG C/min, insulation 115min.
Cooling: under the flowing atmosphere of air, be cooled to 200 DEG C with the speed of 15 DEG C/min from 390 DEG C, at 200 DEG C of insulation 30min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain the cylindric poly tetrafluoroethylene that thickness is 175um, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 162 °, porosity 82%, average pore size 0.45 μm, hot strength 470psi, percentage elongation 320%, when operating for Membrane Materials, flux 26L/m
2h, rejection 99.5%.
Embodiment 3
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the sodium alginate aqueous solution of 5%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in tube furnace, sintering process temperature programmed control, with 5 DEG C/min from room temperature to 100 DEG C, 100 DEG C of insulation 110min, be warming up to 275 DEG C with 10 DEG C/min programming rate from 100 DEG C, 275 DEG C of insulation 110min, are warmed up to 380 DEG C from 275 DEG C, programming rate is 3 DEG C/min, insulation 90min.
Cooling: under the flowing atmosphere of air, be cooled to 190 DEG C with the speed of 5 DEG C/min from 376 DEG C, at 190 DEG C of insulation 40min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain the cylindric poly tetrafluoroethylene that thickness is 189um, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 165 °, porosity 82%, average pore size 0.25 μm, hot strength 485psi, percentage elongation 335%, when operating for Membrane Materials, flux 30L/m
2h, rejection 99.5%.
Embodiment 4
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the aqueous gelatin solution of 7%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 5cm cylinder supporting die, be wound around 6 layers, and deliver to blowing air in tube furnace, sintering process temperature programmed control, with 8 DEG C/min from room temperature to 100 DEG C, 100 DEG C of insulation 100min, be warming up to 280 DEG C with 8 DEG C/min programming rate from 100 DEG C, 280 DEG C of insulation 120min, are warmed up to 385 DEG C from 280 DEG C, programming rate is 4 DEG C/min, insulation 80min.
Cooling: under the flowing atmosphere of argon gas, be cooled to 150 DEG C with the speed of 15 DEG C/min from 388 DEG C, at 150 DEG C of insulation 120min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain thickness be 220um cylindric poly tetrafluoroethylene, cut off and can obtain flat porous membrane.This film hydrophobic contact angle 165 °, porosity 85%, average pore size 0.45 μm, hot strength 495psi, percentage elongation 345%, when operating for Membrane Materials, flux 32L/m
2h, rejection 99.2%.
Embodiment 5
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the polyvinyl alcohol water solution of 13%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 0.5cm cylinder supporting die, be wound around 5 layers, and deliver to logical nitrogen in Muffle furnace, sintering process temperature programmed control, with 15 DEG C/min from room temperature to 120 DEG C, 120 DEG C of insulation 30min, be warming up to 295 DEG C with 3 DEG C/min programming rate from 120 DEG C, 295 DEG C of insulation 120min, are warmed up to 390 DEG C from 295 DEG C, programming rate is 2 DEG C/min, insulation 10min.
Cooling: under the flowing atmosphere of nitrogen, be cooled to 160 DEG C with the speed of 12 DEG C/min from 385 DEG C, at 160 DEG C of insulation 100min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain the tubular membrane that thickness is 178um.This film hydrophobic contact angle 171 °, porosity 85%, average pore size 0.5 μm, hot strength 500psi, percentage elongation 340%, when operating for tubular membrane Membrane Materials, flux 35L/m
2h, rejection 99.6%.
Embodiment 6
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the sodium alginate aqueous solution of 8%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 0.5cm cylinder supporting die, be wound around 5 layers, and deliver to logical argon gas in tube furnace, sintering process temperature programmed control, with 12 DEG C/min from room temperature to 115 DEG C, 115 DEG C of insulation 50min, be warming up to 300 DEG C with 5 DEG C/min programming rate from 115 DEG C, 300 DEG C of insulation 60min, are warmed up to 390 DEG C from 300 DEG C, programming rate is 6 DEG C/min, insulation 30min.
Cooling: under the flowing atmosphere of argon gas, be cooled to 170 DEG C with the speed of 10 DEG C/min from 380 DEG C, at 170 DEG C of insulation 90min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain the tubular membrane that thickness is 178um.This film hydrophobic contact angle 175 °, porosity 89%, average pore size 0.35 μm, hot strength 489psi, percentage elongation 355%, when operating for tubular membrane Membrane Materials, flux 37L/m
2h, rejection 99.6%.
Embodiment 7
The ptfe emulsion of solid content 60% being added drop-wise to mass fraction is stir in the aqueous gelatin solution of 4%, is made into spinning solution.Then electrospinning process is adopted to make polytetrafluoroethylene (PTFE) precursor film.Be wound on diameter 0.1cm cylinder supporting die, be wound around 6 layers, and deliver to blowing air in tube furnace, sintering process temperature programmed control, with 9 DEG C/min from room temperature to 110 DEG C, 110 DEG C of insulation 80min, be warming up to 285 DEG C with 6 DEG C/min programming rate from 110 DEG C, 285 DEG C of insulation 70min, are warmed up to 380 DEG C from 285 DEG C, programming rate is 5 DEG C/min, insulation 60min.
Cooling: under the flowing atmosphere of nitrogen, be cooled to 185 DEG C with the speed of 9 DEG C/min from 370 DEG C, at 185 DEG C of insulation 70min, then cools naturally.
Extract cylinder supporting die out after taking out after cooling, obtain the hollow-fibre membrane that thickness is 214um.This film hydrophobic contact angle 175 °, porosity 85%, average pore size 0.4 μm, hot strength 650psi, percentage elongation 370%, during for hollow-fibre membrane distillation procedure, flux 41L/m
2h, rejection 99.9%.
Claims (5)
1. the preparation method of a poly tetrafluoroethylene, comprise fibroblast carrier system fibre sintering, it is characterized in that: sintering adopts temperature programmed control zonal cooling sintering, under flowing atmosphere, at 90 DEG C ~ 120 DEG C insulation 30 ~ 120min, 260 DEG C ~ 300 DEG C are warmed up to from 90 DEG C ~ 120 DEG C, at 260 DEG C ~ 300 DEG C insulation 30 ~ 120min with the speed of 3 ~ 10 DEG C/min; 370 DEG C ~ 390 DEG C are warmed up to from 260 DEG C ~ 300 DEG C, at 370 DEG C ~ 390 DEG C insulation 5 ~ 120min with the speed of 2 ~ 8 DEG C/min; Cooling processing after sintering, described cooling, under flowing atmosphere, is cooled to 150 ~ 200 DEG C with the speed of 3 ~ 15 DEG C/min from 360 DEG C ~ 400 DEG C, at 150 ~ 200 DEG C of insulation 30 ~ 120min, then naturally cools.
2. the preparation method of poly tetrafluoroethylene as claimed in claim 1, described sintering adopts temperature programmed control zonal cooling sintering, under flowing atmosphere, with 2 ~ 15 DEG C/min from room temperature to 90 DEG C ~ 120 DEG C, at 100 DEG C ~ 120 DEG C insulation 50 ~ 100min, 280 DEG C ~ 300 DEG C are warmed up to from 100 DEG C ~ 120 DEG C, at 280 DEG C ~ 300 DEG C insulation 60 ~ 120min with the speed of 5 ~ 8 DEG C/min; 380 DEG C ~ 390 DEG C are warmed up to from 280 DEG C ~ 300 DEG C, at 380 DEG C ~ 390 DEG C insulation 30 ~ 80min with the speed of 4 ~ 7 DEG C/min.
3. the preparation method of poly tetrafluoroethylene as claimed in claim 1 or 2, comprise preforming step before sintering after system is fine, described preformed is wrapped on supporting die by polytetrafluoroethylene (PTFE) precursor film.
4. the preparation method of poly tetrafluoroethylene as claimed in claim 1, comprises the following steps:
(1) preparation of spinning solution: be made into the homogeneous solution that concentration is 0.5% ~ 30% mass concentration by water-soluble for water-soluble polymer, then stirs and adds ptfe emulsion, obtain uniform mixed liquor; Fibroblast carrier and polytetrafluoroethylene (PTFE) dry weight ratio are in 1:1 ~ 50;
(2) system is fine: adopt the method for spinning or stretching spinning solution to preparation in (1) to carry out spinning and prepare fiber and obtain polytetrafluoroethylene (PTFE) precursor film;
(3) preformed: according to the use specification of expection, the polytetrafluoroethylene (PTFE) precursor film that obtains obtained in (2) is wrapped on the supporting die of respective shapes, form the film of flat, the difformity such as tubular type, hollow fiber form or rolling and specification, thick by winding layer numerical control masking;
(4) sinter: the preformed polytetrafluoroethylene (PTFE) precursor film obtained in (3) is put into high temperature furnace together with supporting die and sinters under the condition passing into flowing atmosphere continuously; Sintering adopts temperature programmed control zonal cooling sintering, with the speed of 3 ~ 10 DEG C/min from room temperature to 120 DEG C ~ 200 DEG C, at 120 DEG C ~ 200 DEG C insulation 30 ~ 120min; 360 DEG C ~ 400 DEG C are warmed up to from 120 DEG C ~ 200 DEG C, at 360 DEG C ~ 400 DEG C insulation 5 ~ 120min with the speed of 2 ~ 8 DEG C/min;
(5) cool: under flowing atmosphere, be cooled to 150 ~ 200 DEG C with the speed of 3 ~ 15 DEG C/min from 360 DEG C ~ 400 DEG C, at 150 ~ 200 DEG C of insulation 30 ~ 120min, then naturally cool.
5. the preparation method of the poly tetrafluoroethylene as described in claim 1,2,3 or 4, described flowing atmosphere is air, nitrogen or inert gas at least one.
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| CN105664733A (en) * | 2016-01-21 | 2016-06-15 | 巨化集团技术中心 | Preparation method of perfluoro hollow fiber composite film |
| CN106669451A (en) * | 2015-11-11 | 2017-05-17 | 重庆润泽医药有限公司 | Polytetrafluoroethylene ultrafine fiber membrane |
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| CN101234296A (en) * | 2008-02-29 | 2008-08-06 | 南京工业大学 | Preparation technique of porous stainless steel-ceramic compound film |
| CN101530750A (en) * | 2009-04-20 | 2009-09-16 | 浙江理工大学 | Preparation method of polytetrafluoroethylene superfine fiber porous membrane |
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