CN107511081A - A kind of preparation method of antipollution PTFE CA/SiNPs composite membranes - Google Patents
A kind of preparation method of antipollution PTFE CA/SiNPs composite membranes Download PDFInfo
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- CN107511081A CN107511081A CN201710958053.8A CN201710958053A CN107511081A CN 107511081 A CN107511081 A CN 107511081A CN 201710958053 A CN201710958053 A CN 201710958053A CN 107511081 A CN107511081 A CN 107511081A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/36—Polytetrafluoroethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2669—Distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
Abstract
The present invention relates to a kind of preparation method of antipollution PTFE CA/SiNPs composite membranes, more particularly to prepares the pollution of surface oil resistant using method of electrostatic spinning and has the method for porous three-dimensional space net structure composite membrane.The present invention super hydrophilic anti-pollution layer in hydrophobic basement membrane PTFE surface constructions by method of electrostatic spinning, is prepared for PTFE CA/SiNPs composite membranes, not only film-forming process is simple for this method, easy to operate, it is easy to accomplish industrialized production；And the composite membrane antifouling property of preparation is good, permeation flux is high, chemical stability is strong, good mechanical properties, retention efficiency high, is with a wide range of applications.
Description
【Technical field】
The present invention relates to a kind of antipollution (polytetrafluoroethylene (PTFE)-cellulose acetate/silicon nanoparticle) PTFE-CA/SiNPs is multiple
The preparation method of film is closed, oil resistant pollution in surface is more particularly to prepared using method of electrostatic spinning and there is porous three-dimensional spatial networks knot
The method of structure composite membrane.When the composite membrane is mixed with the low interfacial energy material such as low concentration crude oil or class alkane suitable for feed liquid
Membrane distillation process, also can be used as microfiltration membranes be applied to industry or medical field micro-filtration and M8003 line filtering etc. process.
【Background technology】
Membrane distillation is the membrane separating process that membrane technology is combined with still-process, and it is using dewatering microporous film as medium.Due to
The hydrophobicity of film, the aqueous solution of both sides can not enter opposite side through fenestra, but due to the hot side aqueous solution and the water of membrane interface
Vapour pressure is higher than cold side, and in the presence of the vapour pressure deficit of film both sides, volatile component is entered through fenestra in vapour form in feed liquid
Entering low temperature side and condensing turns into diffusate, and the high temperature side aqueous solution then turns into concentrate.Solution need not be heated to by membrane distillation process
Boiling point, as long as film both sides maintain the appropriate temperature difference, the process can just be carried out, therefore the low temperature membrane distillation that is otherwise known as.With other
Conventional separation process is compared, and membrane distillation has that separative efficiency is high, operating condition is gentle, to film and material liquid interphase interaction and film
The advantage such as mechanical property requirements are low；In addition, membrane distillation process can handle the brackish water of high concentration, or even solution can be concentrated to
Hypersaturated state and crystallize precipitation, i.e., so-called membrane distillation crystallization technique (Wu Yonglie,《Membrane science and technology》, the Chinese Academy of Sciences
Changchun applied chemistry study institute, 2003).
Membrane material for membrane distillation process should meet two requirements of hydrophobicity and porous, to ensure that water does not penetrate into
Micropore is interior and has higher permeation flux；And in actual applications, when being mixed with low-surface energy substance in feed liquid, film surface is
The absorption pollution of generation organic matter causes blockage of the micro orifice, film surface wetting phenomena.At present, to hydrophobic membrane surface hydrophilic modification, realize anti-
The method of pollution mainly has three classes：First, surface coats, this method needs wet method to preserve, and coat is easily lost in, hydrophily
Can not be lasting.As the A of patent CN 101912740 disclose a kind of method of performing hydrophilic modification on surface of polyvinylidene fluoride microporous membrane.
This method handles pvdf membrane with alkaline oxidiser, acidic reduction agent and glycerite successively, operates than relatively hazardous, and sweet
Oil is attached to film surface only by physisorption, and hydrophilicity persistence is poor；Second, blending modification by copolymerization, this method
Though simple and easy, the membrane material prepared is uneven, and aperture is difficult to control.As the A of patent CN 103272493 disclose a kind of gather
The film hydrophilically modified method of vinylidene, this method is using acrylic acid and two kinds of function monomers of N hydroxymethyl acrylamide, peroxide
Change benzoyl is radical initiator, by adjusting reaction pressure, reaction time, two kinds of monomers use in supercritical carbon dioxide
The conditions such as amount carry out graft modification polymerisation.This method is using the equipment such as autoclave, operational hazards and cost is higher；Third, etc.
Gas ions corrosion or chemical attack, the past polytetrafluoroethylproducts products surface coating polyethylene glycol as the A of CN 101979429 are announced are right
Using plasma processing method carries out surface modification to interface to improve polytetrafluoroethylproducts products surface work energy afterwards, improves its leaching
Lubricant nature and cementability.Though this method of modifying is successfully introduced into hydrophilic radical, membrane superficial tissue is caused necessarily to damage.Moreover,
Though modified hydrophobic membrane shows certain antifouling property but can not be applied in membrane distillation separation process.
Electrostatic spinning is a kind of special fiber fabrication process, and polymer solution or melt carry out injection spinning in highfield
Silk.Under electric field action, the drop at syringe needle can be changed into conical (i.e. " taylor cone ") from spherical, and extend from conical tip
To fiber filaments.This mode can produce the polymer filaments of nanometer grade diameter, and fiber is determined in the netted nothing of three dimensions
To distribution, the antipollution nanofiber mats surface being made up of fiber have porosity is high, specific surface area is big, fiber fine degree with
The advantages that homogeneity is high, draw ratio is big.Electrostatic spinning is carried out by basement membrane of hydrophobic membrane, hydrophobic group membrane aperture and aperture point can be optimized
Cloth and membrane surface structure will not be destroyed；Anti-pollution layer can be brought into close contact with basement membrane, obtain permanent antifouling property.
【The content of the invention】
The invention aims to overcome in the prior art, hydrophobic membrane antifouling property is poor, hydrophilic modifying is unstable and the longevity
Order technical problem that is short and can not being applied in membrane distillation separation process, there is provided a kind of antipollution PTFE-CA/SiNPs composite membranes
Preparation method.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：
(1) preparation of silicon dioxide gel liquid：
0 DEG C of preservation will be placed in after 15.5ml tetraethyl orthosilicates stoste and 10.0ml absolute ethyl alcohol magnetic agitations 1h first；So
After measure 2.5ml deionized waters, 1.0g phosphoric acid and 10.0ml absolute ethyl alcohols magnetic agitation it is well mixed after, mixed with above-mentioned solution
Stirring, obtain that particle diameter distribution is uniform after reacting 3h, the good nano silicon dioxide sol liquid of pattern, silica particle diameter is concentrated
100~200nm is distributed in, is spheroidal nanometer little particle, gel time is more than 72h；Silica concentration is in colloidal sol
12.67wt%；
(2) preparation of cellulose acetate solution：
By dimethyl acetamide (DMAC), dimethylformamide (DMF), 1-METHYLPYRROLIDONE (NMP) or above-mentioned molten
Any two or more mixture in agent：Acetone=6: 3~8: 1 mass ratio, prepared polymer concentration mass fraction be 8%~
12% mixed solution；
(3) preparation of electrostatic spinning precursor solution：The nanometer silicon dioxide particle colloidal sol prepared in step (1) is taken, is added
Enter phosphoric acid or acetic acid stir after mix 3h at room temperature with the cellulose acetate solution prepared in step (2) and can obtain
To the precursor solution to electrostatic spinning, the polymerization containing 5~8% parts by weight in the precursor solution of described electrostatic spinning
Thing, the nano silicon of 1~6% parts by weight, the solvent of 65%~75% parts by weight, other non-solvents of 0~6% parts by weight
Additive；
(4) composite membrane is prepared by method of electrostatic spinning：
It will be placed in after the electrostatic spinning precursor solution standing and defoaming being uniformly dissolved in step (3) in electrospinning device,
Using traditional commerce PTFE, PVDF or PP hydrophobic membranes as basement membrane, each parameter of spinning equipment is arranged to：Syringe needle and roller receiver it
Between distance be 15cm, both end voltage 15kv, syringe fltting speed 1.5ml/h, drum rotation speed degree and syringe needle translational speed point
Wei 100rpm/min and 3.5mm/min, then continuous spinning 20h, you can obtain compound to the antipollution of membrane distillation process
Film；
(5) hot-pressing processing：By made film out in step (4) with compacting is adjacent to before and after glass plate, 60 DEG C~90 are placed in
3h in DEG C baking oven, that is, complete hot press operation.
Pollution resistant composite film of the present invention has the characteristics of following：
Antipollution PTFE-CA/SiNPs composite membranes of the present invention are a kind of parent/hydrophobic composite membranes, its thickness 195 ±
0.15 μm, porosity 46.7%~53%, maximum diameter of hole is less than 0.63 μm, and average pore size is 0.355 μm；LEPw values be 2.38 ±
0.05Bar, underwater crude oil static contact angle are more than 150.0 °；In 35g/l sodium chloride solution direct contact membrane distillation desalinations
Cheng Zhong, its permeation flux is up to 16.5~19.8L/ (m2H), desalting efficiency is more than 99.99%；Toward 35g/l sodium chloride solutions
The middle a certain amount of crude oil of addition is made 1 ‰ concentration crude oil emulsions and carries out direct contact membrane distillation desalination oil resistant test for contamination, its
Permeation flux can maintain 15.5~19.8L/ (m2H), desalting efficiency is more than 99.99%.Film effective run time is all higher than
20h。
[beneficial effect]
The present invention improves spinning formula of liquid on the basis of existing research, in situ in a polymer solution to introduce hydrophilic
Inorganic nanoparticles colloidal sol, super hydrophilic pollution-resistant layer is prepared using method of electrostatic spinning.The method is retaining former hydrophobic basement membrane
Surface obtains superpower resistance tocrocking on the basis of energy；Simultaneously as not only resistance tocrocking is good, water flux is high, chemical steady for composite membrane
It is qualitative strong, and its good mechanical properties, surface roughness are high, retain efficiency high, therefore be with a wide range of applications.
【Embodiment】
The principle and feature of the present invention are described with the following Examples, the given examples are served only to explain the present invention,
It is not intended to limit the scope of the present invention.
Embodiment 1：The preparation of antipollution PTFE-CA/SiNPs composite membranes of the present invention
(1) the certain silicon dioxide gel liquid of particle diameter, pattern is prepared：First by 15.5ml tetraethyl orthosilicates stoste with
0 DEG C of preservation is placed in after 10.0ml absolute ethyl alcohol magnetic agitations 1h；Then 2.5ml deionized waters, 1.0g phosphoric acid and 10.0ml are measured
After absolute ethyl alcohol magnetic agitation is well mixed, mixed with above-mentioned solution, react uniform, the pattern that obtains particle diameter distribution after 3h
Good nano silicon dioxide sol liquid.Silica particle diameter integrated distribution is spheroidal nanometer little particle in 185nm, gel
Time is more than 72h；Silica concentration is 12.67wt% in colloidal sol.
(2) preparation of cellulose acetate solution：Acetone and dimethyl acetamide (DMAC) mass ratio are prepared as 1: 8 mixing
Solvent, then, cellulose acetate is poured into mixed solution and prepares cellulose acetate polymer solution, acetate fiber matter in solution
It is 10% to measure fraction.
(3) preparation of electrostatic spinning precursor solution：10.0g nanometer silicon dioxide particle colloidal sols are taken, add 2.0g phosphoric acid
Presoma for electrostatic spinning can be obtained by mixing with 20.0g cellulose acetate solutions 3h after stirring at room temperature
Solution.
(4) method of electrostatic spinning prepares composite membrane：It is placed in after the solution left standstill deaeration being uniformly dissolved in electrospinning device, with
Traditional commerce PTFE hydrophobic membranes are basement membrane, set continuous spinning 20h after spinning parameter, you can are obtained to the anti-of membrane distillation process
Pollute composite membrane.In spinning process, distance is 15cm between syringe needle and roller receiver, both end voltage 15kv, and syringe pushes away
Enter speed 1.5ml/h, drum rotation speed degree and syringe needle translational speed are respectively 100rpm/min and 3.5mm/min.
(5) hot-pressing processing：By made film out with compacting is adjacent to before and after glass plate, be placed in 3h in 90 DEG C of baking ovens, i.e., it is complete
Into hot press operation.
Embodiment 2：The preparation of antipollution PTFE-CA/SiNPs composite membranes of the present invention
(1) silicon dioxide gel liquid is prepared：First by 15.5ml tetraethyl orthosilicates stoste and 10.0ml absolute ethyl alcohol magnetic force
0 DEG C of preservation is placed in after stirring 1h；Then 2.5ml deionized waters, 1.0g phosphoric acid and 10.0ml absolute ethyl alcohol magnetic agitations is measured to mix
After closing uniformly, mixed with above-mentioned solution, obtain that particle diameter distribution is uniform after reacting 3h, the good nano silicon of pattern
Sol solutionses.Silica particle diameter integrated distribution is spheroidal nanometer little particle, gel time is more than 72h in 185nm；In colloidal sol
Silica concentration is 12.67wt%.
(2) preparation of cellulose acetate solution：Prepare acetone and 1-METHYLPYRROLIDONE (NMP) mass ratio be 1: 4 it is mixed
Bonding solvent, then, cellulose acetate is poured into mixed solution and prepares cellulose acetate polymer solution, acetate fiber in solution
Mass fraction is 12%.
(3) electrostatic spinning precursor solution is prepared：By 10.0g nanometer silicon dioxide particles colloidal sol and 20.0g acetate fibers
Plain solution mixes 3h and obtains the precursor solution for electrostatic spinning at room temperature.
(4) method of electrostatic spinning prepares composite membrane：It is placed in after the solution left standstill deaeration being uniformly dissolved in electrospinning device, with
Traditional commerce PTFE hydrophobic membranes are basement membrane, set continuous spinning 25h after spinning parameter, you can are obtained to the anti-of membrane distillation process
Pollute composite membrane.In spinning process, distance is 20cm between syringe needle and roller receiver, both end voltage 15kv, and syringe pushes away
Enter speed 1.5ml/h, drum rotation speed degree and syringe needle translational speed are respectively 100rpm/min and 3.5mm/min.
(5) hot-pressing processing：By made film out with compacting is adjacent to before and after glass plate, be placed in 3h in 80 DEG C of baking ovens, i.e., it is complete
Into hot press operation.
Embodiment 3：The preparation of antipollution PTFE-CA/SiNPs composite membranes of the present invention
(1) preparation of cellulose acetate solution：Acetone and dimethylformamide (DMF) mass ratio are prepared as 3: 10 mixing
Solvent, then, cellulose acetate is poured into mixed solution and prepares cellulose acetate polymer solution, acetate fiber matter in solution
It is 15% to measure fraction.
(2) preparation of electrostatic spinning precursor solution：1.5g gas phase nano silica dioxide granules are taken, 2.0g acetic acid is added and stirs
3h is mixed at room temperature and obtains the precursor solution for electrostatic spinning with 20.0g cellulose acetate solutions after mixing uniformly.
(3) method of electrostatic spinning prepares composite membrane：It is placed in after the solution left standstill deaeration being uniformly dissolved in electrospinning device, with
Business PTFE hydrophobic membranes are basement membrane, set continuous spinning 25h after spinning parameter, you can obtain to the antipollution of membrane distillation process
Composite membrane.In spinning process, distance is 10cm between syringe needle and roller receiver, and both end voltage 16kv, syringe promotes fast
1.3ml/h is spent, drum rotation speed degree and syringe needle translational speed are respectively 150rpm/min and 3.0mm/min.
(4) hot-pressing processing：By made film out with compacting is adjacent to before and after glass plate, be placed in 5h in 90 DEG C of baking ovens, i.e., it is complete
Into hot press operation.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.
Claims (1)
1. a kind of preparation method of antipollution PTFE-CA/SiNPs composite membranes, the system of antipollution PTFE-CA/SiNPs composite membranes
Preparation Method comprises the following steps：
(1) preparation of nano silicon dioxide sol liquid：
0 DEG C of preservation will be placed in after 15.5ml tetraethyl orthosilicates stoste and 10.0ml absolute ethyl alcohol magnetic agitations 1h first；Then measure
After taking 2.5ml deionized waters, 1.0g phosphoric acid and 10.0ml absolute ethyl alcohols magnetic agitation well mixed, mix and stir with above-mentioned solution
Mix, obtain that particle diameter distribution is uniform after reacting 3h, the good nano silicon dioxide sol liquid of pattern, silica particle diameter is concentrated point
Cloth is spheroidal nanometer little particle, gel time is more than 72h in 100~200nm；Silica concentration is in colloidal sol
12.67wt%；
(2) preparation of cellulose acetate solution：
By in dimethyl acetamide (DMAC), dimethylformamide (DMF), 1-METHYLPYRROLIDONE (NMP) or above-mentioned solvent
Any two or more mixture: acetone=6: 3~8: 1 mass ratio, prepared polymer concentration mass fraction are 8%~12%
Mixed solution；
(3) preparation of electrostatic spinning precursor solution：The nanometer silicon dioxide particle colloidal sol prepared in step (1) is taken, adds phosphorus
Acid or acetic acid mix 3h with the cellulose acetate solution prepared in step (2) after stirring and can used at room temperature
With the precursor solution of electrostatic spinning, the polymer containing 5~8% parts by weight in the precursor solution of described electrostatic spinning, 1
The nano silicon of~6% parts by weight, the solvent of 65%~75% parts by weight, other non-solvents addition of 0~6% parts by weight
Agent；
(4) composite membrane is prepared by method of electrostatic spinning：
It will be placed in after the electrostatic spinning precursor solution standing and defoaming being uniformly dissolved in step (3) in electrospinning device, to pass
Business PTFE, PVDF of uniting or PP hydrophobic membranes are basement membrane, and each parameter of spinning equipment is arranged to：The spacing of syringe needle and roller receiver
It is respectively from for 15cm, both end voltage 15kv, syringe fltting speed 1.5ml/h, drum rotation speed degree and syringe needle translational speed
100rpm/min and 3.5mm/min, then continuous spinning 20h, you can obtain to the pollution resistant composite film of membrane distillation process；
(5) hot-pressing processing：By made film out in step (4) with compacting is adjacent to before and after glass plate, 60 DEG C~90 DEG C bakings are placed in
3h in case, that is, complete hot press operation.
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| CN201710958053.8A CN107511081B (en) | 2017-10-13 | 2017-10-13 | Preparation method of anti-pollution PTFE-CA/SiNPs composite film |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110549443A (en) * | 2019-08-30 | 2019-12-10 | 贵州大学 | Multifunctional wood protective agent prepared from multi-element composite nano silica sol and preparation method thereof |
| CN111235661A (en) * | 2020-03-21 | 2020-06-05 | 王天琦 | Antibacterial material for preventing pediatric pneumonia and manufacturing method thereof |
| CN115058827A (en) * | 2022-07-13 | 2022-09-16 | 中国电子科技集团公司第四十九研究所 | Hydrophobic breathable film applied to humidity sensitive element |
| CN117364291A (en) * | 2023-11-09 | 2024-01-09 | 江苏江南高纤股份有限公司 | Ultra-smooth composite short fiber and preparation method and application thereof |
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| JPS5771607A (en) * | 1980-10-23 | 1982-05-04 | Sumitomo Metal Ind Ltd | Cleaning of osmotic membrane |
| US20050121385A1 (en) * | 2003-09-26 | 2005-06-09 | Sartorius Ag | Adsorption membranes, method of producing same and equipment, including the adsorption membranes |
| CN101337162A (en) * | 2007-07-03 | 2009-01-07 | 天津宝成机械集团有限公司 | Preparation method of filter membrane for desalinating sea water |
| CN103485074A (en) * | 2013-08-09 | 2014-01-01 | 天津工业大学 | Device and method of preparing electrostatic spinning polymer/inorganic particle nano-composite film |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5771607A (en) * | 1980-10-23 | 1982-05-04 | Sumitomo Metal Ind Ltd | Cleaning of osmotic membrane |
| US20050121385A1 (en) * | 2003-09-26 | 2005-06-09 | Sartorius Ag | Adsorption membranes, method of producing same and equipment, including the adsorption membranes |
| CN101337162A (en) * | 2007-07-03 | 2009-01-07 | 天津宝成机械集团有限公司 | Preparation method of filter membrane for desalinating sea water |
| CN103485074A (en) * | 2013-08-09 | 2014-01-01 | 天津工业大学 | Device and method of preparing electrostatic spinning polymer/inorganic particle nano-composite film |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110549443A (en) * | 2019-08-30 | 2019-12-10 | 贵州大学 | Multifunctional wood protective agent prepared from multi-element composite nano silica sol and preparation method thereof |
| CN110549443B (en) * | 2019-08-30 | 2021-06-11 | 贵州大学 | Multifunctional wood protective agent prepared from multi-element composite nano silica sol and preparation method thereof |
| CN111235661A (en) * | 2020-03-21 | 2020-06-05 | 王天琦 | Antibacterial material for preventing pediatric pneumonia and manufacturing method thereof |
| CN111235661B (en) * | 2020-03-21 | 2020-12-11 | 河南省中医院（河南中医药大学第二附属医院） | Antibacterial material for preventing pediatric pneumonia and manufacturing method thereof |
| CN115058827A (en) * | 2022-07-13 | 2022-09-16 | 中国电子科技集团公司第四十九研究所 | Hydrophobic breathable film applied to humidity sensitive element |
| CN117364291A (en) * | 2023-11-09 | 2024-01-09 | 江苏江南高纤股份有限公司 | Ultra-smooth composite short fiber and preparation method and application thereof |
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|---|---|
| CN107511081B (en) | 2020-08-11 |
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