CN101905122B - Self-assembly method for high-load inorganic nano particle hybridized organic membrane - Google Patents
Self-assembly method for high-load inorganic nano particle hybridized organic membrane Download PDFInfo
- Publication number
- CN101905122B CN101905122B CN2010102378350A CN201010237835A CN101905122B CN 101905122 B CN101905122 B CN 101905122B CN 2010102378350 A CN2010102378350 A CN 2010102378350A CN 201010237835 A CN201010237835 A CN 201010237835A CN 101905122 B CN101905122 B CN 101905122B
- Authority
- CN
- China
- Prior art keywords
- nano particle
- membrane
- enveloping solid
- polyanion
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a self-assembly method for a high-load inorganic nano particle hybridized organic membrane, which belongs to the technical field of membranes. The method comprises the following steps of: preparing membrane-forming solution from polycations and polyanions respectively, adding amphoteric oxide nano particles respectively, and adjusting pH values; performing ultrasonic treatment and centrifugation, and replacing solvents to prepare polyion nano particle envelope solution; impregnating a substrate or a basal membrane in the polyion nano particle envelope solution or performing dynamic filtration to form a membrane layer, and performing washing and blow-drying; impregnating the substrate or the basal membrane in the polyion nano particle solution loaded with opposite charges; performing the washing and the blow-drying; and repeating the membrane-forming, the washing and the blow-drying to form an inorganic nano particle hybridized polyelectrolyte membrane. The method has the advantages of hybridizing a polycation layer and a polyanion layer with the nano particles, improving the charge numbers of the nano particles in the double layers and effectively overcoming the defect of easy stripping of organic and inorganic layers of the prepared membrane during hybridization.
Description
Technical field
The present invention relates to the preparation of hybrid organic-inorganic film, particularly utilize the amphoteric oxide nano particle to prepare high capacity nano particle hybridization organic film and the organic infiltrating and vaporizing membrane of preparation inorganic hybridization, belong to the membrane technology field.
Background technology
Along with the fast development of membrane technology, the research of membrane material receives extensive attention.The organic inorganic hybridization film had both had the stability of inoranic membrane, had the surface characteristic that organo-functional group is given again, was one type and used boundless membrane material.At present; The general organic inorganic hybridization membrane preparation method that adopts has sol-gal process, blending method, thermally induced phase separation etc.; But be used for the preparation of perforated membrane mostly; Preparation for the organic-inorganic hybridized osmotic of densification vaporization film then is in the stage at the early-stage, and therefore, development organic inorganic hybridization new technology has important scientific value.
Polyelectrolyte is claimed polyion again, is meant the macromolecule that in main chain or side chain, has many ionogenic ionic groups.This seminar once proposed a kind of self-assembling method with inorganic nano particle hybridization organic membrane (Chinese invention patent application number: 200910236781.3) early stage; But the method for mentioning in this patent only relates to hybridized nanometer particle in the polyanion individual layer, and the load capacity of nano particle in poly ion complexes is limited.
Amphoteric oxide is meant both to can be used as the oxide that acid also can be used as alkali.Promptly under sour environment, their lotus positive electricity; Under alkaline environment, they are bear then.The amphoteric oxide and the polyion of oppositely charged that utilize this characteristic of amphoteric oxide nano particle to propose under acidity or alkali condition react; Form the nano particle enveloping solid of charge positive charge or negative electrical charge; At present; This self-assembling method that utilizes Electrostatic Absorption between the nano particle enveloping solid to prepare the nano particle hybridization film is not also seen relevant report.
Summary of the invention
The present invention provides a kind of self-assembling method of high-load inorganic nano particle hybridized organic membrane, particularly the preparation of amphoteric oxide nano particle hybridization organic film and the organic infiltrating and vaporizing membrane of amphoteric oxide nano particle hybridization.
Amphoteric oxide and the polyion of oppositely charged that this patent utilizes the characteristic of amphoteric oxide nano particle to propose under acidity or alkali condition react; Form the nano particle enveloping solid of charge positive charge or negative electrical charge; Further pass through the electrostatic adsorption of positive and negative charge between the nano particle enveloping solid again; Construct the compound polyelectrolyte film that nano particle is arranged in the double-deck all hydridization of polycation and polyanion; Thereby improve the hydridization amount of inorganic nano-particle in compound polyelectrolyte, form a kind of high-load inorganic nano particle hybridized organic membrane.
This method may further comprise the steps:
(1) polycation is dissolved in the solvent, is mixed with preparation liquid, standing and defoaming; In said polycation solution, add the amphoteric oxide nano particle; Regulate the pH value to alkalescence; Make amphoteric oxide nano particle bear; And the negative electrical charge sum that makes the amphoteric oxide nano particle of adding is lower than polycation positive charge sum, thereby forms polycation nano particle enveloping solid solution; Polyanion is dissolved in the solvent, is mixed with preparation liquid, standing and defoaming; In polyanion solution, add the amphoteric oxide nano particle; Regulate the pH value to acid; Make amphoteric oxide nano particle lotus positive electricity; And the positive charge sum that makes the amphoteric oxide nano particle of adding is lower than polyanion negative electrical charge sum, thereby forms polyanion nano particle enveloping solid solution; For example in embodiment 1, the nanometer ZrO of adding
2Particle positively charged 1/2nd of the polyanion polyacrylic acid positive charge sum that adds up to;
(2) respectively with ultrasonic 30～120 minutes of the polyion solution that has added the amphoteric oxide nano particle in the step (1), nano particle is evenly disperseed after, centrifugal 1～60 minute, centrifugal after with supernatant change into supernatant in the identical isopyknic solvent of solvent;
(3) repeat (2) step 1～10 times, make polyion nano particle enveloping solid solution;
After above-mentioned solution preparation steps, further on substrate, continue assembling according to the following step:
(4) make substrate lotus positive electricity or negative electricity; And substrate is immersed in the step (3) in polyanion nano particle enveloping solid solution or the polycation nano particle enveloping solid solution 10～60 minutes; Make polyanion nano particle enveloping solid or polycation nano particle enveloping solid be adsorbed on substrate surface, form thin layer; According to prior art substrate lotus positive electricity or negative electricity are got final product.
(5) substrate is immersed in the deionized water, the rinsing face also dries up;
(6) substrate was immersed in the step (3) polycation nano particle enveloping solid solution or polyanion nano particle enveloping solid solution 10～60 minutes, polyanion nano particle enveloping solid and the sub-enveloping solid of polycation nano seed are reacted;
(7) film is immersed in the deionized water rinsing face and oven dry;
(8) repeat (4)～(7) step 1-100 time, form the inorganic nano particle hybridization organic film.
Utilize method that the amphoteric oxide nano particle prepares the organic infiltrating and vaporizing membrane of inorganic hybridization after the preparation of above-mentioned (1)-(3) step solution, further on basement membrane, continue to assemble according to the following step:
(4) make basement membrane lotus positive electricity or negative electricity; And 0.01～3.0Mpa pressure or-0.02～-suction function of 0.09MPa under; With step (3) polyanion nano particle enveloping solid solution or polycation nano particle enveloping solid solution membrane surface dynamic filtration 10～60 minutes; Polyanion nano particle enveloping solid or polycation nano particle enveloping solid are trapped in film surface or hole, form separating layer; According to prior art basement membrane lotus positive electricity or negative electricity are got final product.
(5) film is immersed in the deionized water rinsing face and oven dry;
(6) 0.01～3.0Mpa pressure or-0.02～-suction function of 0.09MPa under; Membrane surface dynamic filtration 10～60 minutes, polyanion nano particle enveloping solid and polycation nano particle enveloping solid reacted with step (3) polycation nano particle enveloping solid solution or polyanion nano particle enveloping solid solution;
(7) film is immersed in the deionized water rinsing face and oven dry;
(8) repeat (4)～(7) step 1-10 time, form the organic infiltrating and vaporizing membrane of inorganic nano particle hybridization.
In the method for the invention, described amphoteric oxide nano particle is zirconium dioxide, alundum (Al, manganese dioxide, zinc oxide, chrome green or beryllium oxide, and particle diameter is 1～100 nanometer.
In the method for the invention, described solvent can be water, methyl alcohol, ethanol, propyl alcohol or butanols.
In the method for the invention, described substrate is a rigid basement, can be quartz glass, monocrystalline silicon, calcirm-fluoride; Described basement membrane; Be meant that solution is under pressure-driven power; See through a kind of segregation phenomenon of pellicle; Can be micro-filtration membrane, milipore filter or NF membrane, described basal lamina material is an organic polymer, can be polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, Merlon, polyethylene, polytetrafluoroethylene (PTFE) or shitosan etc.The kit form of basement membrane is tubular membrane, hollow-fibre membrane, flat sheet membrane or rolled film.The membrane aperture of described basement membrane is between 1 nanometer to 100 micron.Said polycation material is diallyl dimethyl ammoniumchloride, polymine, PAH hydrochloride, poly 4 vinyl pyridine, chitin, and the polyanion material is kayexalate, polyacrylic acid, gather sulfonated ethylene.
This method is based on the preparation technology of the organic inorganic hybridization film of self-assembling technique; Earlier directly add the amphoteric oxide nano particle in the charged polyelectrolyte solution; Utilize adjusting pH, repeated ultrasonic and centrifugally operated to make the polymer nano-particle enveloping solid, be assembled on substrate or the basement membrane through layer upon layer electrostatic absorption again.
The principle of technical scheme of the present invention is: the amphoteric oxide nano particle is added in the charged polyelectrolyte solution; Amphoteric oxide is charged to react with polyelectrolyte thereby adjusting pH value makes; The ultrasonic amphoteric oxide nano particle that makes disperses, and the polyelectrolyte envelope is in nanoparticle surface; Centrifugally change supernatant into the equivalent solvent, thereby isolate the polyelectrolyte that is free on nanoparticle surface; The centrifugal polyion nano particle enveloping solid solution that promptly makes of repeated ultrasonic.Substrate or basement membrane are soaked perhaps dynamic filtration in polyion nano particle enveloping solid solution; Polyelectrolyte nano particle structures (gathering cloudy sub-nano particle enveloping solid and polycation nano particle enveloping solid product) are compounded in the film surface, form selective separation layer.Owing to adopt repeated ultrasonic and centrifugal during this method preparation polyion nano particle enveloping solid solution; And between the nano particle enveloping solid owing to there is an electrostatic repulsion effect; Thereby can make the nano particle enveloping solid evenly, stable dispersion is in solution; And the application proposes regulator solution pH value first and makes amphoteric oxide difference lotus positive electricity and negative electricity under acid and alkali condition, further with polyanion and polycation reaction, forms nano particle enveloping solid structure; Through the film forming of absorption assembling layer by layer; Thereby be implemented in polycation and the polyanion layer all hybridized nanometer particles, improve the load capacity of nano particle in bilayer, and can effectively overcome the defective that the organic-inorganic layer of obtained film is prone to peel off.
Description of drawings
Scanning electron microscope analysis is carried out on the film surface of Fig. 1, embodiment 1
Scanning electron microscope analysis is carried out on the film surface of Fig. 2, embodiment 2.
The specific embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done detailed explanation.
Embodiment 1
The employing substrate is a quartz glass, and used polycation material is diallyl dimethyl ammoniumchloride (PDDA, molecular weight are 100000～200000), and polyanion is kayexalate (PSS, molecular weight are 70000), nano zirconia particles (ZrO
2, in the 100nm, 5wt%), the solvent of diallyl dimethyl ammoniumchloride and kayexalate is water.
Assembling condition and method:
(1) with deionized water diallyl dimethyl ammoniumchloride is made into the solution 500ml of 0.94wt%, standing and defoaming adds nano zirconia particles 8ml, and regulating the pH value is 12; With deionized water kayexalate is made into the solution 500ml of 1.2wt%, standing and defoaming adds nano zirconia particles 8ml;
(2) with ultrasonic 120 minutes of diallyl dimethyl ammoniumchloride solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make diallyl dimethyl ammoniumchloride nano particle enveloping solid solution; With ultrasonic 120 minutes of kayexalate solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make kayexalate nano particle enveloping solid solution;
(3) substrate is immersed in the mixed solution of the concentrated sulfuric acid and hydrogen peroxide solution,, makes the substrate bear in 70 ℃ of heating 3 hours;
(4) substrate is immersed in the deionized water, the rinsing face also dries up;
(5) substrate is immersed in diallyl dimethyl ammoniumchloride nano particle enveloping solid solution 30min, makes substrate surface form thin layer;
(6) substrate is immersed in the deionized water rinsing face and oven dry;
(7) substrate is immersed in kayexalate nano particle enveloping solid solution 30min, makes it to react with diallyl dimethyl ammoniumchloride nano particle enveloping solid;
(8) substrate is immersed in the deionized water rinsing face and oven dry;
(9) repeat (5)-(6) step 10 time, repeat (7)-(8) step 9 time, can form the compound number of plies and be 10.5 layers inorganic nano particle hybridization organic film.
The inorganic nano particle hybridization organic film of above-mentioned assembling is utilized step appearance Thickness Measurement by Microwave, record average every layer thickness and be 41
ESEM is (like Fig. 1 before and after the hydridization; 100,000 times of multiplication factors) show, because there are strong interaction in polymer macromolecule and zirconia microparticle surfaces; Nano particle evenly distributes or embeds the film surface; Thereby changed the thickness of film, improved the load capacity of nano particle, made the inorganic nano particle hybridization organic film of compact structure.
Specific embodiment 2
The employing substrate is a quartz glass, and used polycation material is polymine (PEI, molecular weight are 60,000), and polyanion is polyacrylic acid (PAA, molecular weight are 4,000,000), nano zirconia particles (ZrO
2, in the 100nm, 5wt%), polymine and polyacrylic solvent are water.
Assembling condition and method:
(1) with deionized water polymine is made into the solution 500ml of 0.5wt%, standing and defoaming adds nano zirconia particles solution 1ml; With deionized water polyacrylic acid is made into the solution 500ml of 0.05wt%, standing and defoaming adds nano zirconia particles solution 1ml;
(2) with ultrasonic 120 minutes of polyethyleneimine: amine aqueous solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make polyethylene imine nanometer particle enveloping solid solution; With ultrasonic 120 minutes of polyacrylic acid solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make polyacrylic acid nano particle enveloping solid solution;
(3) substrate is immersed in the mixed solution of the concentrated sulfuric acid and hydrogen peroxide solution,, makes the substrate bear in 70 ℃ of heating 3 hours;
(4) substrate is immersed in the deionized water, the rinsing face also dries up;
(5) substrate is immersed in polyethylene imine nanometer particle enveloping solid solution solution 30min, makes substrate surface form thin layer;
(6) substrate is immersed in the deionized water rinsing face and oven dry;
(7) substrate is immersed in polyacrylic acid nano particle enveloping solid solution 30min, makes it to react with polyethylene imine nanometer particle enveloping solid;
(8) substrate is immersed in the deionized water rinsing face and oven dry;
(9) repeat (5)-(6) step 5 time, repeat (7)-(8) step 4 time, can form the compound number of plies and be 5.5 layers inorganic nano particle hybridization organic film.
ESEM is (like Fig. 2 before and after the hydridization; Multiplication factor is 10; 000 times) show that because there are strong interaction in polymer macromolecule and zirconia microparticle surfaces, nano particle evenly distributes or embeds the film surface; Improve the load capacity of nano particle, thereby made the inorganic nano particle hybridization organic film of compact structure.
Specific embodiment 3
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off, membrane area are 28cm
2, used polycation material is diallyl dimethyl ammoniumchloride (PDDA, molecular weight are 100000～200000), polyanion is kayexalate (PSS, molecular weight are 70000), nano zirconia particles (ZrO
2, in the 100nm, 5wt%), the solvent of diallyl dimethyl ammoniumchloride and kayexalate is water.
Assembling condition and method:
(1) with deionized water diallyl dimethyl ammoniumchloride is made into the solution 500ml of 0.94wt%, standing and defoaming adds nano zirconia particles 8ml, and regulating the pH value is 12; With deionized water kayexalate is made into the solution 500ml of 1.2wt%, standing and defoaming adds nano zirconia particles 8ml;
(2) with ultrasonic 120 minutes of diallyl dimethyl ammoniumchloride solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make diallyl dimethyl ammoniumchloride nano particle enveloping solid solution; With ultrasonic 120 minutes of kayexalate solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make the kayexalate nano-particle solution;
(3) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, the polypropylene screen milipore filter is immersed 30min in the 2N NaOH solution, it is modified as flat polyanion basement membrane;
(4) film is immersed in the deionized water rinsing face and oven dry;
(5) under 0.1Mpa pressure, on polyacrylonitrile ultrafiltration film, filter 0.94wt% diallyl dimethyl ammoniumchloride nano particle enveloping solid solution 30min, make the film surface form separating layer;
(6) film is immersed in the deionized water rinsing face and oven dry;
(7) under 0.1Mpa pressure, filter 1.2wt% kayexalate nano particle enveloping solid solution 30min, make it to react with diallyl dimethyl ammoniumchloride nano particle enveloping solid;
(8) film is immersed in the deionized water rinsing face and oven dry;
(9) repeat (5)-(6) step 1 time, can form the compound number of plies and be 1.5 layers the organic infiltrating and vaporizing membrane of flat inorganic nano particle hybridization;
The organic infiltrating and vaporizing membrane of the inorganic nano particle hybridization of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 95wt% ethanol/water system, 50 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 648gm
-2H
-1See through ethanol content 4.3wt% in the liquid, separation factor 350.
Specific embodiment 4
Adopt to do/wetting phase transformation approach spinning uni-endodermis doughnut support membrane polypropylene screen (PAN) material, internal diameter 1.1mm; Molecular cut off 60000; Used polycation material is diallyl dimethyl ammoniumchloride (PDDA, molecular weight are 100000～200000), and polyanion is kayexalate (PSS; Molecular weight is 70000), nano zirconia particles (ZrO
2, in the 100nm, 5wt%), the solvent of diallyl dimethyl ammoniumchloride and kayexalate is water.
Assembling condition and method:
(1) with deionized water diallyl dimethyl ammoniumchloride is made into the solution 500ml of 0.94wt%, standing and defoaming adds nano zirconia particles 8ml, and regulating the pH value is 12; With deionized water kayexalate is made into the solution 500ml of 1.2wt%, standing and defoaming adds nano zirconia particles 8ml;
(2) with ultrasonic 120 minutes of diallyl dimethyl ammoniumchloride solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make diallyl dimethyl ammoniumchloride nano particle enveloping solid solution; With ultrasonic 120 minutes of kayexalate solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make kayexalate nano particle enveloping solid solution;
(3) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, the polypropylene screen milipore filter is immersed 15min in the 2N NaOH solution, it is modified as doughnut polyanion basement membrane;
(4) film is immersed in the deionized water rinsing face and oven dry;
(5) the doughnut basement membrane is put into lucite tube, the epoxy resin end-blocking is used at two ends, processes hollow-fiber module.
(6) utilize circulating pump that diallyl dimethyl ammoniumchloride nano particle enveloping solid solution is pumped into doughnut basement membrane inner chamber; Apply in the fiber outside-negative pressure of 0.08MPa; Aspirate 30min; Make diallyl dimethyl ammoniumchloride nano particle enveloping solid be trapped and adsorb, form separating layer at the fiber inner surface;
(7) film is immersed in the deionized water rinsing face and oven dry;
(8) utilize circulating pump that kayexalate nano particle enveloping solid solution is pumped into doughnut basement membrane inner chamber, apply in the fiber outside-negative pressure of 0.08MPa, aspirate 30min, make it to react with diallyl dimethyl ammoniumchloride nano particle enveloping solid;
(9) film is immersed in the deionized water rinsing face and oven dry;
(10) repeat (6)-(7) step 1 time, can form the compound number of plies and be 1.5 layers the organic infiltrating and vaporizing membrane of doughnut formula inorganic nano particle hybridization.
Measure the mechanical property of film through stretching experiment.To make hollow-fibre membrane silk (external diameter 1.50mm, film thickness 0.135mm, test speed 10mm/min), adopt the stretching strength determination appearance at room temperature to record hot strength 3.56Mpa.
The organic infiltrating and vaporizing membrane of the inorganic nano particle hybridization of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 95wt% ethanol/water system, 50 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: the logical 23gm-2h-1 of infiltration sees through ethanol content 0.09wt% in the liquid, separation factor 2389.8.
Specific embodiment 5
Adopt to do/wetting phase transformation approach spinning uni-endodermis doughnut support membrane polypropylene screen (PAN) material, internal diameter 1.1mm; Molecular cut off 60000; Used polycation material is polymine (PEI, molecular weight are 60000), and polyanion is polyacrylic acid (PAA; Molecular weight is 100000), nano zirconia particles (ZrO
2, in the 100nm, 5wt%) polymine and polyacrylic solvent are water.
Assembling condition and method:
(1) with deionized water polymine is made into the solution 500ml of 0.5wt%, standing and defoaming adds nano zirconia particles solution 1ml; With deionized water polyacrylic acid is made into the solution 500ml of 0.05wt%, standing and defoaming adds nano zirconia particles solution 1ml;
(2) with ultrasonic 120 minutes of polyethyleneimine: amine aqueous solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make polyethylene imine nanometer particle enveloping solid solution; With ultrasonic 120 minutes of polyacrylic acid solution, nano particle is evenly disperseed after, centrifugal 10 minutes, change supernatant into the equal-volume deionized water after centrifugal; Repeat 3 times, make polyacrylic acid nano particle enveloping solid solution;
(3) for making polyacrylonitrile support membrane surface charged, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, the polypropylene screen milipore filter is immersed 15min in the 2N NaOH solution, it is modified as doughnut polyanion basement membrane;
(4) film is immersed in the deionized water rinsing face and oven dry;
(5) the doughnut basement membrane is put into lucite tube, the epoxy resin end-blocking is used at two ends, processes hollow-fiber module.
(6) utilize circulating pump that polyethylene imine nanometer particle enveloping solid solution is pumped into doughnut basement membrane inner chamber; Apply in the fiber outside-negative pressure of 0.08MPa; Aspirate 30min, make polyethylene imine nanometer particle enveloping solid be trapped and adsorb, form separating layer at the fiber inner surface;
(7) film is immersed in the deionized water rinsing face and oven dry;
(8) utilize circulating pump that polyacrylic acid nano particle enveloping solid solution is pumped into doughnut basement membrane inner chamber, apply in the fiber outside-negative pressure of 0.08MPa, aspirate 30min, make it to react with polyethylene imine nanometer particle enveloping solid;
(9) film is immersed in the deionized water rinsing face and oven dry;
(10) repeat (6)-(7) step 1 time, can form the compound number of plies and be 1.5 layers the organic infiltrating and vaporizing membrane of doughnut formula inorganic nano particle hybridization.
Measure the mechanical property of film through stretching experiment.To make hollow-fibre membrane silk (external diameter 1.50mm, film thickness 0.135mm, test speed 10mm/min), adopt the stretching strength determination appearance at room temperature to record hot strength 3.14Mpa.
The organic infiltrating and vaporizing membrane of the inorganic nano particle hybridization of above-mentioned assembling is carried out the infiltration evaporation performance test in the infiltration evaporation membrane cisterna, test condition is: stoste is formed 95wt% ethanol/water system, 50 ℃ of experimental temperatures, film downstream pressure 100Pa.
Recording the infiltration evaporation film properties is: permeation flux 24.7gm
-2H
-1, see through ethanol content 0.6wt% in the liquid, separation factor 2700.
Claims (10)
1. the self-assembling method of a high-load inorganic nano particle hybridized organic membrane, this method may further comprise the steps:
(1) polycation is dissolved in the solvent, is mixed with preparation liquid, standing and defoaming; In said polycation solution, add the amphoteric oxide nano particle; Regulate the pH value to alkalescence; Make amphoteric oxide nano particle bear; And the negative electrical charge sum that makes the amphoteric oxide nano particle of adding is lower than polycation positive charge sum, thereby forms polycation nano particle enveloping solid solution; Polyanion is dissolved in the solvent, is mixed with preparation liquid, standing and defoaming; In polyanion solution, add the amphoteric oxide nano particle; Regulate the pH value to acid; Make amphoteric oxide nano particle lotus positive electricity; And the positive charge sum that makes the amphoteric oxide nano particle of adding is lower than polyanion negative electrical charge sum, thereby forms polyanion nano particle enveloping solid solution;
(2) respectively with ultrasonic 30～120 minutes of the polyion solution that has added the amphoteric oxide nano particle in the step (1), nano particle is evenly disperseed after, centrifugal 1～60 minute, centrifugal after with supernatant change into supernatant in the identical isopyknic solvent of solvent;
(3) repeat (2) step 1～10 times, make polyion nano particle enveloping solid solution;
(4) make substrate or basement membrane lotus positive electricity or negative electricity; And substrate is immersed in the step (3) in polyanion nano particle enveloping solid solution or the polycation nano particle enveloping solid solution 10～60 minutes; Make polyanion nano particle enveloping solid or polycation nano particle enveloping solid be adsorbed on substrate surface, form thin layer;
Perhaps make basement membrane lotus positive electricity or negative electricity; And 0.01～3.0Mpa pressure or-0.02～-suction function of 0.09MPa under; With polyanion nano-particle solution or polycation nano particle solution membrane surface dynamic filtration 10～60 minutes; Polyanion nano particle enveloping solid or polycation nano particle enveloping solid are trapped in film surface or hole, form separating layer;
(5) step (4) substrate or basement membrane are immersed in the deionized water, the rinsing face also dries up;
(6) step (5) substrate was immersed in the step (3) polycation nano particle enveloping solid solution or polyanion nano particle enveloping solid solution 10～60 minutes, polyanion nano particle enveloping solid and the sub-enveloping solid of polycation nano seed are reacted;
Perhaps with step (5) basement membrane 0.01～3.0Mpa pressure or-0.02～-suction function of 0.09MPa under; Membrane surface dynamic filtration 10～60 minutes, polyanion nano particle enveloping solid and polycation nano particle enveloping solid reacted with polycation nano particle enveloping solid solution in the step (3) or polyanion nano particle enveloping solid solution;
(7) substrate or the basement membrane with step (6) is immersed in the deionized water, rinsing face and oven dry;
(8) repeat (4)～(7) step 1-100 time;
(9) substrate of step (8) forms the organic infiltrating and vaporizing membrane of basement membrane formation inorganic nano particle hybridization of inorganic nano particle hybridization organic film or step (8).
2. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1; It is characterized in that; Described amphoteric oxide nano particle is zirconium dioxide, alundum (Al, manganese dioxide, zinc oxide, chrome green or beryllium oxide, and particle diameter is 1～100 nanometer.
3. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1 is characterized in that, described solvent is water, methyl alcohol, ethanol, propyl alcohol or butanols.
4. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1 is characterized in that, described substrate is a rigid basement.
5. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1; It is characterized in that; Said polycation material is diallyl dimethyl ammoniumchloride, polymine, PAH hydrochloride, poly 4 vinyl pyridine, chitin, and the polyanion material is kayexalate, polyacrylic acid, gather sulfonated ethylene.
6. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1 is characterized in that, described basement membrane is micro-filtration membrane, milipore filter or NF membrane,
7. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1 is characterized in that, described basal lamina material is an organic polymer.
8. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1 is characterized in that, the kit form of basement membrane is tubular membrane, hollow-fibre membrane, flat sheet membrane or rolled film.
9. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 1 is characterized in that, the membrane aperture of described basement membrane is between 1 nanometer to 100 micron.
10. the self-assembling method of a kind of high-load inorganic nano particle hybridized organic membrane of claim 7; It is characterized in that said organic polymer basal lamina material is polyacrylonitrile, polysulfones, Kynoar, Merlon, polyethylene, polytetrafluoroethylene (PTFE) or shitosan.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102378350A CN101905122B (en) | 2010-07-23 | 2010-07-23 | Self-assembly method for high-load inorganic nano particle hybridized organic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010102378350A CN101905122B (en) | 2010-07-23 | 2010-07-23 | Self-assembly method for high-load inorganic nano particle hybridized organic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101905122A CN101905122A (en) | 2010-12-08 |
| CN101905122B true CN101905122B (en) | 2012-05-30 |
Family
ID=43260798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010102378350A Expired - Fee Related CN101905122B (en) | 2010-07-23 | 2010-07-23 | Self-assembly method for high-load inorganic nano particle hybridized organic membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101905122B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102671551B (en) * | 2011-03-18 | 2014-03-05 | 中国科学院大连化学物理研究所 | Electro-conductive micro-filtration membrane and preparation method thereof |
| CN102284253A (en) * | 2011-06-13 | 2011-12-21 | 北京工业大学 | Method for assembling organic/inorganic hollow fiber composite membrane |
| CN102580550B (en) * | 2012-03-05 | 2014-04-09 | 中国海洋大学 | Method for producing polyelectrolyte self-assembly composite nanofiltration membrane |
| CN102814165B (en) * | 2012-09-10 | 2014-09-17 | 南昌航空大学 | Method for improving chitosan acidoresistance |
| CN103741477B (en) * | 2014-01-03 | 2016-01-06 | 天津工业大学 | A kind of sulfonic group modified polytetrafluoroethylene fibre self-assembly preparation method thereof |
| CN103816814B (en) * | 2014-03-06 | 2016-01-20 | 北京工业大学 | A kind of porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| CN104014251B (en) * | 2014-06-05 | 2016-09-14 | 北京工业大学 | A kind of preparation method based on inorganic supporting body assembled inorganic particle hydridization polyelectrolyte NF membrane |
| CN105479876A (en) * | 2014-09-27 | 2016-04-13 | 中国石油化工集团公司 | Nano-bionic laminar film and preparation method therefor |
| CN105887478B (en) * | 2015-01-16 | 2020-05-15 | 中国人民解放军军事医学科学院毒物药物研究所 | Multifunctional skin protection material and preparation method and application thereof |
| CN104785124B (en) * | 2015-03-30 | 2017-11-17 | 北京工业大学 | A kind of charged TiO2/ polyelectrolyte composite nanometer filtering film and preparation method and application |
| CN105597557B (en) * | 2015-09-28 | 2017-11-17 | 河北工业大学 | A kind of preparation method being used for from the composite membrane of extracting lithium from salt lake brine |
| CN105642017B (en) * | 2015-12-31 | 2018-06-19 | 天津清科环保科技有限公司 | A kind of polytetrafluoroethylene (PTFE) self-assembled coating filtrate and preparation method thereof |
| CN107081424B (en) * | 2017-05-02 | 2018-12-28 | 常州大学 | A kind of thick titanium or thick titanium alloy powder injection moulding PP Pipe Compound and preparation method thereof |
| CN107880335A (en) * | 2017-11-24 | 2018-04-06 | 苏州大学 | Inorganic/organic hybrid films and preparation method thereof |
| EP3762132A4 (en) | 2018-03-07 | 2022-03-16 | King's Flair Development Ltd. | Functional fibrous membrane, method for manufacturing the same, filter comprising the same |
| CN111530286B (en) * | 2020-04-28 | 2022-02-11 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085840A (en) * | 2007-06-11 | 2007-12-12 | 同济大学 | Method for preparing polyelectrolyte/CdTe nano composite thin film |
| JP2008027586A (en) * | 2006-07-18 | 2008-02-07 | Hitachi Ltd | Polyelectrolyte composition and its use |
| JP2008140608A (en) * | 2006-11-30 | 2008-06-19 | Jsr Corp | Membrane-electrode assembly |
| CN101224393A (en) * | 2007-10-19 | 2008-07-23 | 浙江大学 | Fabricating method of pervaporation membranes by electric field driving polyelectrolyte layer-by-layer self-assembly |
-
2010
- 2010-07-23 CN CN2010102378350A patent/CN101905122B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008027586A (en) * | 2006-07-18 | 2008-02-07 | Hitachi Ltd | Polyelectrolyte composition and its use |
| JP2008140608A (en) * | 2006-11-30 | 2008-06-19 | Jsr Corp | Membrane-electrode assembly |
| CN101085840A (en) * | 2007-06-11 | 2007-12-12 | 同济大学 | Method for preparing polyelectrolyte/CdTe nano composite thin film |
| CN101224393A (en) * | 2007-10-19 | 2008-07-23 | 浙江大学 | Fabricating method of pervaporation membranes by electric field driving polyelectrolyte layer-by-layer self-assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101905122A (en) | 2010-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101905122B (en) | Self-assembly method for high-load inorganic nano particle hybridized organic membrane | |
| CN101700473B (en) | Self-assembly method of inorganic nano particle hybridization organic membrane | |
| CN107029562B (en) | MXene-based composite nanofiltration membrane and preparation method thereof | |
| KR101423757B1 (en) | Manufacturing method of nanofiber-graphene membrane for water-treatment and nanofiber-graphene membrane for water-treatment thereof | |
| CN109666964B (en) | Method for rapidly preparing two-dimensional MXene film through electrophoretic deposition | |
| CN102327746B (en) | Anti-pollution cyclodextrin-polymer composite nano-filtration membrane and preparation method thereof | |
| CN102580566B (en) | Method for in situ generating inorganic nano particles-polyelectrolyte hybrid membrane | |
| CN102824856B (en) | Preparation method for generating inorganic nanoparticle hybrid membrane in situ by using self-assembly technology | |
| JP5855093B2 (en) | POLYIMIDE POROUS WEB, PROCESS FOR PRODUCING THE SAME, AND ELECTROLYTE MEMBRANE CONTAINING THE SAME | |
| CN102743981B (en) | Preparation and application of sodium alginate pervaporation hybrid membrane | |
| Cheng et al. | Enhanced pervaporation performance of polyamide membrane with synergistic effect of porous nanofibrous support and trace graphene oxide lamellae | |
| CN106245232A (en) | Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application | |
| CN110935335B (en) | High-hydrophilicity polymer hybrid membrane and preparation method thereof | |
| CN102824859B (en) | Method for preparing hollow fiber nanofiltration membrane by using thermally induced phase separation/interface cross linking synchronization method | |
| CN103331108A (en) | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane | |
| CN103028331A (en) | Preparation method of hydroxyethyl cellulose-silicon dioxide pervaporation hybrid membrane | |
| CN101284214B (en) | Preparation method of uni-endodermis hollow fiber infiltrating and vaporizing membrane | |
| CN113457448A (en) | Preparation method of double-layer Mxene film based on different interlayer distances | |
| CN102553459A (en) | Preparation method of tubular organic/inorganic pervaporation composite membrane | |
| CN110280148B (en) | Preparation method of polyvinylidene fluoride ultrafiltration membrane modified by hydrophilic graphene | |
| CN103007783A (en) | Preparation method of cellulose ether-ethyl orthosilicate pervaporation hybrid membrane | |
| KR101893458B1 (en) | Graphene membrane and method for manufacturing the same | |
| CN104014251B (en) | A kind of preparation method based on inorganic supporting body assembled inorganic particle hydridization polyelectrolyte NF membrane | |
| CN105903356A (en) | Layer-by-layer self-assembling preparation method for acid-resisting polyelectrolyte compound film | |
| CN101507904A (en) | Composite ultrafiltration membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120530 Termination date: 20140723 |
|
| EXPY | Termination of patent right or utility model |