CN102503156A - Preparation method for super hydrophilic membranes - Google Patents
Preparation method for super hydrophilic membranes Download PDFInfo
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- CN102503156A CN102503156A CN2011103216841A CN201110321684A CN102503156A CN 102503156 A CN102503156 A CN 102503156A CN 2011103216841 A CN2011103216841 A CN 2011103216841A CN 201110321684 A CN201110321684 A CN 201110321684A CN 102503156 A CN102503156 A CN 102503156A
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Abstract
A preparation method for super hydrophilic membranes belongs to the field of membrane technology and comprises the steps of: respectively making polycation and polyanion into membrane casting solution; coating micron particles to form two kinds of micron particle enveloping bodies, of which the surfaces are charged with opposite charges; and coating nano particles to form two kinds of nano particle enveloping bodies, of which the surfaces are charged with opposite charges. The nano particle enveloping bodies, of which the surfaces are charged with positive electricity or negative electricity, are added in micron particle enveloping body solution, of which the surface is charged with negative electricity or positive electricity, so electrical raspberry particle solution, of which the surfaces are charged with positive electricity or negative electricity, are obtained. Substrates are firstly arranged in the micron particle enveloping body solution, of which the surface is charged with positive electricity or negative electricity; and then the substrates are arranged in the electrical raspberry particle solution, of which the surface is charged with opposite charges, the assembling is performed alternately and repeatedly; or the substrates are directly arranged in the raspberry particle solution with two opposite charges to be assembled for a plurality of times alternately and repeatedly, so super hydrophilic membranes are obtained. The preparation method for the super hydrophilic membranes provided in the invention has a simple process and can modulate surface property of membranes flexibly.
Description
Technical field
The present invention relates to a kind of preparation method of super-hydrophilic film, relate in particular to the super-hydrophilic film that a kind of micro-nano-sphere self-assembly forms, belong to the membrane technique field.
Background technology
Surface wettability is the important physicochemical property of solid surface, weighs through the static or dynamic contact angle of liquid.In recent years, ultra-hydrophilic surface has received people's extensive concern as a kind of very special phenomena.The Superhydrophilic surface is meant the surface with contact angle＜5 of water °, its excellent performance, is widely used, can automatically cleaning, antifog, improve surface heat exchange efficiency etc.The formation of ultra-hydrophilic surface generally has two kinds of methods, and its mechanism of action has nothing in common with each other.First kind is to utilize photocatalytic, has ultra hydrophilic performance after making its radiation effect that receives UV-light or visible light; Second method is through the transformation to material surface chemistry and how much micro-nano structures, can make material have super hydrophilicity.The preparation method of ultra-hydrophilic surface mainly comprise sol-gel method, micro-plasma oxidation method, liquid phase deposition, chemical Vapor deposition process and, magnetron sputtering method and self-assembling technique etc.The research of ultra-hydrophilic surface at present mainly is based on TiO
2The research of photic super-hydrophilic film, but TiO
2The existing performance of film also can not satisfy social demands of applications far away, has seriously restricted TiO as initial contact angle is big, spectral response range is less, Superhydrophilic is not lasting etc.
2The application of film.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of micro-nano-sphere self-assembly super-hydrophilic film particularly utilizes the self-assembly of micro-nano particle to regulate and control the method for surface properties.
The preparation method of super-hydrophilic film of the present invention may further comprise the steps:
(1) micron particle is joined in the said polycation solution under ultrasonic state, hatching, centrifugal forms the micron particle enveloping solid of surperficial lotus positive electricity;
(2) the micron particle enveloping solid solution with the surperficial lotus positive electricity of preparation in the step (1) joins under ultrasonic state in the polyanion solution, and hatching, centrifugal forms the electric micron particle enveloping solid of surperficial bear;
(3) repeating step (1) and (2) successively, wherein step (1) is N+1 time, step (2) is N time, can get the micron particle enveloping solid solution of surperficial lotus positive electricity; Step (1) M time, step (2) M time can get the electric micron particle enveloping solid solution of surperficial bear;
(4) nanoparticle is joined under ultrasonic state gather in sun or the anion solutions, ultrasonic, centrifugal, supernatant is changed into and supernatant equal-volume deionized water after centrifugal; Repeat 1～10 time, make and gather sun or negatively charged ion nanoparticle enveloping solid solution;
(5) under the ultrasonic state; Step (4) is gathered in the micron particle enveloping solid solution of negative electricity (or lotus positive electricity) that sun (or negatively charged ion) nanoparticle enveloping solid solution joins the surperficial lotus opposite charges of step (3); Hatching, centrifugal forms surperficial bear electricity (or lotus positive electricity) type raspberry particle;
After above-mentioned solution preparation steps, further on substrate, continue assembling according to the following step:
(6) substrate of bear electricity after the pre-treatment is placed micron particle enveloping solid (or class raspberry particle of the surperficial lotus positive electricity) solution of surperficial lotus positive electricity; Make the micron particle enveloping solid (or class raspberry particle of surperficial lotus positive electricity) of surperficial lotus positive electricity be assembled in substrate surface; Form thin film layer, substrate is taken out oven dry;
(7) substrate in the step (6) is placed surperficial bear electricity type raspberry particle (or micron particle enveloping solid of surperficial bear electricity) solution; The micron particle enveloping solid of type of making raspberry particle and oppositely charged is through the electrostatic adhesion assembling; Form film, substrate is taken out oven dry;
(8) repeating step (6), (7) are N time, can obtain super-hydrophilic film.
Perhaps assemble according to following step:
(9) substrate of bear electricity after the pre-treatment is placed the class raspberry particle solution of surperficial lotus positive electricity, the class raspberry particle assembling that makes surperficial lotus positive electricity is taken out oven dry at substrate surface with substrate;
(10) place a surperficial bear electricity type raspberry particle solution to assemble the substrate in the step (9), substrate is taken out oven dry;
(11) repeating step (9), (10) are N time, also can obtain super-hydrophilic film.
Wherein, step (1), (2), (4) described polycation preferably from polymine, diallyl dimethyl ammoniumchloride, PAH hydrochloride, gather tetrem thiazolinyl pyridine; The polyanion material is selected from ROHM, Lewatit, SPSF.
The described nanoparticle of step (4) is ZIRCONIUM DIOXIDE 99.5, titanium oxide, aluminium sesquioxide, silicon-dioxide, manganous carbonate, lime carbonate, permanent white, and particle diameter is 1～100 nanometer.
The described micron particle of step (1) is silicon-dioxide, manganous carbonate, lime carbonate, permanent white, titanium oxide, aluminium sesquioxide, and particle diameter is 1～5 micron.
The described substrate of step (6) is a hard substrate, can be silica glass, silicon single crystal, Calcium Fluoride (Fluorspan).
Present method is based on the thin film preparation process of self-assembling technique; Respectively micron particle and inorganic nano-particle are directly joined in the charged polyelectrolyte solution earlier; Utilize repeated ultrasonic and centrifugally operated to make polymkeric substance enveloping solid particle; Again nanoparticle enveloping solid solution is joined in the micron particle enveloping solid solution, utilizes repeated ultrasonic and centrifugally operated type of making raspberry particle, utilize at last layer upon layer electrostatic absorption with micron particle and type raspberry particle assembling on substrate.The present invention adopts the static self-assembling technique, utilizes the micro-nano particle to carry out self-assembly, the preparation super-hydrophilic film.Its advantage is that filmogen is abundant, and the preparation method is simple, and can realize the multilayer assembling through the charged change of properties of particle, thus the interfacial property of flexible modulation film.
Description of drawings
The scanning electron microscope analysis picture is carried out on the film surface of Fig. 1, embodiment 1.
Embodiment
Below in conjunction with specific embodiment the present invention is done detailed explanation, but protection scope of the present invention is not limited only to following embodiment.
Embodiment 1
The employing substrate is a silica glass, and used polycation material is polymine (PEI, molecular weight are 60,000), and polyanion is ROHM (PAA, molecular weight are 4,000,000), bicarbonate of ammonia (NH
4HCO
3), manganous sulfate (MnSO
4H
2O), nano zirconia particles (ZrO
2, in the nano particle size 100nm), polymine and polyacrylic solvent are deionized water.
Assembling condition and method:
(1) with NH
4HCO
3And MnSO
4Be dissolved in the deionized water, be configured to the uniform solution of 0.16M and 0.016M respectively, standing and defoaming;
(2) get 200ml MnSO
4Solution adds the 40ml absolute ethyl alcohol, with ultrasonic or magnetic agitation it is mixed, and at magnetic agitation (～600rpm) adding 200ml NH rapidly down
4HCO
3Solution, standing and reacting behind the lasting stirring 15s is until all MnCO that generate
3Micron particle precipitates fully, and the gained particle is collected with centrifuging or membrane filter method fast, with deionized water wash three times, makes MnCO
3Micron particle is dispersed in the water subsequent use;
(3) respectively PEI and PAA are dissolved in the 0.2M NaCl solution, respectively are made into the solution of 2mg/mL, and their PH is adjusted to 6.5, standing and defoaming with the HCl of 0.1M or NaOH solution;
(4) with (2) synthetic MnCO
3Micron particle solution joins under ultrasonic state in the 120ml PEI solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes,, form the MnCO of surperficial lotus positive electricity with the NaCl solution washing of 0.2M three times
3The micron particle enveloping solid is dispersed in the NaCl solution subsequent use;
(5) with the MnCO of the surperficial lotus positive electricity of preparation in (4)
3Micron particle enveloping solid solution joins under ultrasonic state in the 90ml PAA solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form the MnCO of surperficial bear electricity
3The micron particle enveloping solid is dispersed in the NaCl solution it subsequent use;
(6) repeating step is (4) 2 times, (5) 1 times, can get the MnCO of surperficial lotus positive electricity
3Micron particle enveloping solid solution, repeating step (4) 1 times (5) 1 times, can get the electric MnCO of surperficial bear
3Micron particle enveloping solid solution;
(7) with deionized water PEI is made into the solution 500ml of 0.5wt%, standing and defoaming adds nano zirconia particles solution 1ml;
(8) will add ultrasonic 120 minutes of the PEI solution of nano zirconia particles, make the nanoparticle homodisperse after, centrifugal 10 minutes; After centrifugal supernatant is changed into and supernatant equal-volume deionized water; Repeat 3 times, make the PEI nano-particle solution, be dispersed in the NaCl solution subsequent use;
(9) under ultrasonic state, PEI nanoparticle enveloping solid solution is joined the MnCO of surperficial bear electricity
3In the micron particle enveloping solid solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form a type raspberry particle, be dispersed in the NaCl solution it subsequent use;
(10) substrate is placed in the mixing solutions of the vitriol oil and ydrogen peroxide 50,, makes the substrate bear in 70 ℃ of heating 3 hours;
(11) substrate in the step (10) is placed in the deionized water, the rinsing face also dries up;
(12) substrate in the step (11) is placed on the MnCO of surperficial lotus positive electricity
330min in the micron particle enveloping solid solution makes substrate surface form the MnCO of lotus positive electricity
3Micron particle enveloping solid thin film layer takes out substrate, puts into 45 ℃ of baking ovens and dries;
(13), make the MnCO of surperficial lotus positive electricity with in substrate type of the being placed on raspberry particle solution in the step (12) 30 minutes
3A micron particle enveloping solid and a type raspberry particle generation electrostatic adhesion form dense film, and substrate is taken out, and put into 45 ℃ of baking ovens and dry;
(14) repeat (12), (13) 2 times, promptly get super-hydrophilic film.
Utilize the contact angle appearance to measure dynamic contact angle the super-hydrophilic film of above-mentioned assembling, record water droplet and spread near 0 ° of needed time＜1.0s.
Embodiment 2
The employing substrate is a silica glass, and used polycation material is polymine (PEI, molecular weight are 60,000), and polyanion is ROHM (PAA, molecular weight are 4,000,000), micro-calcium carbonate (CaCO
3, micron granularity 1～5um), nano-titania particle (TiO
2, nano particle size 15～50nm), polymine and polyacrylic solvent are deionized water.
Assembling condition and method:
(1) respectively PEI and PAA are dissolved in the 0.2M NaCl solution, respectively are made into the solution of 2mg/mL, and their PH is adjusted to 6.5, standing and defoaming with the HCl of 0.1M or NaOH solution;
(2) with CaCO
3Micron particle solution joins under ultrasonic state in the 120ml PEI solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes,, form the CaCO of surperficial lotus positive electricity with the NaCl solution washing of 0.2M three times
3The micron particle enveloping solid is dispersed in the NaCl solution subsequent use;
(3) with the CaCO of the surperficial lotus positive electricity of preparation in (2)
3Micron particle enveloping solid solution joins under ultrasonic state in the 90ml PAA solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form the CaCO of surperficial bear electricity
3The micron particle enveloping solid is dispersed in the NaCl solution it subsequent use;
(4) repeating step is (2) 2 times, (3) 1 times, can get the CaCO of surperficial lotus positive electricity
3Micron particle enveloping solid solution, repeating step (2) 1 times (3) 1 times, can get the electric CaCO of surperficial bear
3Micron particle enveloping solid solution;
(5) with deionized water PEI is made into the solution 500ml of 0.5wt%, standing and defoaming adds nano-TiO
2Particle solution 1ml;
(6) will add nano-TiO
2Ultrasonic 120 minutes of the PEI solution of particle, make the nanoparticle homodisperse after, centrifugal 10 minutes, supernatant is changed into and supernatant equal-volume deionized water after centrifugal, repeat 3 times, make the PEI nano-particle solution, be dispersed in the NaCl solution subsequent use;
(7) under ultrasonic state, PEI nanoparticle enveloping solid solution is joined the CaCO of surperficial bear electricity
3In the micron particle enveloping solid solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form a type raspberry particle, be dispersed in the NaCl solution it subsequent use;
(8) substrate is placed in the mixing solutions of the vitriol oil and ydrogen peroxide 50,, makes the substrate bear in 70 ℃ of heating 3 hours;
(9) substrate in the step (8) is placed in the deionized water, the rinsing face also dries up;
(10) substrate in the step (9) is placed on the CaCO of surperficial lotus positive electricity
330min in the micron particle enveloping solid solution makes substrate surface form the CaCO of lotus positive electricity
3Micron particle enveloping solid thin film layer takes out substrate, puts into 45 ℃ of baking ovens and dries;
(11), make the CaCO of surperficial lotus positive electricity with in substrate type of the being placed on raspberry particle solution of step (10) 30 minutes
3A micron particle enveloping solid and a type raspberry particle generation electrostatic adhesion form dense film, and substrate is taken out, and put into 45 ℃ of baking ovens and dry;
(12) repeat (10), (11) 2 times, promptly get super-hydrophilic film.
Utilize the contact angle appearance to measure dynamic contact angle the super-hydrophilic film of above-mentioned assembling, record water droplet and spread near 0 ° of needed time＜1.0s.
Embodiment 3
The employing substrate is a silica glass, and used polycation material is polymine (PEI, molecular weight are 60,000) and diallyl dimethyl ammoniumchloride (PDDA; Molecular weight is 100000～200000); Polyanion is Lewatit (PSS, molecular weight are 70000), bicarbonate of ammonia (NH
4HCO
3), manganous sulfate (MnSO
4H
2O), nano zirconia particles (ZrO
2, in the nano particle size 100nm), the solvent of polymine, diallyl dimethyl ammoniumchloride and Lewatit is water.
Assembling condition and method:
(1) with NH
4HCO
3And MnSO
4Be dissolved in the deionized water, be configured to the uniform solution of 0.16M and 0.016M respectively, standing and defoaming;
(2) get 200ml MnSO
4Solution adds the 40ml absolute ethyl alcohol, with ultrasonic or magnetic agitation it is mixed, and at magnetic agitation (～600rpm) adding 200ml NH rapidly down
4HCO
3Solution, standing and reacting behind the lasting stirring 15s is until all MnCO that generate
3Micron particle precipitates fully, and the gained particle is collected with centrifuging or membrane filter method fast, with deionized water wash three times, makes MnCO
3Micron particle is dispersed in the water subsequent use;
(3) respectively PEI, PDDA and PSS are dissolved in the 0.2M NaCl solution, respectively are made into the solution of 2mg/mL, wherein, PEI is adjusted to 6.5 with its PH, standing and defoaming with the HCl solution of 0.1M;
(4) with (2) synthetic MnCO
3Micron particle solution joins under ultrasonic state in the 120ml PEI solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes,, form the MnCO of surperficial lotus positive electricity with the NaCl solution washing of 0.2M three times
3The micron particle enveloping solid is dispersed in the NaCl solution subsequent use;
(5) with the MnCO of the surperficial lotus positive electricity of preparation in (4)
3Micron particle enveloping solid solution joins under ultrasonic state in the 120ml PSS solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form the MnCO of surperficial bear electricity
3The micron particle enveloping solid is dispersed in the NaCl solution it subsequent use;
(6) the electric MnCO of surperficial bear that step (5) is prepared
3Micron particle enveloping solid solution is joining under ultrasonic state in the 120ml PDDA solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form the MnCO of surperficial lotus positive electricity
3The micron particle enveloping solid is dispersed in the NaCl solution it subsequent use;
(7) with deionized water PDDA is made into the solution 500ml of 0.94wt%, standing and defoaming adds nano zirconia particles solution;
(8) will add ultrasonic 120 minutes of the PDDA solution of nano zirconia particles, make the nanoparticle homodisperse after, centrifugal 10 minutes; After centrifugal supernatant is changed into and supernatant equal-volume deionized water; Repeat 3 times, make the PDDA nano-particle solution, be dispersed in the NaCl solution subsequent use;
(9) under ultrasonic state, PDDA nanoparticle enveloping solid solution is joined the MnCO of surperficial bear electricity
3In the micron particle enveloping solid solution, hatch 30 minutes (during slight vibration particle is disperseed) after, centrifugal 5 minutes, use the NaCl solution washing afterwards three times, form a type raspberry particle, be dispersed in the NaCl solution it subsequent use;
(10) substrate is placed in the mixing solutions of the vitriol oil and ydrogen peroxide 50,, makes the substrate bear in 70 ℃ of heating 3 hours;
(11) substrate in the step (10) is placed in the deionized water, the rinsing face also dries up;
(12) substrate in the step (11) is placed on the MnCO of surperficial lotus positive electricity
330min in the micron particle enveloping solid solution makes substrate surface form the MnCO of lotus positive electricity
3Micron particle enveloping solid thin film layer takes out substrate, puts into 45 ℃ of baking ovens and dries;
(13), make the MnCO of surperficial lotus positive electricity with in substrate type of the being placed on raspberry particle solution in the step (12) 30 minutes
3A micron particle enveloping solid and a type raspberry particle generation electrostatic adhesion form dense film, and substrate is taken out, and put into 45 ℃ of baking ovens and dry;
(14) repeat (12), (13) 2 times, promptly get super-hydrophilic film.
Utilize the contact angle appearance to measure dynamic contact angle the super-hydrophilic film of above-mentioned assembling, record water droplet and spread near 0 ° of needed time＜1.2s.
Claims (5)
1. the preparation method of a super-hydrophilic film is characterized in that, may further comprise the steps:
(1) micron particle is joined in the said polycation solution under ultrasonic state, hatching, centrifugal forms the micron particle enveloping solid of surperficial lotus positive electricity;
(2) the micron particle enveloping solid solution with the surperficial lotus positive electricity of preparation in the step (1) joins under ultrasonic state in the polyanion solution, and hatching, centrifugal forms the electric micron particle enveloping solid of surperficial bear;
(3) repeating step (1) and (2) successively, wherein step (1) is N+1 time, step (2) is N time, can get the micron particle enveloping solid solution of surperficial lotus positive electricity; Step (1) M time, step (2) M time can get the electric micron particle enveloping solid solution of surperficial bear;
(4) nanoparticle is joined gather in sun or the anion solutions, ultrasonic, centrifugal, supernatant is changed into and supernatant equal-volume deionized water after centrifugal; Repeat 1～10 time, make and gather sun or negatively charged ion nanoparticle enveloping solid solution;
(5) under the ultrasonic state, step (4) is gathered sun or negatively charged ion nanoparticle enveloping solid solution joins in the micron particle enveloping solid solution of surperficial bear electricity or lotus positive electricity, hatching, centrifugal forms surperficial bear electricity or lotus positive electricity class raspberry particle;
After above-mentioned solution preparation steps, further on substrate, continue assembling according to the following step:
(6) pretreated bear electric substrate is placed the micron particle enveloping solid of surperficial lotus positive electricity or the class raspberry particle solution of surperficial lotus positive electricity; The class raspberry particle assembling of micron particle enveloping solid or surperficial lotus positive electricity that makes surperficial lotus positive electricity is at substrate surface; Form thin film layer, substrate is taken out oven dry;
(7) substrate in the step (6) is placed surperficial bear electricity type raspberry particle or the electric micron particle enveloping solid solution of surperficial bear; The micron particle enveloping solid of type of making raspberry particle and oppositely charged is through the electrostatic adhesion assembling; Form film, substrate is taken out oven dry;
(8) repeating step (6), (7) are N time, can obtain super-hydrophilic film;
Perhaps assemble according to following step:
(9) substrate of bear electricity after the pre-treatment is placed the class raspberry particle solution of surperficial lotus positive electricity, the class raspberry particle assembling that makes surperficial lotus positive electricity is taken out oven dry at substrate surface with substrate;
(10) place a surperficial bear electricity type raspberry particle solution to assemble the substrate in the step (9), substrate is taken out oven dry;
(11) repeating step (9), (10) are N time, also can obtain super-hydrophilic film.
2. according to the described method of claim 1, it is characterized in that, polycation preferably from polymine, diallyl dimethyl ammoniumchloride, PAH hydrochloride, gather tetrem thiazolinyl pyridine; The polyanion material is selected from ROHM, Lewatit, SPSF.
3. according to the described method of claim 1, it is characterized in that described micron particle is silicon-dioxide, manganous carbonate, lime carbonate, permanent white, titanium oxide, aluminium sesquioxide, particle diameter is 1～5 micron.
4. according to the described method of claim 1, it is characterized in that described nanoparticle is ZIRCONIUM DIOXIDE 99.5, titanium oxide, aluminium sesquioxide, silicon-dioxide, manganous carbonate, lime carbonate, permanent white, particle diameter is 1～100 nanometer.
5. according to the described method of claim 1, it is characterized in that described substrate is silica glass, silicon single crystal, Calcium Fluoride (Fluorspan).
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| CN104014251A (en) * | 2014-06-05 | 2014-09-03 | 北京工业大学 | Preparation method for inorganic particle hybrid polyelectrolyte nano-filtration membrane assembled based on inorganic supporting body |
| CN104759214A (en) * | 2015-03-27 | 2015-07-08 | 北京工业大学 | Preparation method of superhydrophilic/superhydrophobic composite nanofiltration membrane |
| CN104759214B (en) * | 2015-03-27 | 2016-11-02 | 北京工业大学 | A kind of preparation method of super-hydrophobicity composite nanometer filtering film |
| CN107848791A (en) * | 2015-07-15 | 2018-03-27 | Hrl实验室有限责任公司 | The semi-passive control of the solidification of dusty material |
| CN108601235A (en) * | 2017-12-28 | 2018-09-28 | 广东光华科技股份有限公司 | The method of insulating substrate electroplating surface metal |
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