CN103316507B - Super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and preparation method and application thereof - Google Patents
Super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and a preparation method and an application thereof. According to the method, fabric mesh with a specification of 100-300 meshes is subjected to ultrasonic cleaning, and is air-dried under normal temperature; a hydrophilic polymer water-sensitive agent and a cross-linking agent are dissolved in water according to a ratio of 1:9-9:1; the mixture is well mixed by magnetic stirring, such that a solution with a concentration of 1-99% is prepared; nano-sol is prepared with a sol-gel method; the solution and the nano-sol are prepared into a mixed solution with a concentration of 1-99%, and the solution is well dispersed through ultrasonic dispersion; the mesh is soaked in the mixed solution and is vertically lifted, or the mesh is directly sprayed by using a high-pressure spraying gun; and the mesh is bake-dried, such that the super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane is obtained. Contact angles of the super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane with water and oil in air are both 0 DEG, and the membrane is super-hydrophilic. Under water, the contact angle of the membrane with oil drops is larger than 150 DEG, and the membrane has an oil drop low adhesion characteristic. The mesh membrane provided by the invention can be used in oil-water mixture separation and oil-containing sewage processing.
Description
Technical field
The present invention relates to water-oil separating film, particularly relate to and there is in air super parents and the water-oil separating nethike embrane and its preparation method and application of super oleophobic properties under water, belong to organic-inorganic hybrid nanometer technical field of function materials.
Background technology
It is reported that the oil that probably has 3,200,000,000 cubic tons every year enters into water body, forms oil-polluted water.Oil-polluted water wide material sources, in industries such as oil, chemical industry, iron and steel, coking, gas generating station, machine-building and food processings, every water directly contacting with oils all contains oil.Oil has the difference of polar oil and non-polar oil, and polar oil derives from animal, biodegradable; Non-polar oil derives from oil and other mineral resources, difficult for biological degradation.Oil is across the sea floating, diffuses to form rapidly the reoxygenation effect of the air-locked oil film obstruction of one deck water body, affects halomereid growth, destroys marine ecology balance.Super hydrophilic super oleophobic film has in air super hydrophilic, super hydrophilic super oleophobic properties in water, in the time of oily waste water contact membranes surface, under the stimulation of water film surface occur re-assemble from super-hydrophobic become super hydrophilic, thereby water can only down permeate endlessly under gravity and capillary force effect, and surface remains super oleophobic property, thereby the effect of water-oil separating stayed surface always and reaches by oil, and due to the potential oil repellency of film, oil all the time cannot polluted membrane surface, is a kind of real antipollution, Non-energy-consumption, long-life, high efficiency diffusion barrier.
Publication number is that the Chinese invention patent application of CN102029079A discloses and has the oil-water separating net of super oleophobic properties under water, although this netting gear has oil-water separation, but the preparation of this film needs light initiation polymerization, the reaction time is 60～100min, and preparation method is simple not.Publication number is that the Chinese patent application of CN102716676A discloses with shitosan preparation and has the method for the oil-water separating net of super oleophobic properties under water, does not still relate to organic inorganic hybridization.And these two patent film forming matters used are all complete water-soluble polymer, cause the resistance to water of nethike embrane poor.
Summary of the invention
The object of the invention is to prepare and a kind ofly have in air and the water-oil separating nethike embrane and preparation method thereof of super oleophobic properties under water of super hydrophilic while under water.
Another object of the present invention is to provide the application of super water-oil separating nethike embrane hydrophilic and super oleophobic under water in the water-oil separating of oil-polluted water.
It is of the present invention that to have super water-oil separating nethike embrane hydrophilic and super oleophobic properties under water be using 100～300 object screen of fabric as base material, adopt the method for dip-coating or spraying to be coated with the hydrophilic polymer clad doped with inorganic nano-particle of micron thickness in the above, on clad, there is the projection of nanoscale, thereby obtain a kind of super water-oil separating nethike embrane hydrophilic and super oleophobic under water simultaneously.
Water-oil separating nethike embrane of the present invention has the composite construction of special nanometer and micron, the mesh of micro-meter scale, the You Ji of micron thickness ?the raised structures of nano-scale on inorganic doping clad and clad, water-oil separating nethike embrane of the present invention is 0 ° at air to water and oily contact angle, but has under water super oleophobic properties.
The object of the invention is achieved through the following technical solutions:
The preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water, comprises the steps:
(1) by 100～300 object screen of fabric ultrasonic cleaning, normal temperature dries;
(2), by soluble in water in the ratio of 1:9～9:1 to the agent of hydrophilic polymer water-sensitive and crosslinking agent, it is 1～99% solution that magnetic agitation is evenly mixed with solution concentration; Described water-sensitive agent is selected from one or both in polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, diallyl QAS polymer, poly, poly-aspartate, poly-epoxy succinic acid, carboxymethyl cellulose, carboxyethyl cellulose, xanthans and natural plant gum; Described crosslinking agent be polyacrylic acid, polymethylacrylic acid, Ju Bing Xi Suan ?acrylate copolymer, Ju Jia base Bing Xi Suan ?a kind of in acrylate copolymer, Hydroxylated acrylic resin, amino resins and urethane acrylate or two kinds;
(3) Cai with Rong Jiao ?gel method, taking tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide as raw material, with alcohols and water in mass ratio 1:5～5:1 be mixed with cosolvent, by raw material and cosolvent in mass ratio 1:1～1:5 be mixed in 20～80 DEG C of waters bath with thermostatic control, stirring, after 5～10min, drip catalyst, insulation 4～5h, obtains Nano sol; Described alcohols is one or more in ethanol, propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and isobutanol; Described catalyst is hydrochloric acid, nitric acid, boric acid, sulfuric acid, ammoniacal liquor, sodium acid carbonate or NaOH;
(4) by the Nano sol in the solution in step (2) and step (3) in mass ratio the ratio of 1:9～9:1 to be mixed with concentration be 1～99% mixed solution, ultrasonic being uniformly dispersed;
(5) silk screen obtaining in step (1) is immersed in the mixed solution in step (4), after soaking 5～20min, it is vertically lifted, or adopt high-pressure spray gun direct spraying, by soak or spraying after silk screen hang over and in constant-temperature vacuum baking oven, maintain the temperature at 100～200 DEG C of oven dry; Must super water-oil separating nethike embrane hydrophilic and super oleophobic under water.
For further realizing the object of the invention, described screen of fabric is preferably stainless steel cloth, copper mesh, aluminium wire netting, nylon mesh, polyvinyl silk screen, aramid fiber silk screen, terylene silk net or acrylic fibre fabric web.The supersonic frequency of described ultrasonic cleaning is 20～40KHz, and power bracket is 100～150W.The supersonic frequency of described ultrasonic dispersion is 20～40KHz, and power bracket is 300～500W.Described ultrasonic cleaning, for first clean by ultrasonic washing with clean water, then with absolute ethyl alcohol or acetone ultrasonic cleaning, then uses distilled water ultrasonic cleaning clean.The speed of described dropping catalysis is preferably 1～10ml/min.Nano particle diameter in described Nano sol is controlled at 10～500nm, and nano particle mass content is 20～35%.
Super water-oil separating nethike embrane hydrophilic and super oleophobic under water, its above-mentioned preparation method makes; Described water-oil separating nethike embrane is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with micron thickness in 100～300 object screen of fabric, on clad, be the spherical protuberances that is uniform-distribution with at many levels micro-meter scale simultaneously, on micro-meter scale projection and micron be uniform-distribution with the spherical protuberances of nanoscale in projection interval, the thickness of the clad of described micron thickness be 11 ?50 microns; The spherical protuberances particle diameter of described micro-meter scale is 1～50 micron; The particle diameter of the spherical protuberances of described nano-scale width be 10 ?900 nanometers; Described water-oil separating nethike embrane is 0 ° to water and oily contact angle in air, under water the contact angle of oil droplet is greater than to 150 °.
The application of water-oil separating nethike embrane super hydrophilic and super oleophobic under water described in the present invention also provides in the separation of oil water mixture and the processing of oil-polluted water.Contain rapeseed oil, linseed oil, soybean oil, peanut oil, corn oil, cottonseed oil, olive oil, sesame oil, rice bran oil, camellia oil, sunflower seeds wet goods edible oil as can be used for; The long chain alkanes such as dodecane, tridecane, the tetradecane, pentadecane, hexadecane; Benzene,toluene,xylene, trimethylbenzene, ethylbenzene, propyl benzene, styrene and other aromatic hydrocarbon; The organic matters such as methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, vinylacetate, ethyl acetate, butyl acetate, carbon tetrachloride, carrene, diiodomethane; The water-oil separating of crude oil, gasoline, kerosene, diesel oil, all kinds of solvent naphtha, lubricated wet goods.
Inorganic nano-particle rich surface hydroxyl of the present invention, and not containing other organic groups, particle diameter is 10～500nm.
The aperture of the mesh of described micro-meter scale be 30 ?170 microns; The aperture of the mesh of described micro-meter scale be 10 ?100 microns; The thickness of the clad of described micron thickness be 11 ?50 microns; The height of the projection of described nano-scale width be 10 ?900 nanometers.
With respect to prior art, tool of the present invention has the following advantages:
1) the prepared water-oil separating film of the present invention carries out water-oil separating and relies on gravity and capillary force completely, thereby have with low cost, energy consumption is lower, good separating effect, speed are fast, without other chemical addition agents, have no side effect and secondary pollution, the anti-oil droplet of automatically cleaning pollutes, and nethike embrane easily reclaims repeatedly recycling, can be used for preparing on a large scale.
2) when the prepared water-oil separating film of the present invention is processed, water flux is large, simple to operate, and except material Transfer energy consumption, without additional energy source consumption, film surface has self-cleaning function, is easy to clean and recycling, and the decline of membrane flux is slow.
3) raw material that the preparation of water-oil separating nethike embrane of the present invention adopts are all cheap and easy to get, and all there is no toxicity, and environmental friendliness can not cause secondary pollution, also can not produce injury to operator's health;
4) manufacture craft of the present invention and equipment are simple, are easy to realize, and are applicable to large-scale production on a large scale.
Brief description of the drawings
Fig. 1 is embodiment 1 rich surface hydroxyl nano silicon infrared spectrogram.
Fig. 2 is the clean blank stainless steel cloth surface water contact angle (91.7 °) of embodiment 1.
Fig. 3 is embodiment 1 micro-nano structure stainless steel cloth film coated surface water contact angle (0 °).
Fig. 4 is that 200 times of the blank stainless steel cloth of 300 orders amplify SEM figure.
Fig. 5 is that 200 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 6 is that 1000 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 7 is that 10000 times of embodiment 1 gained nethike embrane amplify SEM figure.
Fig. 8 a is the effect schematic diagram of embodiment 1 when applying nethike embrane separating oil aqueous mixtures and starting.
Fig. 8 b is the effect schematic diagram of embodiment 1 when applying nethike embrane separating oil aqueous mixtures and finishing.
Detailed description of the invention
Embodiment 1: Ju Yi Xi Chun ?polyacrylic acid/nanometer SiO
2the preparation of stainless steel cloth water-oil separating nethike embrane
(1) by a 15 × 15mm
2300 object stainless steel cloths immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 150W, under 40KHz, ultrasonic cleaning 8min, hangs up at normal temperatures and dries;
(2) in 500ml beaker, add the hot water of 95 DEG C of 180g, add 20g polyvinyl alcohol and polyacrylic acid by 1:1 mass ratio, stir in the following heating edge of magnetic agitation, then put aside and naturally cool to room temperature;
(3) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, take 0.5g mass concentration and be 25% ammoniacal liquor, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1ml/min with constant flow pump, after insulation 4h, discharging prepares the Nano silica sol of the about 10nm of particle diameter, and nano particle mass content is 20%.Adopt the structure of the nano particle of Fourier's infrared tester test synthesized, from accompanying drawing 1 infrared spectrogram, at 3400cm
?1there is a strong absworption peak at place, for Qiang Ji ?the absworption peak of OH, 930cm
?1place for silanol base Si ?the stretching vibration peak of OH, 1000～1100cm
?1locate strong and wide absworption peak for Si ?the stretching vibration absworption peak of O, this place also exist simultaneously Si ?O ?the stretching vibration absworption peak of Si (Fourth Ring body).Illustrate tetraethoxysilane all hydrolytic condensation generated the nanometer SiO of rich surface hydroxyl
2.
(4) by the Ju Yi Xi Chun of the Nano silica sol in step (3) and step (2) gained ?polyacrylic acid solution be that 1:1 mixes by solute mass ratio, being diluted with water and being mixed with concentration is 1% solution, at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) 10min in mixed solution stainless steel cloth immersion step (4) clean step (1) being obtained, to ensure that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 30min in the constant-temperature vacuum drying box of 150 DEG C.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness at 300 order stainless steel wires on the net, as shown in Figure 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, as shown in Figure 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 1 micron, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, as shown in Figure 7.
(6) in air, adopt the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) to be respectively 91.7 ° and 0 ° to the contact angle of 3 microliters of water, see accompanying drawing 2 and 3, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with No. 100 solvent naphthas 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and No. 100 solvent naphthas are blocked on film all the time, on even telolemma, redness does not all have residual, reach oil-water separation, seen shown in Fig. 8 a and Fig. 8 b.
Embodiment 2: Ju Yi bis-Chun ?urethane acrylate/nanometer SiO
2the preparation of copper mesh water-oil separating nethike embrane
(1) by a 15 × 15mm
2100 object copper mesh immerse respectively in order in distilled water, ethanol, distilled water respectively at 100W, under 20KHz, clean 10min, hang up at normal temperatures and dry;
(2) in 500ml beaker, add the hot water of 95 DEG C of 180g, add 20g polyethylene glycol and urethane acrylate by 1:5 mass ratio, stir in the following heating edge of magnetic agitation, then put aside and naturally cool to room temperature;
(3) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 80 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, take 0.5g mass concentration and be 25% hydrochloric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1ml/min with constant flow pump, after insulation 4h, discharging prepares the Nano silica sol of particle diameter 500nm, and nano particle mass content is 35%.The structure that adopts the nano particle of Fourier's infrared tester test synthesized, resulting structures figure is similar to Fig. 1.
(4) by the Ju Yi Xi Chun of the Nano silica sol in step (3) and step (2) gained ?urethane acrylate solution mix by solute mass ratio 1:9, adding water and being mixed with concentration is 5% solution, at 300W, under 20KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) mixed solution that adopts high-pressure spray gun under the pressure of 0.6Mpa, step (4) to be obtained is sprayed at the clean copper mesh surface of step (1), be to toast 30min in the constant-temperature vacuum drying box of 120 DEG C to ensure the coating of 10 microns of silk screen surface uniform distribution one decks, to hang over temperature.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness on 300 order copper mesh, to similar shown in Fig. 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, to similar shown in Fig. 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 7.
(6) in air, adopt the contact angle of the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) to 3 microliters of water, similar with 3 to accompanying drawing 2 respectively, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with diesel oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and diesel oil is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 3: poly-dimethyl diallyl Lvization An ?polyacrylic acid/nanometer SiO
2the preparation of aluminium wire netting water-oil separating nethike embrane
(1) by a 15 × 15mm
2200 object aluminium wire nettings immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 150W, under 40KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) in 500ml beaker, add the deionized water of 180g, add 20g PAA ?g ?PDDA block copolymer, under magnetic agitation, stir;
(3) in four-hole boiling flask, add 50g tetramethoxy-silicane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, take 0.5g mass concentration and be 25% sodium acid carbonate, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 5h, discharging prepares the Nano silica sol of particle diameter 200nm, and nano particle mass content is 35%.The structure that adopts the nano particle of Fourier's infrared tester test synthesized, resulting structures figure is similar to Fig. 1;
(4) by the PAA of the Nano silica sol in step (4) and step (3) gained ?g ?PDDA solution mix by solute mass ratio 9:1, adding water and being mixed with concentration is 99% solution, at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) 8min in mixed solution aluminium wire netting immersion step (5) clean step (1) being obtained, to ensure that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 60min in the constant-temperature vacuum drying box of 100 DEG C.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness on 300 order copper mesh, to similar shown in Fig. 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, to similar shown in Fig. 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 7.
(6) in air, adopt the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (6) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with dodecane 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and dodecane is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 4: Ju Yangization Yi Xi ?polyacrylic acid/nanometer SiO
2the preparation of nylon mesh water-oil separating nethike embrane
(1) by a 15 × 15mm
2300 object nylon mesh immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 100W, under 20KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) in 500ml beaker, add the deionized water of 180g, add 20g PAA ?g ?PEG block copolymer, under magnetic agitation, stir;
(3) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, take 0.5g mass concentration and be 25% sulfuric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the Nano silica sol of the about 20nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.The structure that adopts the nano particle of Fourier's infrared tester test synthesized, resulting structures figure is similar to Fig. 1;
(4) by the PAA of the Nano silica sol in step (4) and step (3) gained ?g ?PEG solution mix by solute mass ratio 1:9, add water and be mixed with the solution of mass concentration 10%, at 300W, under 20KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) 10min in mixed solution nylon mesh immersion step (5) clean step (1) being obtained, to ensure that gauze is fully soaked into, then vertically to lift that hanging over temperature is to toast 60min in the constant-temperature vacuum drying box of 100 DEG C.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness on 300 order copper mesh, to similar shown in Fig. 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, to similar shown in Fig. 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 7.
(6) in air, adopt the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (6) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with 1 rapeseed oil 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and rapeseed oil is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 5
Suo Jia base Xian Wei Su ?amino resins/nanometer SiO
2the preparation of polyvinyl silk screen water-oil separating nethike embrane
(1) by a 15 × 15mm
2300 object polyvinyl silk screens immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 100W, under 20KHz, ultrasonic cleaning 5min, hangs up at normal temperatures and dries;
(2) in 500ml beaker, add the more than 95 DEG C hot water of 180g, add 15g carboxymethyl cellulose, 5gHMMM amino resins stirs in the following heating edge of magnetic agitation, then puts aside and naturally cools to room temperature;
(3) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, take 0.5g mass concentration and be 25% nitric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the Nano silica sol of the about 50nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.The structure that adopts the nano particle of Fourier's infrared tester test synthesized, resulting structures figure is similar to Fig. 1;
(4) the carboxymethyl cellulose mixed solution of the Nano silica sol in step (3) and step (2) gained is mixed by solute mass ratio 9:1, be mixed with concentration and be 1% solution, at 40W, under 30KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) 10min in mixed solution stainless steel cloth immersion step (4) clean step (1) being obtained, to ensure that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 30min in the constant-temperature vacuum drying box of 150 DEG C.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness on 300 order copper mesh, to similar shown in Fig. 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, to similar shown in Fig. 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 7.
(6) in air, adopt the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with trimethylbenzene 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and trimethylbenzene is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 6
Ju Ma Lai Suan ?Hydroxylated acrylic resin/nano-TiO
2the preparation of aramid fiber silk screen oil-water separating net film
(1) by a 15 × 15mm
2300 object aramid fiber silk screens immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 100W, under 20KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) in 500ml beaker, add the more than 95 DEG C hot water of 180g, add 15g poly, 5g Hydroxylated acrylic resin stirs in the following heating edge of magnetic agitation, then puts aside and naturally cools to room temperature;
(3) in four-hole boiling flask, add 50g purity titanium tetraethoxide, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, taking 0.5g mass concentration and be 25% NaOH adds in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the nano-titanium colloidal sol of the about 50nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.The structure that adopts the nano particle of Fourier's infrared tester test synthesized, resulting structures figure is similar to Fig. 1;
(4) by the Ju Ma Lai Suan of the nano-titanium colloidal sol in step (3) and step (2) gained ?hydroxy acrylic acid mixed solution in mass ratio 1:1 mix, add water and be mixed with the solution of concentration 1%, at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) 10min in mixed solution stainless steel cloth immersion step (4) clean step (1) being obtained, to ensure that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 30min in the constant-temperature vacuum drying box of 150 DEG C.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness on 300 order copper mesh, to similar shown in Fig. 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, to similar shown in Fig. 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 7.
(6) in air, adopt the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with methyl methacrylate 1:1 mixing and stirring by volume, oil-water mixture is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and methyl methacrylate is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Embodiment 7: Huang Yuan Jiao ?Hydroxylated acrylic resin/nano-TiO
2the preparation of terylene silk net water-oil separating nethike embrane
(1) by a 15 × 15mm
2300 object terylene silk nets immerse respectively in order in distilled water, ethanol or acetone, distilled water respectively at 150W, under 40KHz, ultrasonic cleaning 10min, hangs up at normal temperatures and dries;
(2) in 500ml beaker, add the more than 95 DEG C hot water of 180g, add 15g xanthans, 5g Hydroxylated acrylic resin stirs in the following heating edge of magnetic agitation, then puts aside and naturally cools to room temperature;
(3) in four-hole boiling flask, add 50g tetraethoxysilane, 100g absolute ethyl alcohol and 20g deionized water, 35 DEG C of water bath with thermostatic control heating are also constantly stirred, after stirring, take 0.5g mass concentration and be 25% boric acid, add in 30g deionized water, splash in four-hole boiling flask with the speed of 1.5ml/min with constant flow pump, after insulation 4h, the nano-titanium colloidal sol of the about 50nm of particle diameter left and right is prepared in discharging, and nano particle mass content is 35%.The structure that adopts the nano particle of Fourier's infrared tester test synthesized, resulting structures figure is similar to Fig. 1;
(4) by the Huang Yuan Jiao of the Nano silica sol in step (3) and step (2) gained ?Hydroxylated acrylic resin mixed solution mix by solute mass ratio 1:1, adding water and being mixed with concentration is 99% solution, at 500W, under 40KHz, ultrasonic dispersion 10min is uniformly dispersed with guarantee;
(5) 5min in mixed solution terylene silk net immersion step (4) clean step (1) being obtained, to ensure that silk screen is fully soaked into, then vertically to lift that hanging over temperature is to toast 60min in the constant-temperature vacuum drying box of 150 DEG C.
Adopt the contact angle of Dataphysics OCA40 Micro type Surface Contact angle tester test water on nethike embrane, with surface topography and the relative dimensions of the S ?3700N of HIT type sem observation nethike embrane.The visible water-oil separating nethike embrane of scanning electron microscope (SEM) photograph that is 200 times in multiplication factor by the surface of film is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with 50 micron thickness on 300 order copper mesh, to similar shown in Fig. 5; The ESEM picture that is 1000 times in multiplication factor exists the micropore of 40 micron pore size as seen in silk screen interval, and micropore is around all the projection of micro-nano coarse structure simultaneously, to similar shown in Fig. 6; Further amplify, be that the ESEM picture of 10000 times is visible in multiplication factor, in the distributing projection of micro-nano compound structure of the surface uniform of film, wherein the particle diameter of micron ball is 10 microns, simultaneously on micron ball and exist the nanosphere that particle diameter is 100nm between micron ball interval, to similar shown in Fig. 7.
(6) in air, adopt the silk screen obtaining in surface tension tester (OCA) measuring process (1) empty silk screen and step (5) similar with 3 to accompanying drawing 2 respectively to the contact angle of 3 microliters of water, prove that this nethike embrane has super hydrophilicity.
(7) silk screen obtaining in step (5) being placed on to 500ml beaker mouth rubber band fixes and makes film be bowl-shape downwards, water is dyed to redness with red ink, with hexadecane 4:1 mixing and stirring by volume, add 0.2g neopelex, magnetic agitation 15min makes O/W emulsion, emulsion is poured in this bowl-shape film, hydrophilic polymer water absorption and swelling, red water is infiltration downwards continually, and hexadecane is blocked on film all the time, on even telolemma redness all do not have residual, thereby reached oil-water separation.
Claims (9)
1. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water, is characterized in that comprising the steps:
(1) by 100～300 object screen of fabric ultrasonic cleaning, normal temperature dries;
(2) agent of hydrophilic polymer water-sensitive and crosslinking agent are pressed to the mass ratio of 1:9～9:1 soluble in water, it is 1～99% solution that magnetic agitation is evenly mixed with solution concentration; Described water-sensitive agent is selected from one or both in polyvinyl alcohol, polyethylene glycol, polyethylene glycol oxide, diallyl QAS polymer, poly, poly-aspartate, poly-epoxy succinic acid, carboxymethyl cellulose, carboxyethyl cellulose, xanthans and natural plant gum; Described crosslinking agent be polyacrylic acid, polymethylacrylic acid, Ju Bing Xi Suan ?acrylate copolymer, Ju Jia base Bing Xi Suan ?a kind of in acrylate copolymer, Hydroxylated acrylic resin, amino resins and urethane acrylate or two kinds;
(3) Cai with Rong Jiao ?gel method, taking tetraethoxysilane, tetramethoxy-silicane or purity titanium tetraethoxide as raw material, with alcohols and water in mass ratio 1:5～5:1 be mixed with cosolvent, by raw material and cosolvent in mass ratio 1:1～1:5 be mixed in 20～80 DEG C of waters bath with thermostatic control, stirring, after 5～10min, drip catalyst, insulation 4～5h, obtains Nano sol; Described alcohols is one or more in ethanol, propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol and isobutanol; Described catalyst is hydrochloric acid, nitric acid, boric acid, sulfuric acid, ammoniacal liquor, sodium acid carbonate or NaOH;
(4) by the Nano sol in the solution in step (2) and step (3) in mass ratio the ratio of 1:9～9:1 to be mixed with concentration be 1～99% mixed solution, ultrasonic being uniformly dispersed;
(5) silk screen obtaining in step (1) is immersed in the mixed solution in step (4), after soaking 5～20min, it is vertically lifted, or adopt high-pressure spray gun direct spraying, by soak or spraying after silk screen hang over and in constant-temperature vacuum baking oven, maintain the temperature at 100～200 DEG C of oven dry; Must super water-oil separating nethike embrane hydrophilic and super oleophobic under water.
2. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, it is characterized in that: described screen of fabric is stainless steel cloth, copper mesh, aluminium wire netting nylon mesh, polyvinyl silk screen, aramid fiber silk screen, terylene silk net or acrylic fibre fabric web.
3. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: the supersonic frequency of described ultrasonic cleaning is 20～40KHz, and power bracket is 100～150W.
4. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: the supersonic frequency of described ultrasonic dispersion is 20～40KHz, and power bracket is 300～500W.
5. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, it is characterized in that: described ultrasonic cleaning is for first clean by ultrasonic washing with clean water, then with absolute ethyl alcohol or acetone ultrasonic cleaning, then use distilled water ultrasonic cleaning clean.
6. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: the speed of described dropping catalysis is 1～10ml/min.
7. the preparation method of super water-oil separating nethike embrane hydrophilic and super oleophobic under water according to claim 1, is characterized in that: the nano particle diameter in described Nano sol is controlled at 10～500nm, nano particle mass content is 20～35%.
8. super water-oil separating nethike embrane hydrophilic and super oleophobic under water, is characterized in that, it is made by preparation method described in claim 1 ?7 any one; Described water-oil separating nethike embrane is the hydrophilic polymer clad doped with inorganic nano-particle that is coated with micron thickness in 100～300 object screen of fabric, on clad, be the spherical protuberances that is uniform-distribution with at many levels micro-meter scale simultaneously, on micro-meter scale projection and micron be uniform-distribution with the spherical protuberances of nanoscale in projection interval, the thickness of the clad of described micron thickness be 11 ?50 microns; The spherical protuberances particle diameter of described micro-meter scale is 1～50 micron; The particle diameter of the spherical protuberances of described nano-scale width be 10 ?900 nanometers; Described water-oil separating nethike embrane is 0 ° to water and oily contact angle in air, under water the contact angle of oil droplet is greater than to 150 °.
9. the application of super water-oil separating nethike embrane hydrophilic and super oleophobic under water claimed in claim 8 in the separation of oil water mixture and the processing of oil-polluted water.
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Families Citing this family (48)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112473323B (en) * | 2020-11-06 | 2022-05-31 | 中物院成都科学技术发展中心 | Industrial acetone tail gas separation and recovery device |
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| CN113265879B (en) * | 2021-04-29 | 2022-09-09 | 东莞理工学院 | Multi-crosslinking super-hydrophilic fabric and preparation method thereof |
| CN114345404B (en) * | 2021-12-28 | 2023-09-19 | 万华化学集团股份有限公司 | Phenol hydroxylation catalyst and preparation method thereof, and phenol hydroxylation method |
| CN114505061B (en) * | 2022-01-24 | 2023-01-06 | 华南理工大学 | Super-hydrophilic/underwater super-oleophobic copper mesh and preparation method and application thereof |
| CN114703665B (en) * | 2022-05-11 | 2023-08-04 | 嘉兴学院 | Super-hydrophilic-super-oleophobic self-healing fabric and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5748305A (en) * | 1980-09-05 | 1982-03-19 | Nitto Electric Ind Co Ltd | Membrane separation treatment of oil containing waste water |
| JPS62176509A (en) * | 1986-01-30 | 1987-08-03 | Idemitsu Petrochem Co Ltd | Oil-water separation method and device therefor |
| JPH0338292A (en) * | 1989-06-30 | 1991-02-19 | Nagakiyo Kogyo Kk | Apparatus for removing spillage oil |
| US20070131611A1 (en) * | 2005-12-13 | 2007-06-14 | General Electric Company | Membrane-based article and associated method |
| WO2009002747A2 (en) * | 2007-06-22 | 2008-12-31 | Aspen Systems, Inc. | Convenient substance-recovery system and process |
| CN102698471B (en) * | 2012-05-16 | 2014-10-22 | 清华大学 | Oil-water separating mesh film and preparation method thereof |
| CN102728104A (en) * | 2012-07-12 | 2012-10-17 | 北京航空航天大学 | Corrosion-resistant oil-water separation mesh membrane as well as preparation method and applications thereof |
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