CN106868712A - A kind of Membrane Materials nano fibrous membrane and preparation method thereof - Google Patents
A kind of Membrane Materials nano fibrous membrane and preparation method thereof Download PDFInfo
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- CN106868712A CN106868712A CN201510923571.7A CN201510923571A CN106868712A CN 106868712 A CN106868712 A CN 106868712A CN 201510923571 A CN201510923571 A CN 201510923571A CN 106868712 A CN106868712 A CN 106868712A
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4282—Addition polymers
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Abstract
The invention provides a kind of Membrane Materials nano fibrous membrane and preparation method thereof, the nano fibrous membrane is made up of nanofiber and the nanometer branched structure being distributed on nanofiber.The method of the invention simply will spraying (or spraying) technology and electrostatic spinning technique synchronization implementation, joint Membrane Materials nano fibrous membrane of the preparation with ultra-hydrophobicity.Preparation method of the present invention is simple, process is easily controllable, preparation process that need not be complicated and expensive equipment for after-treatment, prepared nano fibrous membrane voidage is high, not only film surface has uniform, excellent super-hydrophobicity, also ensure that its internal each layer all has a super-hydrophobicity by the plane that nanofiber is constituted, therefore the anti-wettability of film can be greatly enhanced, effectively solve the problem that membrane flux is low, be easy to wetting.
Description
Technical field
The invention belongs to Membrane Materials field, it is related to a kind of Membrane Materials nano fibrous membrane and preparation method thereof, more particularly to a kind of Membrane Materials nano fibrous membrane with super-hydrophobic ability and preparation method thereof.
Background technology
Membrane Materials are a kind of a kind of emerging liquid separation technologies that Conventional espresso technique is combined with membrane separation technique, it drives vapor to be condensed in low temperature side through hydrophobic film using the steam pressure difference that the temperature difference that film two is surveyed is produced, and the water and nonvolatile element at material liquid end are trapped, realize that material is separated with this.Due to there is high salt-stopping rate, can have huge application potential in fields such as highly concentrated saline treatment, desalinizations using low-grade energy and used heat.
How effectively, simply one big problem of current influence film distillation technology large-scale application is the hydrophily leakage of film, prepare the hydrophobicity with stabilization, and the Membrane Materials film of even super-hydrophobicity is the study hotspot in current Membrane Materials field.It is thought that if static contact angle of the water on film surface is more than or equal to 150 °, roll angle is less than 10 °, then the film has super-hydrophobicity.
The product film for Membrane Materials of production is not quantified also in the market, the current preparation method appeared in the newspapers is mostly first to prepare porous hydrophobic membrane, then modifying super hydrophobicity is carried out on the surface of perforated membrane again, the preparation method of wherein perforated membrane has traditional phase inversion, sintering process, method of electrostatic spinning etc., and in these methods, method of electrostatic spinning can prepare the nano fibrous membrane that porosity is up to more than 80%, and pore-size distribution is easy to regulation and control.The method such as the method for modifying super hydrophobicity has electrochemical deposition, chemical vapor deposition, template and ion is modifies.These Membrane Materials preparation methods need more complicated process step or special processing equipment mostly, the hydrophobic membrane that these are modified by surface simultaneously, its super-hydrophobicity is only limited to the surface of film, when by prolonged operation, or in the case where hydraulic pressure increases, the surface that water can penetrate progressively through film soaks the internal layer of film, once the top layer of film and internal layer are all wetted, not only the porosity of film can decline, and the temperature difference of film both sides can also be reduced, flux depression even hydrophily is caused to leak, so that it cannot be guaranteed that the long-time steady operation of Membrane Materials process.
CN 103263856A disclose a kind of preparation method of Membrane Materials electrostatic spinning hydrophobic nanofiber perforated membrane, including：Hydrophobic function polymeric material is dissolved in solvent, the polymer spinning solution of 1~35wt% is obtained, electrostatic spinning is carried out, hydrophobic nanofiber perforated membrane is obtained, then is heat-treated, obtain final product Membrane Materials electrostatic spinning hydrophobic nanofiber perforated membrane.But the hydrophobic nanofiber perforated membrane that the method is prepared remains the problem of flux depression even hydrophily leakage in During Process of Long-term Operation.
The content of the invention
The step of for Membrane Materials preparation method in the prior art, is complicated, equipment is special, the membrane flux of prepared film is undesirable, film hydrophobic performance is unstable and it cannot be guaranteed that the problems such as the operation steady in a long-term of Membrane Materials process, the invention provides a kind of Membrane Materials nano fibrous membrane with ultra-hydrophobicity and preparation method thereof.Of the invention simply to spray (or spraying) technology and electrostatic spinning technique synchronization implementation, joint prepares the Membrane Materials nano fibrous membrane with ultra-hydrophobicity.
The preparation method that the present invention is provided, its equipment requirement is low, and process is simple, and controllability is strong, can effectively prepare, the high performance membrane distillation nano fibrous membrane of surface and internal layer super-hydrophobicity all with stabilization high with porosity.
It is that, up to this purpose, the present invention uses following technical scheme：
In a first aspect, the invention provides a kind of Membrane Materials nano fibrous membrane, the nano fibrous membrane is by nanofiber and is distributed in the nanometer branched structure of nanofiber surface and constitutes；The nanometer branched structure is made up of nano-particle.
The nanometer branched structure composition is uniformly scattered in nanofiber surface.
Preferably, the nano-particle be nano silicon, nano titanium oxide, nano zine oxide, nanometer di-iron trioxide, Nano Silver, nano-titanium, nano-calcium carbonate or nano-sized clay in any one or at least two combination；The combination is typical but non-limiting examples have：The combination of nano silicon and nano titanium oxide, the combination of nano zine oxide and nanometer di-iron trioxide, the combination of Nano Silver, nano-titanium and nano-calcium carbonate, the combination of nano-titanium, nano-calcium carbonate and nano-sized clay, the combination of nano silicon, nano titanium oxide, nano zine oxide, nanometer di-iron trioxide, Nano Silver and nano-titanium, combination of nano silicon, nano titanium oxide, nano zine oxide, nanometer di-iron trioxide, Nano Silver, nano-titanium, nano-calcium carbonate and nano-sized clay etc..
Used as preferred scheme of the invention, the nanofiber is made up of hydrophobic polymer.
Preferably, the hydrophobic polymer be Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene, polystyrene, polypropylene, polypropylene or polyethylene in any one or at least two combination；The combination is typical but non-limiting examples have：The combination of Kynoar and polytetrafluoroethylene (PTFE), the combination of Kynoar-hexafluoropropene and polystyrene, the combination of polypropylene, polypropylene and polyethylene, the combination of Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene and polystyrene, combination of Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoropropene, polystyrene, polypropylene, polypropylene and polyethylene etc..
As preferred scheme of the invention, the porosity of the nano fibrous membrane is 70~90%, such as 70%, 75%, 80%, 85% or 90% etc., static contact angle is 150~160 °, such as 150 °, 153 °, 155 °, 157 ° or 160 ° etc., and roll angle is 3~10 °, such as 3 °, 4 °, 5 °, 6 °, 7 °, 8 °, 9 ° or 10 ° etc., the porosity of more preferably described nano fibrous membrane is 80~90%, and static contact angle is 155~160 °, and roll angle is 3~7 °.
Second aspect, the invention provides the preparation method of above-mentioned Membrane Materials nano fibrous membrane, the described method comprises the following steps：
(1) hydrophobic polymer is dissolved in organic matter solvent and is made electrostatic spinning liquid；
(2) nano-particle is scattered in nano-particle dispersant and is made spraying or spray liquid；
(3) electrostatic spinning liquid is drawn into silk with electrostatic spinning apparatus and is collected on receiver, while preparing nano fibrous membrane to spraying or spray liquid is sprayed on receiver with spraying or sprayer unit.
Wherein, electrostatic spinning liquid is drawn into silk with electrostatic spinning apparatus and is collected on the receiver of ground connection.
Used as preferred scheme of the invention, the spraying or spray liquid and the usage ratio of electrostatic spinning liquid are 1:(1~20), such as 1:1、1:2、1:4、1:6、1:8、1:10、1:12、1:14、1:16、1:18 or 1:20 etc..If electrostatic spinning liquid is with the usage ratio of spraying or spray liquid more than this scope, it will the hydrophobicity and porosity of influence film.
Preferably, hydrophobic polymer is made electrostatic spinning liquid by weight portion meter with organic matter solvent by consisting of in step (1)：
10~30 parts of hydrophobic polymer
70~90 parts of organic matter solvent；
Wherein, the weight portion of hydrophobic polymer can be 10 parts, 13 parts, 15 parts, 17 parts, 20 parts, 23 parts, 25 parts, 27 parts or 30 parts etc.；The weight portion of organic matter solvent can be 70 parts, 73 parts, 75 parts, 77 parts, 80 parts, 83 parts, 85 parts, 87 parts or 90 parts etc..
Preferably, hydrophobic polymer is made electrostatic spinning liquid by weight portion meter with organic matter solvent by consisting of in step (1)：
20~25 parts of hydrophobic polymer
75~80 parts of organic matter solvent.
Preferably, the organic solvent be dimethylformamide, dimethylacetylamide, methyl pyrrolidone, tetrahydrofuran, acetone or dimethyl sulfoxide (DMSO) in any one or at least two combination；The combination is typical but non-limiting examples have：The combination of dimethylformamide and dimethylacetylamide, the combination of methyl pyrrolidone, tetrahydrofuran and acetone, the combination of methyl pyrrolidone, tetrahydrofuran, acetone and dimethyl sulfoxide (DMSO), the combination of dimethylformamide, dimethylacetylamide, methyl pyrrolidone and tetrahydrofuran, combination of dimethylformamide, dimethylacetylamide, methyl pyrrolidone, tetrahydrofuran, acetone and dimethyl sulfoxide (DMSO) etc..
Preferably, nano-particle is made spraying or spray liquid by weight portion meter with nano-particle dispersant by consisting of in step (2)：
1~20 part of nano-particle
80~99 parts of nano-particle dispersant；
Wherein, the weight portion of nano-particle can be 1 part, 3 parts, 5 parts, 7 parts, 10 parts, 13 parts, 15,17 parts or 20 parts etc.；The weight portion of nano-particle dispersant can be 80 parts, 83 parts, 85 parts, 87 parts, 90 parts, 93 parts, 95 parts, 97 parts or 99 parts etc..
Preferably, nano-particle is made spraying or spray liquid by weight portion meter with nano-particle dispersant by consisting of in step (2)：
5~15 parts of nano-particle
85~95 parts of nano-particle dispersant.
Preferably, the nano-dispersing agent be acetone, ethanol, dimethylformamide, dimethylacetylamide, methyl pyrrolidone, tetrahydrofuran or dimethyl sulfoxide (DMSO) in any one or at least two combination；The combination is typical but non-limiting examples have：The combination of acetone and ethanol, the combination of ethanol, dimethylformamide and dimethylacetylamide, the combination of methyl pyrrolidone, tetrahydrofuran, acetone and dimethyl sulfoxide (DMSO), the combination of acetone, ethanol, dimethylformamide, dimethylacetylamide and methyl pyrrolidone, combination of acetone, ethanol, dimethylformamide, dimethylacetylamide, methyl pyrrolidone, tetrahydrofuran and dimethyl sulfoxide (DMSO) etc..
As preferred scheme of the invention, electrostatic spinning liquid is drawn into the spinning voltage of silk for 8~20kV with electrostatic spinning apparatus in step (3), such as 8kV, 10kV, 12kV, 14kV, 16kV, 18kV or 20kV etc..
Preferably, the reception distance of the receiver that electrostatic spinning liquid is drawn into silk and is collected in during receiver with electrostatic spinning apparatus in step (3) is 10~30cm, such as 10cm, 13cm, 15cm, 17cm, 20cm, 23cm, 25cm, 27cm or 30cm etc..
Used as preferred scheme of the invention, the middle spraying of step (3) or sprayer unit are 5~25cm, such as 5cm, 7cm, 10cm, 13cm, 15cm, 17cm, 20cm, 23cm or 25cm to the jet length of spraying or spray liquid is sprayed on receiver.The nanostructured skewness if the jet length is too small, the structure of film can be injected spraying or spray liquid destruction；If the jet length is excessive, nanostructured combines insecure and injection spraying or spray liquid in nanometer film and can not be received by the receiver completely.
Used as preferred scheme of the invention, spraying or sprayer unit in step (3) are any one in aerial spraying device, electrostatic spraying apparatus or electrostatic atomizer.
As preferred scheme of the invention, the described method comprises the following steps：
(1) hydrophobic polymer is dissolved in organic matter solvent and is made electrostatic spinning liquid；
(2) nano-particle is scattered in nano-particle dispersant and is made spraying or spray liquid；
(3) it is 1 by spraying or spray liquid and the usage ratio of electrostatic spinning liquid:(1~20), under conditions of spinning voltage is 8~20kV, electrostatic spinning liquid is drawn into silk with electrostatic spinning apparatus and is collected on receiver, the reception distance of receiver is 10~30cm, simultaneously with spraying or sprayer unit to injection spraying or spray liquid on receiver, its jet length is 5~25cm, prepares nano fibrous membrane.
Compared with prior art, the invention has the advantages that：
(1) hydrophobic performance of the Membrane Materials nano fibrous membrane prepared by the method for the invention is excellent, and, up to 150~160 °, roll angle can as little as in 3~10 °, while the porosity of film may be up to 80~90% for contact angle.
(2) present invention will spray (or spraying) technology and electrostatic spinning technique synchronization implementation, it is prepared by the two joint, not only ensure that the nano fibrous membrane for obtaining has uniform ultra-hydrophobicity, also ensure that its internal each layer all has super-hydrophobicity by the plane that nanofiber is constituted, liquid is prevented further to be permeated in film after the surface of film is wetted, it is ensured that the operation of Membrane Materials process stabilization.
(3) preparation method of the present invention is simple, and process is easily controllable, it is not necessary to complicated preparation process and the equipment for after-treatment of costliness.
Brief description of the drawings
Fig. 1 is the schematic device of preparation method use in the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph and contact angle schematic diagram of the Membrane Materials nano fibrous membrane prepared in the embodiment of the present invention 1；
Wherein：1- electrostatic spinning solutions, 2- electrostatic spinning apparatus, 3- electrostatic spinning power supplys, 4- reception devices, 5- electrostatic spray power supplys, 6- electrostatic atomizers, 7- electrostatic spray films.
Specific embodiment
Below in conjunction with several specific embodiments; exemplary illustration and help further understand the present invention; but embodiment detail is merely to the explanation present invention; whole technical schemes under present inventive concept are not represented; therefore should not be construed as the technical scheme total to the present invention to limit, some are changed in technical staff, the unsubstantiality without departing from inventive concept; for example simply changed with the technical characteristic with same or similar technique effect or replaced, belong to the scope of the present invention.
Embodiment 1：
The present embodiment carries out the preparation of Membrane Materials nano fibrous membrane using device as shown in Figure 1, described device includes electrostatic spinning solution 1, electrostatic spinning apparatus 2, electrostatic spinning power supply 3, reception device 4, electrostatic spray power supply 5, electrostatic atomizer 6 and electrostatic spray film 7.
Preparation method is as follows：
(1) electrostatic spinning liquid is configured in 20 parts of Kynoar being dissolved in into 24 parts of acetone and 56 parts of dimethylacetylamides；
(2) 5 parts of hydrophobic nano-silicas are dispersed in 95 parts of dimethylformamides and are configured to spray liquid；
(3) electrostatic spinning liquid for preparing step (1) loads electrostatic spinning apparatus, and the spray liquid that step (2) is prepared loads electrostatic atomizer, and the spray liquid is 1 with the usage ratio of electrostatic spinning liquid:10, it is 1.5mlh to set electrostatic spinning liquid sample introduction flow velocity-1, it is 0.5mlh to set electrostatic spray film sample introduction flow velocity-1；Spinning voltage as 8kV is set, the reception distance of receiver is 10cm, and electrostatic atomizer is 5cm with the jet length of receiver, and the voltage of electrostatic atomizer is 11kV.Start electrostatic spinning apparatus and electrostatic atomizer, the nano fibrous membrane for just having ultra-hydrophobicity is obtained after synchronization combining spraying and spinning 3h.It is used for subsequent characterizations and Membrane Materials application after prepared film is dried into 24h in 40 DEG C of baking ovens, its scanning electron microscope (SEM) photograph is as shown in Figure 2.
The porosity of obtained nano fibrous membrane is 85%, and static contact angle is 160 °, and roll angle is 3 °, stable by the Membrane Materials procedural test of 150 hours, hydrophilic osmotic does not occur.
Embodiment 2：
The present embodiment is adopted and prepare with the following method Membrane Materials nano fibrous membrane：
(1) 25 parts of Kynoar are dissolved in 75 parts of dimethylacetylamides and are configured to electrostatic spinning liquid；
(2) 10 parts of hydrophobic nano-silicas are dispersed in 90 parts of dimethylformamides and are configured to spray coating liquor；
(3) electrostatic spinning liquid for preparing step (1) loads electrostatic spinning apparatus, and the spray coating liquor that step (2) is prepared loads aerial spraying device, and the spray coating liquor is 1 with the usage ratio of electrostatic spinning liquid:2, it is 2.0mlh to set electrostatic spinning liquid sample introduction flow velocity-1, setting air spray equipment sample introduction flow velocity is 0.8mlh-1；Spinning voltage as 10kV is set, the reception distance of receiver is 15cm, and aerial spraying device is 10cm with the jet length of receiver.Start electrostatic spinning apparatus and aerial spraying device, the nano fibrous membrane for just having ultra-hydrophobicity is obtained after synchronization combining spraying and spinning 3h.It is used for subsequent characterizations and Membrane Materials application after prepared film is dried into 24h in 40 DEG C of baking ovens.
The porosity of obtained nano fibrous membrane is 87%, and static contact angle is 155 °, and roll angle is 5 °, stable by the Membrane Materials procedural test of 150 hours, hydrophilic osmotic does not occur.
Embodiment 3：
The present embodiment is adopted and prepare with the following method Membrane Materials nano fibrous membrane：
(1) 20 parts of Kynoar are dissolved in 85 parts of dimethylacetylamides and are configured to electrostatic spinning liquid；
(2) 15 parts of hydrophobic nano-silicas are dispersed in 90 parts of dimethylformamides and are configured to spray coating liquor；
(3) electrostatic spinning liquid for preparing step (1) loads electrostatic spinning apparatus, and the spray coating liquor that step (2) is prepared loads electrostatic spraying apparatus, and the spray coating liquor is 1 with the usage ratio of electrostatic spinning liquid:20, it is 2.0mlh to set electrostatic spinning liquid sample introduction flow velocity-1, it is 0.8mlh to set electrostatic masking liquid sample introduction flow velocity-1；Spinning voltage as 15kV is set, the reception distance of receiver is 20cm, and electrostatic spraying apparatus are 20cm with the jet length of receiver, and the voltage of electrostatic spraying apparatus is 15kV.Start electrostatic spinning apparatus and electrostatic spraying apparatus, the nano fibrous membrane for just having ultra-hydrophobicity is obtained after synchronization combining spraying and spinning 3h.It is used for subsequent characterizations and Membrane Materials application after prepared film is dried into 24h in 40 DEG C of baking ovens.
The porosity of obtained nano fibrous membrane is 85%, and static contact angle is 155 °, and roll angle is 5 °, stable by the Membrane Materials procedural test of 150 hours, hydrophilic osmotic does not occur.
Embodiment 4：
The present embodiment is adopted and prepare with the following method Membrane Materials nano fibrous membrane：
(1) 30 parts of polytetrafluoroethylene (PTFE) are dissolved in 75 parts of tetrahydrofurans and are configured to electrostatic spinning liquid；
(2) 1 part of hydrophobic nano zinc oxide is dispersed in 99 parts of methyl pyrrolidones and is configured to spray liquid；
(3) electrostatic spinning liquid for preparing step (1) loads electrostatic spinning apparatus, and the spray liquid that step (2) is prepared loads electrostatic atomizer, and the spray liquid is 1 with the usage ratio of electrostatic spinning liquid:10, it is 2.0mlh to set electrostatic spinning liquid sample introduction flow velocity-1, it is 0.8mlh to set electrostatic spray film sample introduction flow velocity-1；Spinning voltage as 20kV is set, the reception distance of receiver is 30cm, and electrostatic atomizer is 25cm with the jet length of receiver, and the voltage of electrostatic atomizer is 18kV.Start electrostatic spinning apparatus and electrostatic atomizer, the nano fibrous membrane for just having ultra-hydrophobicity is obtained after synchronization combining spraying and spinning 3h.It is used for subsequent characterizations and Membrane Materials application after prepared film is dried into 24h in 40 DEG C of baking ovens.
The porosity of obtained nano fibrous membrane is 85%, and static contact angle is 155 °, and roll angle is 5 °, stable by more than 150 Membrane Materials procedural test, hydrophilic osmotic does not occur.
Embodiment 5：
Electrostatic spinning liquid is configured to except 10 parts of Kynoar-hexafluoropropenes being dissolved in 90 parts of methyl pyrrolidones in step (1)；Be dispersed in for 15 parts of hydrophobic nano-titanium dioxides spray liquid be configured in 85 parts of acetone by step (2), and spray liquid and the usage ratio of electrostatic spinning liquid are 1 in step (3):Outside 1, other steps are in the same manner as in Example 1 with material amounts.
The porosity of obtained nano fibrous membrane is 86%, and static contact angle is 160 °, and roll angle is 4 °, stable by the Membrane Materials procedural test of 150 hours, hydrophilic osmotic does not occur.
Embodiment 6：
Electrostatic spinning liquid is configured to except 10 parts of polystyrene being dissolved in 90 parts of dimethyl sulfoxide (DMSO)s in step (1)；Be dispersed in 20 parts of hydrophobic nanoscale calcium carbonates in 80 parts of dimethyl sulfoxide (DMSO)s and be configured to outside spray liquid by step (2), and other steps are in the same manner as in Example 1 with material amounts.
The porosity of obtained nano fibrous membrane is 85%, and static contact angle is 155 °, and roll angle is 6 °, stable by the Membrane Materials procedural test of 150 hours, hydrophilic osmotic does not occur.
Comparative example 1：
The comparative example 1 prepares nano fibrous membrane using electrostatic spinning combination Technology for Heating Processing, electrospinning device is in the same manner as in Example 1, Technology for Heating Processing is identical with CN 103263856A, the porosity of obtained nano fibrous membrane is 60%, static contact angle is 130 °, roll angle is 60 °, is hydrophilic osmotic by the Membrane Materials procedural test of 35 hours, and its hydrophobic performance is all much not enough compared with the present invention is implemented with anti-wettability, operation stability.
Comparative example 2：
Carried out when electrostatic spinning is different with spraying or spraying process in the comparative example, first carry out electrostatic spinning, then sprayed again or spraying process, the porosity of obtained nano fibrous membrane is 88%, static contact angle is 158 °, roll angle is 5 °, but is hydrophilic osmotic occur by the Membrane Materials procedural test of 70 hours.
The result of integrated embodiment 1-6 and comparative example 1-2 can be seen that, the porosity of the Membrane Materials nano fibrous membrane prepared by the method for the invention is high, up to 80~90%, hydrophobicity is excellent, and static contact angle is up to 150~160 °, roll angle can as little as be 3~10 °, nanofiber surface is firmly combined with nanometer branched structure, film is had the hydrophobic performance of stabilization, crosses the Membrane Materials procedural test of 150 hours, it is stable, there is not hydrophilic osmotic.The present invention will spray (or spraying) technology and electrostatic spinning technique synchronization implementation, it is prepared by the two joint, not only ensure that the nano fibrous membrane surface for obtaining has uniform ultra-hydrophobicity, also ensure that its internal each layer all has super-hydrophobicity by the plane that nanofiber is constituted, therefore the anti-wettability of film can be greatly enhanced, so as to ensure the operation steady in a long-term of Membrane Materials process.Preparation method of the present invention is simple, and process is easily controllable, it is not necessary to complicated preparation process and the equipment for after-treatment of costliness.
Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the invention is not limited in above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention, addition, the selection of concrete mode to the equivalence replacement and auxiliary element of each raw material of product of the present invention etc., all fall within protection scope of the present invention and it is open within the scope of.
Claims (10)
1. a kind of Membrane Materials nano fibrous membrane, it is characterised in that the nano fibrous membrane by nanofiber with
And it is distributed in the nanometer branched structure composition of nanofiber surface.
2. Membrane Materials nano fibrous membrane according to claim 1, it is characterised in that the Nanowire
Dimension is made up of hydrophobic polymer；
Preferably, the hydrophobic polymer is Kynoar, polytetrafluoroethylene (PTFE), Kynoar-hexafluoro third
In alkene, polystyrene, polypropylene, polypropylene or polyethylene any one or at least two combination.
3. the Membrane Materials nano fibrous membrane according to claim 1-2, it is characterised in that the nanometer
Branched structure is made up of nano-particle；
Preferably, the nano-particle is nano silicon, nano titanium oxide, nano zine oxide, receives
In rice di-iron trioxide, Nano Silver, nano-titanium, nano-calcium carbonate or nano-sized clay any one or at least
Two kinds of combination.
4. the Membrane Materials nano fibrous membrane according to claim any one of 1-3, it is characterised in that institute
It is 70~90% to state the porosity of nano fibrous membrane, and static contact angle is 150~160 °, and roll angle is 3~10 °；
Preferably, the porosity of the nano fibrous membrane is 80~90%, and static contact angle is 155~160 °,
Roll angle is 3~7 °.
5. the preparation method of the Membrane Materials nano fibrous membrane according to claim any one of 1-4, it is special
Levy and be, the described method comprises the following steps：
(1) hydrophobic polymer is dissolved in organic matter solvent and is made electrostatic spinning liquid；
(2) nano-particle is scattered in nano-particle dispersant and is made spraying or spray liquid；
(3) electrostatic spinning liquid is drawn into silk with electrostatic spinning apparatus and is collected on receiver, while with spray
Apply or sprayer unit is to spraying or spray liquid is sprayed on receiver, prepare nano fibrous membrane.
6. preparation method according to claim 5, it is characterised in that the spraying or spray liquid with it is quiet
The usage ratio of Electrospun liquid is 1:(1~20)；
Preferably, hydrophobic polymer is made up of weight portion meter with organic matter solvent by consisting of in step (1)
Electrostatic spinning liquid：
10~30 parts of hydrophobic polymer
70~90 parts of organic matter solvent；
Preferably, hydrophobic polymer is made up of weight portion meter with organic matter solvent by consisting of in step (1)
Electrostatic spinning liquid：
20~25 parts of hydrophobic polymer
75~80 parts of organic matter solvent；
Preferably, the organic solvent be dimethylformamide, dimethylacetylamide, methyl pyrrolidone,
In tetrahydrofuran, acetone or dimethyl sulfoxide (DMSO) any one or at least two combination；
Preferably, nano-particle presses consisting of system with nano-particle dispersant by weight portion meter in step (2)
Into spraying or spray liquid：
1~20 part of nano-particle
80~99 parts of nano-particle dispersant；
Preferably, nano-particle presses consisting of system with nano-particle dispersant by weight portion meter in step (2)
Into spraying or spray liquid：
5~15 parts of nano-particle
85~95 parts of nano-particle dispersant；
Preferably, the nano-dispersing agent be acetone, ethanol, dimethylformamide, dimethylacetylamide,
In methyl pyrrolidone, tetrahydrofuran or dimethyl sulfoxide (DMSO) any one or at least two combination.
7. the preparation method according to claim 5 or 6, it is characterised in that with quiet in step (3)
The spinning voltage that electrostatic spinning liquid is drawn into silk is 8~20kV by electric spinning device；
Preferably, with electrostatic spinning apparatus electrostatic spinning liquid is drawn into silk in step (3) and is collected in reception
The reception distance of the receiver during device is 10~30cm.
8. the preparation method according to claim 5 or 6, it is characterised in that the middle spray of step (3)
Apply or sprayer unit is 5~25cm to the jet length of spraying or spray liquid is sprayed on receiver.
9. the preparation method according to claim any one of 5-8, it is characterised in that in step (3)
Spraying or sprayer unit be aerial spraying device, electrostatic spraying apparatus or electrostatic atomizer in any one.
10. the preparation method according to claim any one of 5-9, it is characterised in that methods described bag
Include following steps：
(1) hydrophobic polymer is dissolved in organic matter solvent and is made electrostatic spinning liquid；
(2) nano-particle is scattered in nano-particle dispersant and is made spraying or spray liquid；
(3) it is 1 by spraying or spray liquid and the usage ratio of electrostatic spinning liquid:(1~20), be in spinning voltage
Under conditions of 8~20kV, electrostatic spinning liquid is drawn into silk with electrostatic spinning apparatus and is collected on receiver,
Receiver reception distance be 10~30cm, while with spraying or sprayer unit on receiver spray spraying or
Spray liquid, its jet length is 5~25cm, prepares nano fibrous membrane.
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