CN109593220A - A kind of preparation method of hydrophily ordered porous membrane material - Google Patents
A kind of preparation method of hydrophily ordered porous membrane material Download PDFInfo
- Publication number
- CN109593220A CN109593220A CN201811550708.9A CN201811550708A CN109593220A CN 109593220 A CN109593220 A CN 109593220A CN 201811550708 A CN201811550708 A CN 201811550708A CN 109593220 A CN109593220 A CN 109593220A
- Authority
- CN
- China
- Prior art keywords
- hydrophily
- porous membrane
- ordered porous
- membrane material
- sol evenning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a kind of preparation methods of hydrophily ordered porous membrane material, the following steps are included: S1: polymer and cationic surfactant are dissolved in organic solvent, it is configured to solution, the mass ratio of the cationic surfactant and polymer is 0.0015 ~ 0.1；S2: prepared solution is added drop-wise to substrate surface, and substrate is placed on the rotating platform of sol evenning machine；S3: being passed through air into sol evenning machine, and air stream is made to blow to solution, controls the air speed being passed through, the temperature and relative humidity of sol evenning machine chamber interior, while starting sol evenning machine and controlling its revolving speed；S4: after organic solvent all volatilization, stop sol evenning machine rotation, take out substrate and obtain hydrophily ordered porous membrane material.The present invention prepares the hydrophily ordered porous thin-film material of different pore size by simple adjustment preparation parameter, and easy to operate, preparation cost is low.
Description
Technical field
The present invention relates to polymer porous membrane Material Fields, more particularly to a kind of hydrophily ordered porous membrane material
Preparation method.
Background technique
Ordered porous polymer thin-film material refers to the high score for the micron or nano grade pore structure that surface has height regular
Sub- material.The pore structure of these high-sequentials imparts its big specific surface area and spatial volume, low-density, unique optical
The features such as energy, superficial roughness, thus in biological medicine, organizational project, photoelectric material, self-cleaning material, super hydrophobic surface etc.
Field has a wide range of applications.
From 1994Et al. prepare first case polymer using breathing pattern method (Breath figure) and have
Since sequence porous membrane, this method prepares ordered porous polymer thin-film material most because its simple, efficient feature has become
Common method.
The polymer for being used to prepare porous film material needs to have good film forming characteristics, therefore these polymer are usual
It is all hydrophobic.Further, since the presence of film surface pore structure significantly increases the surface roughness of material.Therefore,
The surface of most polymer thin-film materials is all in hydrophobicity, and aqueous solution enters less than in the micropore on surface.However, porous thin
The many of film but require surface in hydrophily using (such as biological medicine, organizational project etc.), and aqueous solution is needed to enter these
In micropore.
In order to improve the surface wettability of porous film material, a kind of method is that ultraviolet lighting is utilized after preparing material
Method introduce on the surface of the material hydrophilic group (Lei Li, Caikang Chen, Jian Li, Aijuan Zhang,
Xinyu Liu, Bin Xu, Shubin Gao, Guanghui Jin and Zhi Ma, Robust and hydrophilic
polymeric films with honeycomb pattern and their cell scaffold applications,
J.Mater.Chem.,2009,19,2789–2796；Multiple-periodic structures of self-
organized honeycomb-patterned films and polymer nanoparticles hybrids,Hiroshi
Yabu,Kouta Inoue,Masatsugu Shimomura,Colloids and Surfaces A:
Physicochem.Eng.Aspects,2006,284–285,301–304).Another method is the complicated stimuli responsive of synthesis
Property polymer, and porous membrane is prepared with this.After film preparation is good, then by the environmental stimulus factor (such as temperature, pH,
CO2, voltage etc.) hydrophily that changes the certain groups in surface, into face realize film surface it is hydrophilic promoted (Hongyao Yin,
Anne-Laure Bulteau,Yujun Feng,Laurent Billon,CO2-Induced Tunable and
Reversible Surface Wettability of Honeycomb Structured Porous Films for Cell
Adhesion, Adv.Mater.Interfaces, 2016,201500623；Liping Heng,Jie Li,Muchen Li,
Dongliang Tian,Li-Zhen Fan,Lei Jiang,and Ben Zhong Tang,Ordered Honeycomb
Structure Surface Generated by Breath Figures for Liquid Reprography,Advanced
Functional Materials, 2014,24,7241-7248；Pierre Escal′,Wim Van Camp,Filip Du
Prez,Laurent Rubatat,Laurent Billon,and Maud Save,Highly structured pH-
responsive honeycomb films by a combination of a breath figure process and in
situ thermolysis of a polystyrene-block-poly(ethoxy ethyl acrylate)precursor,
Polym.Chem.,2013,4,4710).However, the above method or Structure of need is special, synthesis is complicated polymer or
Complicated post-processing is needed, is not only difficult to operate, but also significantly increase cost.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of preparations of hydrophily ordered porous membrane material
Method can prepare the hydrophily ordered porous thin-film material of different pore size by simple adjustment preparation parameter.
The purpose of the present invention is achieved through the following technical solutions: a kind of preparation of hydrophily ordered porous membrane material
Method, comprising the following steps:
S1: polymer and cationic surfactant are dissolved in organic solvent, are configured to solution, the cationic surface
The mass ratio of activating agent and polymer is 0.0015~0.1；
S2: prepared solution is added drop-wise to substrate surface, and substrate is placed on the rotating platform of sol evenning machine；
S3: being passed through air into sol evenning machine, and air stream is made to blow to solution, controls the air speed being passed through, sol evenning machine chamber
Internal temperature and relative humidity, while starting sol evenning machine and controlling its revolving speed；
Using organic solvent in polymer solution under the brushing of wet air, it can quickly volatilize and be produced in solution surface
Raw low temperature interface, makes the water vapour in air condense to form micron or nanoscale drop, the hydrophilic radical in solution passes through
Hydrogen bond action stablizes the arrangement of water droplet and formation rule.
S4: after organic solvent all volatilization, stop sol evenning machine rotation, take out substrate and obtain hydrophily ordered porous membrane
Material.
The pore structure of ordered arrangement, in this process, ordered arrangement have just been obtained after solvent and water droplet all volatilize completely
Condensing drip acted in effect as the template of pore structure.
The polymer is polylactic acid, and raw material sources are abundant and can regenerate, cheap.
The general formula of the cationic surfactant are as follows:
Wherein, the integer that n is 6~14, X are Cl or Br.
The cationic surfactant is dodecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium chloride
Krafft point is low (close to room temperature), can be dissolved in water droplet under room temperature state and quickly volatilize.
The organic solvent is effumability organic solvent, is saved drying time, hydrophily ordered porous membrane molding speed
Degree is fast.
The organic solvent includes one of methylene chloride, chloroform, carbon disulfide, benzene, toluene or a variety of
Combination, low boiling point is easy to volatilize, and raw material is easy to get, at low cost.
Polymer concentration is 10~50mg/mL, the cationic surfactant concentration in the step S1 acquired solution
For 0.05~5.0mg/mL.
Substrate in the step S2 is glass, and compared to silicon wafer, cost is relatively low.
Air stream blows to solution right above solution in the step S3, brushes air uniformly on solution, is formed
More regular drop.
The air speed being passed through in the step S3 is 100~300L/h, and sol evenning machine chamber room temperature is 20~28 DEG C,
Relative humidity is 60%~90%, and the revolving speed of the sol evenning machine is 0~50rpm.
The beneficial effects of the present invention are:
1) the ordered porous thin-film material surface prepared by the present invention is in hydrophily, is without further any processing
Aqueous solution can be made to be directly entered in the micropore on surface, it is easy to operate, step is few.
2) concentration, the concentration of cationic surfactant, polymer that the present invention passes through polymer concentration in adjusting solution
Concentration and the ratio of cationic surfactant concentration, temperature can adjust the aperture of ordered porous thin-film material, pitch of holes,
The parameters such as hole density.
3) polymer and cationic surfactant used in the present invention are commercial prod, cheap, are not necessarily to
Cumbersome synthesis can be obtained.
Detailed description of the invention
Fig. 1 is the scanning electron microscope image of ordered porous membrane obtained in the embodiment of the present invention one；
Fig. 2 is the scanning electron microscope image of ordered porous membrane obtained in the embodiment of the present invention two；
Fig. 3 is the scanning electron microscope image of ordered porous membrane obtained in the embodiment of the present invention three.
Specific embodiment
Below in conjunction with embodiment, technical solution of the present invention is clearly and completely described, it is clear that described
Embodiment is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field
Technical staff's every other embodiment obtained under the premise of not making the creative labor belongs to what the present invention protected
Range.
Embodiment one
S1: polylactic acid and dodecyl trimethyl ammonium chloride, prepared polymer and dodecyl are dissolved in chloroform
Trimethyl ammonia chloride ammonium concentration is respectively the solution of 20mg/mL and 0.2mg/mL；
S2: the 40 above-mentioned solution of μ L are pipetted in substrate of glass, and are placed on the rotating platform of sol evenning machine；
S3: being passed through the humid air of the test tube by filling water with the rate of 100L/h, and controls sol evenning machine chamber interior temperature
Degree is 24 DEG C, relative humidity 80%, while adjusting sol evenning machine and being started with the revolving speed of 20rpm.
S4: solvent all volatilizees after about 2min, stops sol evenning machine rotation, takes out substrate and obtains hydrophily ordered porous membrane.
Scanning electron microscope observation (attached drawing 1) shows that the surface of the perforated membrane all distributed orderly aligned micropore
Structure, micro-pore diameter are about 2.8 μm, and micropore is in hexangle type ordered arrangement.
Water droplet contact angle test is carried out to it using contact angle measurement.Water droplet contact angle test shows the perforated membrane
Contact angle is 46 °, shows that the perforated membrane is hydrophily.
Embodiment two
S1: polylactic acid and dodecyl trimethyl ammonium chloride, prepared polymer and dodecyl are dissolved in chloroform
Trimethyl ammonia chloride ammonium concentration is respectively the solution of 20mg/mL and 1mg/mL；
S2: the 40 above-mentioned solution of μ L are pipetted in substrate of glass, and are placed on the rotating platform of sol evenning machine；
S3: being passed through the humid air of the test tube by filling water with the rate of 100L/h, and controls sol evenning machine chamber interior temperature
Degree is 24 DEG C, relative humidity 80%, while adjusting sol evenning machine and being started with the revolving speed of 20rpm.
S4: solvent all volatilizees after about 2min, stops sol evenning machine rotation, takes out substrate and obtains hydrophily ordered porous membrane.
Scanning electron microscope observation (attached drawing 2) shows that the surface of the perforated membrane all distributed orderly aligned micropore
Structure, micro-pore diameter are about 6.4 μm, and micropore is in hexangle type ordered arrangement.
Water droplet contact angle test is carried out to it using contact angle measurement.Water droplet contact angle test shows the perforated membrane
Contact angle is 48 °, shows that the perforated membrane is hydrophily.
Embodiment three
S1: polylactic acid and dodecyl trimethyl ammonium chloride, prepared polymer and dodecyl are dissolved in chloroform
Trimethyl ammonia chloride ammonium concentration is respectively the solution of 30mg/mL and 0.5mg/mL；
S2: the 80 above-mentioned solution of μ L are pipetted in substrate of glass, and are placed on the rotating platform of sol evenning machine；
S3: being passed through the humid air of the test tube by filling water with the rate of 100L/h, and controls sol evenning machine chamber interior temperature
Degree is 26 DEG C, relative humidity 80%, while adjusting sol evenning machine and being started with the revolving speed of 20rpm.
S4: solvent all volatilizees after about 2min, stops sol evenning machine rotation, takes out substrate and obtains hydrophily ordered porous membrane.
Scanning electron microscope observation (attached drawing 3) shows that the surface of the perforated membrane all distributed orderly aligned micropore
Structure, micro-pore diameter are about 5.2 μm, and micropore is in hexangle type ordered arrangement.
Water droplet contact angle test is carried out to it using contact angle measurement.Water droplet contact angle test shows the perforated membrane
Contact angle is 50 °, shows that the perforated membrane is hydrophily.
Example IV
S1: polylactic acid and cetyl trimethylammonium bromide, prepared polymer and dodecyl are dissolved in chloroform
Trimethyl ammonia chloride ammonium concentration is respectively the solution of 50mg/mL and 5mg/mL；
S2: the 100 above-mentioned solution of μ L are pipetted in silicon wafer substrate, and are placed on the rotating platform of sol evenning machine；
S3: being passed through the humid air of the test tube by filling water with the rate of 300L/h, and controls sol evenning machine chamber interior temperature
Degree is 28 DEG C, relative humidity 90%, while adjusting sol evenning machine and being started with the revolving speed of 50rpm；
S4: solvent all volatilizees after about 2min, stops sol evenning machine rotation, takes out substrate and obtains hydrophily ordered porous membrane.
Embodiment five
S1: polylactic acid and octyltrimethylammonium chloride, prepared polymer and dodecyl front three are dissolved in chloroform
Ammonium chloride concentration is respectively the solution of 10mg/mL and 0.05mg/mL；
S2: the 100 above-mentioned solution of μ L are pipetted in polyester base, and are placed on the rotating platform of sol evenning machine；
S3: being passed through the humid air of the test tube by filling water with the rate of 200L/h, and controls sol evenning machine chamber interior temperature
Degree is 20 DEG C, relative humidity 60%, spin coating machine speed 0rpm.
S4: solvent all volatilizees after about 2min, stops sol evenning machine rotation, takes out substrate and obtains ordered porous membrane.
Embodiment six
S1: polylactic acid and dodecyl trimethyl ammonium bromide, prepared polymer and dodecyl are dissolved in chloroform
Trimethylammonium bromide concentration is respectively the solution of 50mg/mL and 0.3mg/mL；
S2: the 200 above-mentioned solution of μ L are pipetted in substrate of glass, and are placed on the rotating platform of sol evenning machine；
S3: being passed through the humid air of the test tube by filling water with the rate of 300L/h, and controls sol evenning machine chamber interior temperature
Degree is 28 DEG C, relative humidity 80%, while adjusting sol evenning machine and being started with the revolving speed of 40rpm.
S4: solvent all volatilizees after about 2min, stops sol evenning machine rotation, takes out substrate and obtains hydrophily ordered porous membrane.
The above is only a preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein
Form should not be regarded as an exclusion of other examples, and can be used for other combinations, modifications, and environments, and can be at this
In the text contemplated scope, modifications can be made through the above teachings or related fields of technology or knowledge.And those skilled in the art institute into
Capable modifications and changes do not depart from the spirit and scope of the present invention, then all should be in the protection scope of appended claims of the present invention
It is interior.
Claims (10)
1. a kind of preparation method of hydrophily ordered porous membrane material, which comprises the following steps:
S1: polymer and cationic surfactant are dissolved in organic solvent, are configured to solution, the cation surface activating
The mass ratio of agent and polymer is 0.0015~0.1；
S2: prepared solution is added drop-wise to substrate surface, and substrate is placed on the rotating platform of sol evenning machine；
S3: being passed through air into sol evenning machine, and air stream is made to blow to solution, controls the air speed being passed through, sol evenning machine chamber interior
Temperature and relative humidity, while starting sol evenning machine and controlling its revolving speed；
S4: after organic solvent all volatilization, stop sol evenning machine rotation, take out substrate and obtain the ordered porous membrane material of hydrophily
Material.
2. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1, it is characterised in that: described
Polymer is polylactic acid.
3. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1, which is characterized in that the sun
The general formula of ionic surface active agent are as follows:Wherein, the integer that n is 6~14, X are Cl or Br.
4. a kind of preparation method of hydrophily ordered porous membrane material according to claim 3, it is characterised in that: described
Cationic surfactant is dodecyl trimethyl ammonium chloride.
5. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1, it is characterised in that: described
Organic solvent is effumability organic solvent.
6. a kind of preparation method of hydrophily ordered porous membrane material according to claim 5, it is characterised in that: described
Organic solvent includes one of methylene chloride, chloroform, carbon disulfide, benzene, toluene or a variety of combinations.
7. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1, it is characterised in that: the step
Polymer concentration is 10~50mg/mL in rapid S1 acquired solution, and the cationic surfactant concentration is 0.05~5.0mg/
mL。
8. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1, it is characterised in that: the step
Substrate in rapid S2 is glass.
9. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1, it is characterised in that: the step
Air stream blows to solution right above solution in rapid S3.
10. a kind of preparation method of hydrophily ordered porous membrane material according to claim 1 or claim 7, it is characterised in that: institute
The air speed being passed through in the step S3 stated is 100~300L/h, and sol evenning machine chamber room temperature is 20~28 DEG C, and relative humidity is
60%~90%, the revolving speed of the sol evenning machine is 0~50rpm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811550708.9A CN109593220B (en) | 2018-12-18 | 2018-12-18 | Preparation method of hydrophilic ordered porous membrane material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811550708.9A CN109593220B (en) | 2018-12-18 | 2018-12-18 | Preparation method of hydrophilic ordered porous membrane material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109593220A true CN109593220A (en) | 2019-04-09 |
| CN109593220B CN109593220B (en) | 2020-09-29 |
Family
ID=65962683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811550708.9A Active CN109593220B (en) | 2018-12-18 | 2018-12-18 | Preparation method of hydrophilic ordered porous membrane material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109593220B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980045A (en) * | 2021-03-26 | 2021-06-18 | 四川大学 | Redox-responsive ordered porous membrane material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778145A (en) * | 2016-03-24 | 2016-07-20 | 常州时创能源科技有限公司 | Method for preparing large-area orderly porous membrane |
-
2018
- 2018-12-18 CN CN201811550708.9A patent/CN109593220B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105778145A (en) * | 2016-03-24 | 2016-07-20 | 常州时创能源科技有限公司 | Method for preparing large-area orderly porous membrane |
Non-Patent Citations (1)
| Title |
|---|
| 何小维: "《功能性碳水化合物及其应用技术丛书 医药用碳水化合物》", 31 January 2016, 中国轻工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112980045A (en) * | 2021-03-26 | 2021-06-18 | 四川大学 | Redox-responsive ordered porous membrane material and preparation method thereof |
| CN112980045B (en) * | 2021-03-26 | 2023-03-14 | 四川大学 | Redox-responsive ordered porous membrane material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109593220B (en) | 2020-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101270260B (en) | Super-hydrophobic surface coating material and preparation method thereof | |
| Wang et al. | A robust transparent and anti-fingerprint superhydrophobic film | |
| Wang et al. | Reversible superhydrophobic coatings on lifeless and biotic surfaces via dry-painting of aerogel microparticles | |
| CN105217601A (en) | A kind of preparation method with the porous hollow carbon ball of high-specific surface area | |
| CN105860120B (en) | A kind of super-hydrophobic polypropylene film and preparation method thereof | |
| CN105440747A (en) | Super-hydrophobic nanometer coating, manufacturing method and super-hydrophobic nanometer coating object | |
| CN105778145B (en) | The preparation method of large-area ordered porous membrane | |
| KR101122253B1 (en) | The manufacturing method of superhydrophilic and superhydrophobic silica coating layer | |
| Yu et al. | Breath figure fabrication of honeycomb films with small molecules through hydrogen bond mediated self-assembly | |
| CN105858592B (en) | Super-hydrophobic surface formed on basis of dihydrazide derivative molecular gel | |
| CN103937017A (en) | Preparation method of nanopore cellular membrane | |
| Liu et al. | Facile preparation of super-hydrophobic fabrics composed of fibres with microporous or microspherical coatings using the static breath figure method | |
| CN103861471A (en) | Method for synthetizing NaA type molecular sieve membrane in seed crystal aerosol | |
| Tao et al. | Sol–gel preparation of moisture-resistant antireflective coatings from novel hollow silica nanoparticles | |
| CN105085953A (en) | Method for preparing polylactic acid super-hydrophobic membranes by aid of phase separation process | |
| CN109593220A (en) | A kind of preparation method of hydrophily ordered porous membrane material | |
| Zheng et al. | Fabrication of self‐cleaning poly (vinylidene fluoride) membrane with micro/nanoscaled two‐tier roughness | |
| CN105925113B (en) | Waterproof and breathable styrene block copolymer composite coating material and its preparation and use | |
| CN105088538B (en) | A kind of preparation method of hydrophobin coating | |
| CN101157768A (en) | Super-hydrophobic high-density polyethylene film and preparation method thereof | |
| CN109126479B (en) | Silver nanowire-fluorinated ethylene propylene super-hydrophobic porous membrane and preparation method thereof | |
| JPWO2016167285A1 (en) | Structure-controlled metal halide crystals and perovskite compound crystals | |
| CN102838772B (en) | Super-hydrophobic polypropylene film | |
| Chung et al. | Self-assembled perpendicular growth of organic nanoneedles via simple vapor-phase deposition: one-step fabrication of a superhydrophobic surface | |
| CN108841036B (en) | A kind of CO2Responsiveness ordered porous membrane material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |