CN109157928A - A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof - Google Patents
A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof Download PDFInfo
- Publication number
- CN109157928A CN109157928A CN201810996163.8A CN201810996163A CN109157928A CN 109157928 A CN109157928 A CN 109157928A CN 201810996163 A CN201810996163 A CN 201810996163A CN 109157928 A CN109157928 A CN 109157928A
- Authority
- CN
- China
- Prior art keywords
- functionalization graphene
- filter membrane
- functionalization
- high polymer
- nanometer fiber
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
- B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0001—Making filtering elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/56—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of cyclic compounds with one carbon-to-carbon double bond in the side chain
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nonwoven Fabrics (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof, belongs to air cleaning and membrane material preparation technical field.The filter membrane contains high polymer nanometer fiber and functionalization graphene layer, and functionalization graphene layer inserts in inside high polymer nanometer fiber, and the two is mutually overlapping.Preparation method is: the dispersion liquid and Polymer Solution of the functionalization graphene of various concentration is respectively configured, using electrospinning device, two kinds of dispersion liquids are respectively placed in two syringes and carry out spraying spinning, make to form filter membrane in functionalization graphene layer insertion high polymer nanometer fiber.The filter membrane can effectively adsorb NH3、CO、NO2Equal polluted gas, and smog, pollen, PM in energy high efficiency filter air2.5Etc. tiny particles contents, significantly promote filter efficiency, realize air cleaning;It can also be used for personal protection device (such as mask), be beneficial to health.
Description
Technical field
The present invention relates to a kind of efficient intercalation formula nanofiber filter membranes, belong to air cleaning and membrane material technology of preparing neck
Domain.
Background technique
Due to economic rapid growth and industrialization and the automobile to increase sharply uses and urbanization, and China is just by serious big
The influence of pellet (PM) in gas, global air pollution is increasingly severe, and the health of the mankind is on the hazard, weather
Deteriorate and the damage of the ecosystem is also on the rise.Efficiently, economic, energy-efficient filter membrane is to solve the problems, such as the ideal hand
Section.However the shortcomings that can not overcoming there are many existing fiber filter films, as fibre diameter is relatively thick (micro- from several microns to tens
Rice) and synthetic aperture it is larger, filter particulate efficiency it is relatively low, film heaviness etc..Currently, having developed number of ways to prepare
Nano fibrous membrane is used for separate fine particles, including mutually separates, templated synthesis, corona treatment and fusion method.But in these sides
In method, most of there are still filter efficiency is low and the high problem of energy consumption.Thus developing one kind can simply prepare and high efficiency filter
The filter membrane of various pollutants, and be applied to most important in production and living.The technology simple and powerful as one kind,
Tunica fibrosa is prepared under nanometer and submicron-scale, electrostatic spinning has been obtained for more and more paying close attention to.
But existing filter membrane function is more single in the market, is only capable of filtering some large particles, is not able to satisfy high efficiency filter
Demand.
Summary of the invention
The purpose of the present invention is a kind of improvement to common macromolecular filtering film, imitate the filter membrane with higher filtering
Rate does not increase complicated preparation process.
Technology of the invention is as follows:
A kind of nanofiber filter membrane of functionalization graphene intercalation, it is characterised in that: the filter membrane contains high molecular nanometer fibre
Peacekeeping functionalization graphene layer, the functionalization graphene layer insert in inside high polymer nanometer fiber, mutually overlapping between the two.
It is using electrostatic that functionalization graphene layer of the present invention, which is inserted in inside high polymer nanometer fiber and mutually overlapped,
The synchronous realization of spinning technique.
Preferably, the functionalization graphene layer be by graphene oxide, redox graphene, hydroxylating graphene and
One or more of carboxylated graphene material is formed.
Preferably, the high polymer nanometer fiber be by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone,
The nanofiber that one or more of bisphenol-a polysulfone, polystyrene and nylon material is formed.
The preparation method of the nanofiber filter membrane of a kind of functionalization graphene intercalation provided by the invention, it is characterised in that should
Method includes the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, before being configured to functionalization graphene
Drive liquid and high molecular material precursor liquid;
2) electrospinning device is used, macromolecule precursor liquid and functionalization graphene precursor liquid are respectively placed in syringe
It is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6-
1.0mm/min makes functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, can make functionalization graphene
Layer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
Preferably, the mass-volume concentration of the functionalization graphene precursor liquid is 0.01-0.5g/mL, high molecular material
The mass-volume concentration of precursor liquid is 0.5-2g/10mL.
Preferably, the organic solvent is using n,N-Dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide
One or more of mixing.
The present invention has the following advantages that and high-lighting technical effect: the present invention is in conventional nano fiber membrane preparation process
In, insertions function graphite alkene layer, so that the functional group abundant using functionalization graphene surface greatly improves fine grained
The strainability of object can effectively adsorb NH3、CO、NO2Equal polluted gas, and smog, pollen, PM in energy high efficiency filter air2.5
Etc. tiny particles contents.Preparation method simple process simultaneously, can one-pass molding, preparation efficiency is high, effectively reduces production cost.
Detailed description of the invention
Fig. 1 is the schematic diagram of preparation method of the present invention.
Fig. 2 is the nanofiber filter membrane SEM figure for being a kind of functionalization graphene intercalation provided by the invention.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and examples.
Fig. 1 is the schematic diagram of preparation method of the present invention, which includes the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, before being configured to functionalization graphene
Drive liquid and high molecular material precursor liquid;The mass-volume concentration of functionalization graphene precursor liquid is preferably 0.01-0.5g/mL, high
The mass-volume concentration of molecular material precursor liquid is preferably 0.5-2g/10mL;The organic solvent uses volatile N, N-
The mixing of one or more of dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide;The functionalization graphene layer
It is by one or more of graphene oxide, redox graphene, hydroxylating graphene and carboxylated graphene material shape
At;The high polymer nanometer fiber is gathered by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone, bisphenol A-type
The nanofiber that one of sulfone, polystyrene and nylon Hu different materials are formed.
2) electrospinning device is used, macromolecule precursor liquid 1 and functionalization graphene precursor liquid 2 are respectively placed in syringe
It is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6-
1.0mm/min making functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, functionalization graphene can be made
Layer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
Fig. 2 is the nanofiber filter membrane SEM figure for being a kind of functionalization graphene intercalation provided by the invention.The Nanowire
Dimension filter membrane contains functionalization graphene layer 4 and high polymer nanometer fiber 3, and functionalization graphene layer inserts in high polymer nanometer fiber
Portion, it is mutually overlapping between the two;It is to adopt that the functionalization graphene layer, which is inserted in inside high polymer nanometer fiber and mutually overlapped,
With the synchronous realization of electrostatic spinning process.
Embodiment 1:
Step A, graphene oxide, eccentric cleaning drying are prepared using improved Hummer method.
Step B, 10mg graphene oxide and polyacrylonitrile n,N-Dimethylformamide dispersion liquid are prepared respectively, and it is poly- to weigh 1g
10mLN is added in acrylonitrile, and in dinethylformamide, stirring makes precursor liquid be uniformly dispersed, and weighs 10mg graphene oxide and adds
Enter in 10mL n,N-Dimethylformamide, stirring ultrasound keeps its evenly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connects
Device 20.5cm, voltage 10kV, fltting speed 0.8mm/min are received, 10mg graphene oxide is inserted into polyacrylonitrile fibre, is formed
The nanofiber filter membrane of graphene oxide insertion.
Embodiment 2:
Step A, redox graphene, eccentric cleaning freeze-drying are prepared.
Step B, 15mg redox graphene and bisphenol-a polysulfone ethylene glycol dispersion liquid are prepared, 1.5g bisphenol A-type is weighed
Polysulfones is added in 10mL ethylene glycol, and stirring makes precursor liquid be uniformly dispersed, then weigh 15mg redox graphene, and 10mL is added
In ethylene glycol, stirring ultrasound makes precursor liquid be uniformly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connects
Device 18cm, voltage 15kV, fltting speed 1mm/min are received, 15mg redox graphene is inserted into bisphenol-a polysulfone fiber,
Form the nanofiber filter membrane of redox graphene intercalation.
Embodiment 3:
Step A, hydroxylating graphene, eccentric cleaning drying are prepared.
Step B, 5mg hydroxylating graphene and polyvinylpyrrolidone N-Methyl pyrrolidone dispersion liquid are prepared, 2g is weighed
Polyvinyl alcohol is added in 10mL N-Methyl pyrrolidone, and stirring makes precursor liquid be uniformly dispersed, then weigh 5mg hydroxyl graphite
Alkene is added in 10mL N-Methyl pyrrolidone, and stirring ultrasound makes precursor liquid be uniformly dispersed.
Step C, configured two kinds of precursor solutions are placed on electrospinning device with syringe, needle tip distance connects
Device 20cm, voltage 8kV, fltting speed 0.6mm/min are received, by the polyvinyl pyrrolidone fibers of 5mg hydroxylating graphene intercalation
In, form the nanofiber filter membrane of hydroxylating graphene intercalation.
Claims (7)
1. a kind of nanofiber filter membrane of functionalization graphene intercalation, it is characterised in that: the filter membrane contains high polymer nanometer fiber
(3) it inserts in inside high polymer nanometer fiber with functionalization graphene layer (4), the functionalization graphene layer, mutually hands between the two
It is folded.
2. a kind of nanofiber filter membrane of functionalization graphene intercalation according to claim 1, it is characterised in that: described
Functionalization graphene layer, which is inserted in inside high polymer nanometer fiber and mutually overlapped, to be realized using electrostatic spinning process is synchronous.
3. a kind of nanofiber filter membrane of functionalization graphene intercalation as claimed in claim 1 or 2, it is characterised in that: described
Functionalization graphene layer is by one in graphene oxide, redox graphene, hydroxylating graphene and carboxylated graphene
What kind or different materials were formed.
4. a kind of nanofiber filter membrane of functionalization graphene intercalation as claimed in claim 1 or 2, it is characterised in that: described
High polymer nanometer fiber be by polyacrylonitrile, polypropylene, Polyurethane, polyvinylpyrrolidone, bisphenol-a polysulfone, polyphenyl second
The nanofiber that one or more of alkene and nylon material are formed.
5. a kind of preparation method of the nanofiber filter membrane of functionalization graphene intercalation as described in claim 1, feature exist
In this method comprises the following steps:
1) functionalization graphene and high molecular material are added separately in organic solvent, are configured to functionalization graphene precursor liquid
With high molecular material precursor liquid;
2) electrospinning device is used, macromolecule precursor liquid (1) and functionalization graphene precursor liquid (2) are respectively placed in syringe
It is interior, and technological parameter is set are as follows: spray head distance between two tips receiver distance is 18-20.5cm, voltage 8-20kV, fltting speed 0.6-
1.0mm/min makes functionalization graphene layer is synchronous with high polymer nanometer fiber forming process to carry out, can make functionalization graphene
Layer inserts in inside high polymer nanometer fiber, forms mutually overlapping nanofiber filter membrane.
6. a kind of preparation method of the nanofiber filter membrane of functionalization graphene intercalation as claimed in claim 5, feature exist
In: the mass-volume concentration of the functionalization graphene precursor liquid is 0.01-0.5g/mL, the quality of high molecular material precursor liquid
Volumetric concentration is 0.5-2g/10mL.
7. such as a kind of preparation method of the nanofiber filter membrane of functionalization graphene intercalation described in claim 5 or 6, feature
Be: the organic solvent uses one of N,N-dimethylformamide, N-Methyl pyrrolidone and dimethyl sulfoxide or several
The mixing of kind.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810996163.8A CN109157928A (en) | 2018-08-29 | 2018-08-29 | A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810996163.8A CN109157928A (en) | 2018-08-29 | 2018-08-29 | A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109157928A true CN109157928A (en) | 2019-01-08 |
Family
ID=64893102
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810996163.8A Pending CN109157928A (en) | 2018-08-29 | 2018-08-29 | A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109157928A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110284263A (en) * | 2019-06-13 | 2019-09-27 | 上海交通大学 | The preparation method of lamination composite nano fiber |
CN112619622A (en) * | 2020-12-23 | 2021-04-09 | 广州大学 | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof |
WO2022183215A1 (en) * | 2021-02-26 | 2022-09-01 | Merit Medical Systems, Inc. | Fibrous constructs with therapeutic material particles |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103147226A (en) * | 2013-02-07 | 2013-06-12 | 江西师范大学 | Method for preparing high dielectric constant polymer-based nano composite material |
CN105568401A (en) * | 2015-12-12 | 2016-05-11 | 大连理工大学 | Ultrasonic atomization assisted electrospinning technique |
CN106245232A (en) * | 2016-07-27 | 2016-12-21 | 山东大学 | Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application |
CN107583377A (en) * | 2017-08-24 | 2018-01-16 | 清华大学 | A kind of air-filtering membrane of functionalization graphene modification and preparation method thereof |
-
2018
- 2018-08-29 CN CN201810996163.8A patent/CN109157928A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103147226A (en) * | 2013-02-07 | 2013-06-12 | 江西师范大学 | Method for preparing high dielectric constant polymer-based nano composite material |
CN105568401A (en) * | 2015-12-12 | 2016-05-11 | 大连理工大学 | Ultrasonic atomization assisted electrospinning technique |
CN106245232A (en) * | 2016-07-27 | 2016-12-21 | 山东大学 | Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application |
CN107583377A (en) * | 2017-08-24 | 2018-01-16 | 清华大学 | A kind of air-filtering membrane of functionalization graphene modification and preparation method thereof |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110284263A (en) * | 2019-06-13 | 2019-09-27 | 上海交通大学 | The preparation method of lamination composite nano fiber |
CN110284263B (en) * | 2019-06-13 | 2022-03-08 | 上海交通大学 | Preparation method of laminated composite nanofiber |
CN112619622A (en) * | 2020-12-23 | 2021-04-09 | 广州大学 | Nano composite fiber membrane capable of efficiently removing ionic dye and heavy metal ions in water, and preparation method and application thereof |
WO2022183215A1 (en) * | 2021-02-26 | 2022-09-01 | Merit Medical Systems, Inc. | Fibrous constructs with therapeutic material particles |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109157928A (en) | A kind of nanofiber filter membrane of functionalization graphene intercalation and preparation method thereof | |
CN105483939B (en) | A kind of preparation method of porous graphene nano fibrous membrane | |
CN107583377A (en) | A kind of air-filtering membrane of functionalization graphene modification and preparation method thereof | |
Jia et al. | Flexible ceramic fibers: Recent development in preparation and application | |
CN103774345B (en) | A kind of preparation method of efficient low-resistance antibacterial purification of air filter membrane | |
CN106807250B (en) | A kind of preparation method of graphene oxide/silica/high molecular polymer composite nanometer filtering film | |
CN104014196B (en) | A kind of high absorption nanofiber composite filter material and preparation method thereof | |
CN104689724A (en) | Organic and inorganic composite nanofiber membrane filtering material and preparation method thereof | |
CN104611995A (en) | Air filter paper and preparation method thereof | |
CN103898676A (en) | Cellulose acetate/ titanium dioxide composite nanofiber adsorption film and preparation method thereof | |
CN108452690A (en) | The preparation method of efficient low-resistance multilayered structure Electrospun nano-fibers composite membrane | |
CN105568401A (en) | Ultrasonic atomization assisted electrospinning technique | |
CN112495200B (en) | Preparation method of mixed matrix membrane with high-speed gas transmission channel | |
CN105597575B (en) | A kind of degradable biological base air filter film and preparation method thereof | |
Zhang et al. | Recent developments of electrospun nanofibrous materials as novel adsorbents for water treatment | |
CN104213202A (en) | Spinning solution and method for preparing antibacterial air filtering membrane by spinning solution | |
CN106245232A (en) | Graphene oxide@high polymer nano fiber multilayer film and its preparation method and application | |
CN104178930A (en) | Nanofiber membrane and preparing method thereof | |
CN108465297A (en) | A kind of preparation method of super-hydrophobic electret filter for air purification | |
CN110368718A (en) | A kind of superoleophobic nethike embrane of the super-hydrophilic and underwater of 3 D-printing and preparation method thereof | |
CN109289327B (en) | Antibacterial efficient air filtering membrane and preparation method thereof | |
CN106757767A (en) | A kind of preparation and application of high intensity beta cyclodextrin/cellulose acetate composite nano-fiber membrane | |
CN108998892A (en) | A kind of preparation method of chitosan-graphene oxide/polyacrylonitrile double-layer nanometer tunica fibrosa | |
CN103879120A (en) | Fibroin nanofiber haze protection product based on waste cocoon silk raw materials | |
CN102600667B (en) | Air filter material based on carbon nano tube 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 | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190108 |