CN108774808A - A kind of polyimide nanofiber membrane and preparation method thereof that there is the surface of crosslinking pattern to coat zirconium dioxide - Google Patents
A kind of polyimide nanofiber membrane and preparation method thereof that there is the surface of crosslinking pattern to coat zirconium dioxide Download PDFInfo
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- CN108774808A CN108774808A CN201810603290.7A CN201810603290A CN108774808A CN 108774808 A CN108774808 A CN 108774808A CN 201810603290 A CN201810603290 A CN 201810603290A CN 108774808 A CN108774808 A CN 108774808A
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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
- D01D5/0015—Electro-spinning characterised by the initial state of the material
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- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
A kind of polyimide nanofiber membrane and preparation method thereof that there is the surface of crosslinking pattern to coat zirconium dioxide.Pass through Preparation of Polyimide Nanofibers by Electrospinning film first, the polymer solution treatment of zirconium dioxide is used in combination, it is subsequently placed in the ammonia atmosphere of weak aqua ammonia formation and handles the regular hour, finally using heat treatment, the polyimide nanofiber membrane of the surface cladding zirconium dioxide with crosslinking pattern is finally obtained.The method implementation process of the present invention is simple, and coating efficiency is high, and application prospect is good.
Description
Technical field
The invention belongs to polyimide fiber technical field of membrane, are coated more particularly, to a kind of surface with crosslinking pattern
Polyimide nanofiber membrane of zirconium dioxide and preparation method thereof.
Background technology
The many merits such as there is lithium ion battery environmentally protective, service life to grow tall, low temperature adaptability is strong, therefore in recent years
More and more favored by researchers.Lithium ion battery separator is the key that one of layer assembly in lithium ion battery, lithium from
Very important effect is played in sub- battery.First, it can be in direct contact to avoid lithium battery positive and negative anodes, prevent short circuit, simultaneously
It may ensure that when charge and discharge ion normal through ensureing the normal work of battery.The performance of lithium ion battery separator will be straight
Connecing influences the performance of battery, and therefore, the research of diaphragm material becomes the hot issue in current Study on Li-ion batteries.
Electrostatic spinning is otherwise known as Electrospun, in recent years, due to the fast development of nanotechnology, electrostatic spinning technique is got over
More to cause the concern of countries in the world researcher, it is increasingly becoming the method for using most generally to produce nanofiber in the world.Profit
The features such as nanofiber prepared with method of electrostatic spinning has diameter small, large specific surface area, it is concurrent to be widely used in multiple fields
Important function is waved, such as filtering material, biological medicine functional material, sensor material, electrode material, reinforcing material, sound-absorbing material
Deng.
Polyimide material has excellent high temperature resistant, low temperature resistant, high-strength and high-modulus, high creep resistant, high dimensionally stable, low-heat
The coefficient of expansion, high electric insulation, low-k and loss, radiation hardness, it is corrosion-resistant the advantages that, while have vacuum volatilization it is point low,
The characteristics of condensable material that volatilizees waits space materials less.Nano level PI fibers not only have the various features of polyimides, also have
The advantages of large specific surface area, is particularly suitable for storage, conversion and the protection of environment of energy etc..It is covered by surface inorganic particulate
The method of load prepares polyimide/inorganic particle composite material, imparts the more characteristics of polyimide nano-fiber, and work as
Preceding research hotspot.Such as once to have prepared polyimides/zirconium dioxide using sol-gel method multiple by patent CN105970485A
Close nano fibrous membrane.The method that the present invention uses is simple, and zirconium dioxide inorganic nano layer is evenly coated, and obtained composite Nano is fine
Tieing up film has higher porosity and imbibition rate and excellent mechanical property, is ideal as lithium ion battery separator
Candidate material.
Invention content
The present invention provides it is a kind of have crosslinking pattern surface coat zirconium dioxide polyimide nanofiber membrane and
Preparation method.The nano fibrous membrane combines the advantages of polyimides and zirconium dioxide, has high porosity, excellent
Chemical stability, thermal dimensional stability and excellent mechanical performance.Its detailed process prepared is prepared by method of electrostatic spinning
Polyamic acid nano fibrous membrane, then makes polyamic acid be partially converted into polyimides through Overheating Treatment, be placed on titanium dioxide
The regular hour is impregnated in the poly liquid solution of zirconium to take out, and is then placed in the steam atmosphere of weak aqua ammonia and is handled the regular hour,
Form one layer of zirconia sol on the surface of fiber makes zirconia sol be converted into zirconium dioxide finally through Overheating Treatment
And cross-linked structure is formed, finally obtain the polyimide nanofiber membrane of the surface cladding zirconium dioxide with crosslinking pattern.
Surface with crosslinking pattern coats the preparation method of the polyimide nanofiber membrane of zirconium dioxide, specific to walk
It is rapid as follows:
A:It is 1 in mass ratio by ethyl alcohol and deionized water:1 is made into mixed solvent, and zirconates is dissolved in the mixing solvent,
The hydrogen peroxide of mass fraction 30% is added, reacts 20min, obtains the poly liquid solution of zirconium dioxide;
B:Use method of electrostatic spinning that polyamic acid nanofiber is made for the polyamic acid solution of 8%-30% in solid content
Film, stroke control of going forward side by side heating hot-imide processing keep the temperature 1-2h from room temperature to 200-250 DEG C, it is sub- to obtain incomplete acyl
The polyimide nanofiber membrane of amination;
C:The polyimide nanofiber membrane of incomplete imidizate is immersed in the zirconium dioxide polymer obtained by step A
In solution, it is ultrasonically treated 5-10min;
D:The polyimide nanofiber membrane handled by step C is placed in ammonia atmosphere, at 40-70 DEG C of constant temperature
Manage 1-4h;
E:The polyimide nanofiber membrane obtained by D step process is heated into 2h under the conditions of 300 DEG C, is had
It is crosslinked the polyimide nanofiber membrane of the surface cladding zirconium dioxide of pattern.
Wherein, the zirconates described in step A is zirconium nitrate, citric acid zirconium, zirconium chloride and zirconium oxychloride, in solution zirconium from
A concentration of 0.5-4mol/L of son;The molar ratio of hydrogen peroxide and zirconates is 4-6.Ammonia atmosphere in step D is molten by weak aqua ammonia
Liquid heating volatilization is formed, a concentration of 0.001mol/L-0.005mol/L of weak aqua ammonia.
Compared with prior art, this method has following excellent results:
1. preparation process of the present invention is simple, condition easily meets, easy repetition easy to operate, and can lead in processing procedure
The adjusting of preparation technology parameter is crossed, realizes the controllable of zirconium dioxide layer thickness.
2. prepared by the present invention has the polyimide nanofiber membrane of the surface cladding zirconium dioxide of crosslinking pattern, have
High porosity, excellent chemical stability, thermal dimensional stability and excellent mechanical performance.
3. the present invention prepares the polyimide nanofiber membrane of surface cladding zirconium dioxide, caused secondly zirconium oxide layer also has
It is close uniform, the high feature of adhesive force.
Description of the drawings
Fig. 1 is the polyimide nano fibre that there is the surface of crosslinking pattern to coat zirconium dioxide prepared according to embodiment 1
Tie up the scanning electron microscope (SEM) photograph of film, 200000 times of amplification factor.
Fig. 2 is the polyimide nano fibre that there is the surface of crosslinking pattern to coat zirconium dioxide prepared according to embodiment 2
Tie up the scanning electron microscope (SEM) photograph of film, 200000 times of amplification factor.
Fig. 3 is the polyimide nano fibre that there is the surface of crosslinking pattern to coat zirconium dioxide prepared according to embodiment 3
Tie up the scanning electron microscope (SEM) photograph of film, 200000 times of amplification factor.
Fig. 4 is the polyimide nano fibre that there is the surface of crosslinking pattern to coat zirconium dioxide prepared according to embodiment 4
Tie up the scanning electron microscope (SEM) photograph of film, 200000 times of amplification factor.
Fig. 5 is the polyimide nano fibre that there is the surface of crosslinking pattern to coat zirconium dioxide prepared according to embodiment 5
Tie up the scanning electron microscope (SEM) photograph of film, 200000 times of amplification factor.
Specific implementation mode
With reference to specific embodiment, invention is expanded on further.It should be noted that:Following embodiment is only to illustrate this
It invents and not limits technical solution described in the invention.Therefore, although this specification with reference to following embodiments to this hair
It is bright to have been carried out detailed description, it will be appreciated, however, by one skilled in the art that still can modify to the present invention or
Equivalent replacement;And all do not depart from technical solution and its improvement of the spirit and scope of the present invention, should all cover in the present invention
Right in.
Embodiment 1
PMDA/ODA system polyamic acid tunica fibrosas are prepared, polyimide nanofiber membrane is obtained after hot imidization, is placed in
In the zirconium poly liquid solution of 1mol/L, after being ultrasonically treated 5min, it is placed in 1h in weak aqua ammonia steam atmosphere, is finally obtained through Overheating Treatment
The polyimide nanofiber membrane of zirconium dioxide is coated to the surface with crosslinking pattern.(1) it is 1 to weigh molar ratio:1 equal benzene
ODA, is all dissolved in the N of 30ml, N- dimethyl by tetracarboxylic acid dianhydride (PMDA) 2.0g, 4,4 '-diaminodiphenyl ether (ODA) 1.8g
In formamide (DMF) solvent, mechanical agitation, after ODA is fully dissolved in DMF, under conditions of ice-water bath, PMDA is added in substep,
After obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is fitted into the syringe of 20ml, is answered
Polyamic acid tunica fibrosa is prepared with electrostatic spinning technique, electrostatic spinning machine design parameter is spinning voltage:20kV;Spinning temperature
Degree:Room temperature;Spinning humidity:20%;Syringe needle diameter:No. 12;Receiving roll rotating speed:80.0m/min;Receive distance:20cm.
The polyamic acid tunica fibrosa prepared is placed in 12h in super-clean bench;Gained polyamic acid tunica fibrosa is placed in hot stove, with 2 DEG C/
The heating rate of min is gradually warming up to 300 DEG C, and keeps 2h, to which polyimide nanofiber membrane be made.(2) 20ml is measured
Deionized water, 25ml absolute ethyl alcohols are uniformly mixed in beaker.14g zirconium oxychlorides are weighed, ethyl alcohol and deionized water are added to
In the mixed solvent, and stirring makes it fully dissolve.Measure 7.87mlH2O2, it is added in beaker, fully reacts 20min, obtains two
The poly liquid solution of zirconium oxide.(3) polyimide nanofiber membrane is immersed in the poly liquid solution of titanium dioxide zirconium dioxide,
It is ultrasonically treated 5min, taking-up is dried.(4) nano fibrous membrane that previous step is handled is placed in the steam atmosphere of weak aqua ammonia
In, keep 60 DEG C of constant temperature to handle 1h.(5) nano fibrous membrane that previous step is handled is placed in 300 DEG C of baking ovens and keeps the temperature 2h, obtained
The polyimide nanofiber membrane of zirconium dioxide is coated to surface, gained fiber morphology is as shown in Fig. 1.
Embodiment 2
PMDA/ODA system polyamic acid tunica fibrosas are prepared, polyimide nanofiber membrane is obtained after hot imidization, is placed in
In the zirconium poly liquid solution of 2mol/L, after being ultrasonically treated 5min, it is placed in 1h in weak aqua ammonia steam atmosphere, is finally obtained through Overheating Treatment
The polyimide nanofiber membrane of zirconium dioxide is coated to the surface with crosslinking pattern.(1) it is 1 to weigh molar ratio:1 equal benzene
ODA, is all dissolved in the N of 30ml, N- dimethyl by tetracarboxylic acid dianhydride (PMDA) 2.0g, 4,4 '-diaminodiphenyl ether (ODA) 1.8g
In formamide (DMF) solvent, mechanical agitation, after ODA is fully dissolved in DMF, under conditions of ice-water bath, PMDA is added in substep,
After obtaining the polyamic acid solution of modest viscosity, after mechanical agitation 2h, polyamic acid solution is fitted into the syringe of 20ml, is answered
Polyamic acid tunica fibrosa is prepared with electrostatic spinning technique, electrostatic spinning machine design parameter is spinning voltage:20kV;Spinning temperature
Degree:Room temperature;Spinning humidity:20%;Syringe needle diameter:No. 12;Receiving roll rotating speed:80.0m/min;Receive distance:20cm.
The polyamic acid tunica fibrosa prepared is placed in 12h in super-clean bench;Gained polyamic acid tunica fibrosa is placed in hot stove, with 2 DEG C/
The heating rate of min is gradually warming up to 300 DEG C, and keeps 2h, to which polyimide nanofiber membrane be made.(2) 20ml is measured
Deionized water, 25ml absolute ethyl alcohols are uniformly mixed in beaker.28g zirconium oxychlorides are weighed, ethyl alcohol and deionized water are added to
In the mixed solvent, and stirring makes it fully dissolve.Measure 7.87ml H2O2, it is added in beaker, fully reacts 20min, obtains
The poly liquid solution of zirconium dioxide.(3) polyimide nanofiber membrane is immersed in the poly liquid solution of zirconium dioxide, ultrasound
5min is handled, taking-up is dried.(4) nano fibrous membrane that previous step is handled is placed in the steam atmosphere of weak aqua ammonia, is protected
Hold 60 DEG C of constant temperature processing 1h.(5) nano fibrous membrane that previous step is handled is placed in 300 DEG C of baking ovens and keeps the temperature 2h, obtain table
Bread covers the polyimide nanofiber membrane of zirconium dioxide, and gained fiber morphology is as shown in Fig. 2.
Embodiment 3
BTDA/ODA system polyamic acid tunica fibrosas are prepared, polyimide nanofiber membrane is obtained after hot imidization, is placed in
In the zirconium poly liquid solution of 2mol/L, after being ultrasonically treated 5min, it is placed in 1h in weak aqua ammonia steam atmosphere, is finally obtained through Overheating Treatment
The polyimide nanofiber membrane of zirconium dioxide is coated to the surface with crosslinking pattern.(1) it is 1 to weigh molar ratio:1 BTDA
ODA is all dissolved in n,N-Dimethylformamide (DMF) solvent of 30ml by 2.0g, 4,4 '-diaminodiphenyl ethers (ODA) 1.8g
In, mechanical agitation, after ODA is fully dissolved in DMF, under conditions of ice-water bath, BTDA is added in substep, obtains the poly- of modest viscosity
After amide acid solution, after mechanical agitation 2h, polyamic acid solution is fitted into the syringe of 20ml, using electrostatic spinning technique system
For polyamic acid tunica fibrosa is gone out, electrostatic spinning machine design parameter is spinning voltage:20kV;Spinning temperature:Room temperature;Spinning humidity:
20%;Syringe needle diameter:No. 12;Receiving roll rotating speed:80.0m/min;Receive distance:20cm.The polyamide that will be prepared
Sour tunica fibrosa is placed in 12h in super-clean bench;Gained polyamic acid tunica fibrosa is placed in hot stove, with the heating rate of 2 DEG C/min by
Step is warming up to 300 DEG C, and keeps 2h, to which polyimide nanofiber membrane be made.(2) measure 20ml deionized waters, 25ml without
Water-ethanol is uniformly mixed in beaker.28g zirconium oxychlorides are weighed, the in the mixed solvent of ethyl alcohol and deionized water is added to, and are stirred
Mixing makes it fully dissolve.Measure 7.87mlH2O2, it is added in beaker, fully reacts 20min, obtains the polymer of zirconium dioxide
Solution.(3) polyimide nanofiber membrane is immersed in the poly liquid solution of zirconium dioxide, is ultrasonically treated 5min, taking-up is dried in the air
It is dry.(4) nano fibrous membrane that previous step is handled is placed in the steam atmosphere of weak aqua ammonia, keeps 60 DEG C of constant temperature processing
1h.(5) nano fibrous membrane that previous step is handled is placed in 300 DEG C of baking ovens and keeps the temperature 2h, obtain surface cladding zirconium dioxide
Polyimide nanofiber membrane, gained fiber morphology is as shown in Fig. 3.
Embodiment 4
ODPA/ODA system polyamic acid tunica fibrosas are prepared, polyimide nanofiber membrane is obtained after hot imidization, is placed in
In the zirconium poly liquid solution of 2mol/L, after being ultrasonically treated 5min, it is placed in 1h in weak aqua ammonia steam atmosphere, is finally obtained through Overheating Treatment
The polyimide nanofiber membrane of zirconium dioxide is coated to the surface with crosslinking pattern.(1) it is 1 to weigh molar ratio:1 ODPA
ODA is all dissolved in n,N-Dimethylformamide (DMF) solvent of 30ml by 2.0g, 4,4 '-diaminodiphenyl ethers (ODA) 1.8g
In, mechanical agitation, after ODA is fully dissolved in DMF, under conditions of ice-water bath, ODPA is added in substep, obtains the poly- of modest viscosity
After amide acid solution, after mechanical agitation 2h, polyamic acid solution is fitted into the syringe of 20ml, using electrostatic spinning technique system
For polyamic acid tunica fibrosa is gone out, electrostatic spinning machine design parameter is spinning voltage:20kV;Spinning temperature:Room temperature;Spinning humidity:
20%;Syringe needle diameter:No. 12;Receiving roll rotating speed:80.0m/min;Receive distance:20cm.The polyamide that will be prepared
Sour tunica fibrosa is placed in 12h in super-clean bench;Gained polyamic acid tunica fibrosa is placed in hot stove, with the heating rate of 2 DEG C/min by
Step is warming up to 300 DEG C, and keeps 2h, to which polyimide nanofiber membrane be made.(2) measure 20ml deionized waters, 25ml without
Water-ethanol is uniformly mixed in beaker.28g zirconium oxychlorides are weighed, the in the mixed solvent of ethyl alcohol and deionized water is added to, and are stirred
Mixing makes it fully dissolve.Measure 7.87mlH2O2, it is added in beaker, fully reacts 20min, obtains the polymer of zirconium dioxide
Solution.(3) polyimide nanofiber membrane is immersed in the poly liquid solution of zirconium dioxide, is ultrasonically treated 5min, taking-up is dried in the air
It is dry.(4) nano fibrous membrane that previous step is handled is placed in the steam atmosphere of weak aqua ammonia, keeps 60 DEG C of constant temperature processing
1h.(5) nano fibrous membrane that previous step is handled is placed in 300 DEG C of baking ovens and keeps the temperature 2h, obtain surface cladding zirconium dioxide
Polyimide nanofiber membrane, gained fiber morphology is as shown in Fig. 4.
Embodiment 5
6FDA/ODA system polyamic acid tunica fibrosas are prepared, polyimide nanofiber membrane is obtained after hot imidization, is placed in
In the zirconium poly liquid solution of 2mol/L, after being ultrasonically treated 5min, it is placed in 1h in weak aqua ammonia steam atmosphere, is finally obtained through Overheating Treatment
The polyimide nanofiber membrane of zirconium dioxide is coated to the surface with crosslinking pattern.(1) it is 1 to weigh molar ratio:1 6FDA
ODA is all dissolved in n,N-Dimethylformamide (DMF) solvent of 30ml by 4.0g, 4,4 '-diaminodiphenyl ethers (ODA) 1.8g
In, mechanical agitation, after ODA is fully dissolved in DMF, under conditions of ice-water bath, 6FDA is added in substep, obtains the poly- of modest viscosity
After amide acid solution, after mechanical agitation 2h, polyamic acid solution is fitted into the syringe of 20ml, using electrostatic spinning technique system
For polyamic acid tunica fibrosa is gone out, electrostatic spinning machine design parameter is spinning voltage:20kV;Spinning temperature:Room temperature;Spinning humidity:
20%;Syringe needle diameter:No. 12;Receiving roll rotating speed:80.0m/min;Receive distance:20cm.The polyamide that will be prepared
Sour tunica fibrosa is placed in 12h in super-clean bench;Gained polyamic acid tunica fibrosa is placed in hot stove, with the heating rate of 2 DEG C/min by
Step is warming up to 300 DEG C, and keeps 2h, to which polyimide nanofiber membrane be made.(2) measure 20ml deionized waters, 25ml without
Water-ethanol is uniformly mixed in beaker.28g zirconium oxychlorides are weighed, the in the mixed solvent of ethyl alcohol and deionized water is added to, and are stirred
Mixing makes it fully dissolve.Measure 7.87ml H2O2,It is added in beaker, fully reacts 20min, obtain the polymer of zirconium dioxide
Solution.(3) polyimide nanofiber membrane is immersed in the poly liquid solution of zirconium dioxide, is ultrasonically treated 5min, taking-up is dried in the air
It is dry.(4) nano fibrous membrane that previous step is handled is placed in the steam atmosphere of weak aqua ammonia, keeps 60 DEG C of constant temperature processing
1h.(5) nano fibrous membrane that previous step is handled is placed in 300 DEG C of baking ovens and keeps the temperature 2h, obtain surface cladding zirconium dioxide
Polyimide nanofiber membrane, gained fiber morphology is as shown in Fig. 5.
Claims (3)
1. a kind of preparation method for the polyimide nanofiber membrane that there is the surface of crosslinking pattern to coat zirconium dioxide, feature
It is to include the following steps:
A:It is 1 in mass ratio by ethyl alcohol and deionized water:1 is made into mixed solvent, and zirconates is dissolved in the mixing solvent, is added
The hydrogen peroxide of mass fraction 30% reacts 20min, obtains the poly liquid solution of zirconium dioxide;
B:Use method of electrostatic spinning that polyamic acid nano fibrous membrane is made for the polyamic acid solution of 8%-30% in solid content, and
Program-controlled heating hot-imide processing is carried out to keep the temperature 1-2h from room temperature to 200-250 DEG C, obtain incomplete imidizate
Polyimide nanofiber membrane;
C:The polyimide nanofiber membrane of incomplete imidizate is immersed in the zirconium dioxide poly liquid solution obtained by step A
In, it is ultrasonically treated 5-10min;
D:The polyimide nanofiber membrane handled by step C is placed in ammonia atmosphere, 40-70 DEG C of constant temperature handles 1-
4h;
E:The polyimide nanofiber membrane obtained by D step process is heated into 2h under the conditions of 300 DEG C, obtains that there is crosslinking
The polyimide nanofiber membrane of the surface cladding zirconium dioxide of pattern.
2. according to the method for claim 2, which is characterized in that zirconates described in step A be zirconium nitrate, citric acid zirconium,
Zirconium chloride and zirconium oxychloride, a concentration of 0.5-4mol/L of zirconium ion in solution;The molar ratio of hydrogen peroxide and zirconates is 4-
6。
3. according to the method for claim 2, which is characterized in that the ammonia atmosphere in step D is waved by dilute ammonia solution heating
Hair is formed, a concentration of 0.001mol/L-0.005mol/L of weak aqua ammonia.
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CN111472055A (en) * | 2020-04-03 | 2020-07-31 | 北京宇程科技有限公司 | High-temperature-resistant polymer nanofiber membrane densely coated with zirconium dioxide layer on surface and preparation method thereof |
CN113494020A (en) * | 2020-04-05 | 2021-10-12 | 北京化工大学 | Method for coating surface of polyimide nanofiber membrane with boehmite ceramic layer |
CN113529404A (en) * | 2020-04-17 | 2021-10-22 | 北京化工大学 | Polyimide nanofiber membrane with surface uniformly coated with controllable nano zirconium dioxide inorganic layer and preparation method thereof |
CN113622089A (en) * | 2021-09-08 | 2021-11-09 | 北京化工大学常州先进材料研究院 | Polyimide/cerium dioxide composite nanofiber membrane and preparation method thereof |
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