CN102817178A - Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane - Google Patents
Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane Download PDFInfo
- Publication number
- CN102817178A CN102817178A CN2012103337338A CN201210333733A CN102817178A CN 102817178 A CN102817178 A CN 102817178A CN 2012103337338 A CN2012103337338 A CN 2012103337338A CN 201210333733 A CN201210333733 A CN 201210333733A CN 102817178 A CN102817178 A CN 102817178A
- Authority
- CN
- China
- Prior art keywords
- polyvinyl alcohol
- spinning
- solution
- nano film
- preparation
- 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
Images
Abstract
The invention provides a method for improving the heat stability and mechanical property of a polyvinyl alcohol nanofiber membrane. The prepared polyvinyl alcohol nanofiber membrane has important application value in the fields of filtration, catalysis, fiber reinforcement, wound repair, tissue engineering, drug release and the like. The polyvinyl alcohol nanofiber membrane is prepared by mainly utilizing an electrostatic spinning technology and the polyvinyl alcohol nanofiber membrane with heat stability and mechanical property obviously improved is obtained by adding a few nontoxic and harmless third components with low cost and good water solubility to a polymer solution to directly carry out electrostatic spinning in the solution preparation process. The preparation method has the beneficial effects that the preparation method is simple to operate and has the advantages of low cost and obvious effect; the spinning process is stable; and the fibers have small diameters, are narrow in distribution and are light and pollution-free.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to the method that electrostatic spinning technique prepares nano fibrous membrane and improves nano fibrous membrane heat endurance and mechanical property.
Background technology
Electrostatic spinning is current unique technology that can prepare continuous superfine nano fiber, and this technology can be spun into nanofiber with the polymer (like polyolefin, polyamide, polyester, aromatic polyamide, polyacrylamide, acrylate copolymer and various biopolymer such as DNA, polypeptide, other conducting polymer or opto-electrical polymers etc.) that various traditional spining technology is used.Electrostatic spinning technique is through applying high-tension electricity between spinning head and receiving pole, and polymer solution forms taylor cone at spinning head under action of high voltage; Continue to increase voltage to certain value, have that a jet body forms and fly to receiving pole at a high speed, a series of crooked erratic processes of jet body process receive high-speed stretch, and in flight course owing to solvent evaporates solidify to form the superfine nano fiber.When polymer fiber diameter is reduced to nanoscale by micron order, some absorbing performances can appear in fiber, as high-specific surface area, surface-functionalized, improve the fibre machinery performance through the controlling fiber institutional framework.These performances make the electrostatic spinning polymer nanofiber in a lot of fields, like fields such as filtration, catalysis, fiber reinforcement, wound repair, organizational project, medicament slow releases, have important use and are worth.
Polyvinyl alcohol is a kind of hydrophily semicrystalline polymeric, because its good chemical stability, heat resistance, good physical property, biocompatibility and with low cost, and be with a wide range of applications.Polyvinyl alcohol obtains broad research owing to its property in electrostatic spinning, like the influence to polyvinyl alcohol nano film pattern such as spinning parameter, SOLUTION PROPERTIES, solution concentration, polymer molecular weight, alcoholysis degree.But also fewer about the heat endurance of the polyvinyl alcohol nano film of electrostatic spinning preparation and mechanical property research.Generally electrostatic spinning system nanofiber film dynamic performance is poor in addition, has limited some application of nanofiber like this.
There is bibliographical information to pass through polyvinyl alcohol and other materials (like silica; CNT; Titanium dioxide etc.) mix and to carry out electrostatic spinning and can obtain composite nano fiber, the heat endurance and the mechanical property of the nano fibrous membrane through these methods preparations are increased.But these methods prepare in the process, and institute's substance is not easy even dispersion, need multistep to handle; The amount of adding in addition is bigger, and cost is also than higher; Through introducing the polyvinyl alcohol nano film that chemical cross-linking agent can obtain chemical crosslinking; Its resistance to water and mechanical property are increased; But this method prepares in the process, uses aldehydes and strong acid to come cross-linking polyvinyl alcohol as catalyst usually, has certain toxicity; Cross-linking reaction is wayward in whole spinning process in addition, and tunica fibrosa biocompatibility after crosslinked and degradability descend.
Through adding the 3rd good component with low cost on a small quantity, nontoxic, water-soluble in polymer solution; Directly carry out electrostatic spinning; Chemical reaction not taking place and not having influence under the prerequisite of polyvinyl alcohol nano film biocompatibility and degradability, obtain the polyvinyl alcohol nano film that heat endurance and mechanical property significantly improve.This method can overcome some shortcomings that said method exists, for the good polyvinyl alcohol nano of electrostatic spinning processability provides a kind of new method.
Summary of the invention
The invention reside in provides a kind of new method that improves electrostatic spinning polyvinyl alcohol nano film heat endurance and mechanical property; This method is simple to operate, and is with low cost, and effect is remarkable; Environmental protection provides a kind of new method for improving electrostatic spinning nano tunica fibrosa heat endurance and mechanical property.
The present invention realizes through following technical scheme:
The present invention mainly utilizes electrostatic spinning technique, uses water as solvent, in poly-vinyl alcohol solution, adds a series of inorganic compounds, and the nano fibrous membrane heat endurance and the mechanical property of preparation significantly improve.
A kind of preparation method who improves polyvinyl alcohol electrostatic spinning nano fibrous membrane heat endurance and mechanical property, its step is following:
The preparation of A, electrostatic spinning solution: adding in the entry PVAC polyvinylalcohol fully, dissolving obtains solution; The concentration of PVA is 8wt% ~ 20wt%; Then sodium chloride, potassium chloride, sodium sulphate, sodium carbonate, sodium acid carbonate, NaOH or boric acid are added above-mentioned solution; Addition is 0.01 wt% ~ 3.0wt%, continues in the interpolation process to stir, and leaves standstill and obtains the homogeneous transparent spinning solution;
B, electrostatic spinning technique prepare nano fibrous membrane: the poly-vinyl alcohol solution of the inorganic-containing compound of the abundant dissolving that will prepare is packed in the syringe, and is fixed on the propeller of electrostatic spinning apparatus, prepares the polyvinyl alcohol nano film through electrostatic spinning.Spinning temperature is 20 ~ 50 ℃, and the spinning solution fltting speed is 0.001 ~ 0.005mm/s, and spinning voltage is 10 ~ 45kV, and spinning head is 8 ~ 25cm to the distance of receiving pole, time of reception 5-10h;
C, nano fibrous membrane post processing: the tunica fibrosa of preparation is carried out dried in vacuum drying chamber, drying at room temperature is stored in the drier subsequent use;
D, the batten that the nano fibrous membrane of above-mentioned preparation is cut into 50mm * 10mm carry out extension test, and every kind of tunica fibrosa is measured five times; Nano fibrous membrane with preparation carries out thermogravimetic analysis (TGA) respectively in addition.
Preparation method of the present invention is simple, and spinning process is stable, uses common inorganic compound with low cost; Directly the heat endurance and the mechanical property of the polyvinyl alcohol nano film of electrostatic spinning preparation significantly improve; Make it filter, biology, aspects such as medicament slow release have broader applications and are worth.
Description of drawings
Pure polyvinyl alcohol nano film of Fig. 1 (A) and polyvinyl alcohol nano film (B) SEM (SEM) photo that adds NaCl1.0wt%.
The pure polyvinyl alcohol nano film of Fig. 2 (Pure-PVA) and polyvinyl alcohol nano film (PVA-NaCl1.0wt%) TENSILE STRENGTH that adds NaCl1.0wt%-curve contrast.
Pure polyvinyl alcohol nano film of Fig. 3 (Pure-PVA) and polyvinyl alcohol nano film (PVA-NaCl1.0wt%) thermogravimetic analysis (TGA) (TG) the curve contrast that adds NaCl1.0wt%.
The specific embodiment
Specifically describe the present invention through embodiment below.
Embodiment 1:
The preparation of pure polyvinyl alcohol nano film: 1, take by weighing 1.6g polyvinyl alcohol (alcoholysis degree is 80%) in the 50mL conical flask, add distilled water, be mixed with the homogeneous transparent solution of 8%wt; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 20 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 10kV, and spinning head is 8cm apart from the distance of receiving pole, receives through 10h and obtains the uniform pure polyvinyl alcohol nano film of thickness; 3, then above-mentioned tunica fibrosa is put into the dry 24h of vacuum drying chamber, fully remove moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 210nm.
Contain the preparation of the polyvinyl alcohol nano film of NaCl (1.0wt%): 1, take by weighing 1.6g polyvinyl alcohol (alcoholysis degree is 80%) and put into the 50mL conical flask; Add distilled water; With the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; Then add 1.0% NaCl, continue dissolving and be stirred to homogeneous transparent; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus; Through conduit solution is incorporated into the constant temperature and humidity temperature device for spinning from syringe, maintains the temperature at 20 ℃ and relative humidity 30%, the spinning solution fltting speed is 0.001mm/s; Spinning voltage is 10kV, receives through 10h and obtains the nano fibrous membrane that thickness contains NaCl1.0wt% uniformly; 3, the film for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 308nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.0MPa; The average ultimate tensile strength that contains the polyvinyl alcohol nano film of 1.0wt%NaCl is: 4.4MPa.Pure polyvinyl alcohol nano film initial decomposition temperature (temperature of correspondence when referring to thermal weight loss 5%, down together) is 250 ℃; The initial decomposition temperature that contains the polyvinyl alcohol nano film of 1.0wt%NaCl is 299 ℃.Above result shows: the heat endurance and the mechanical property that contain the polyvinyl alcohol nano film of NaCl significantly improve.
Embodiment 2:
The preparation of pure polyvinyl alcohol nano film: 1, take by weighing 4.0g polyvinyl alcohol (alcoholysis degree is 99%) in the 50mL conical flask, add distilled water, be mixed with the homogeneous transparent solution of 20%wt; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 45kV, and spinning head is 15cm apart from the distance of receiving pole, receives through 5h and obtains the uniform pure polyvinyl alcohol nano film of thickness; 3, then above-mentioned tunica fibrosa is put into the dry 24h of vacuum drying chamber, fully remove moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 340nm.
Contain the preparation of the polyvinyl alcohol nano film of NaCl (0.001wt%): 1, take by weighing 4g polyvinyl alcohol (alcoholysis degree is 99%) and put into the 50mL conical flask; Add distilled water; With the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; The NaCl that then adds 0.001wt% continues dissolving and is stirred to homogeneous transparent; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 45kV, and spinning head is 15cm apart from the distance of receiving pole, receives through 5h and obtains the polyvinyl alcohol nano film that thickness contains NaCl0.001wt% uniformly.3, the film for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 450nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.8MPa; The average ultimate tensile strength that contains the polyvinyl alcohol nano film of 0.001wt%NaCl is: 4.3MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 270 ℃; The initial decomposition temperature that contains the polyvinyl alcohol nano film of 0.001wt%NaCl is 304 ℃.Above result shows: the heat endurance and the mechanical property that contain the polyvinyl alcohol nano film of NaCl significantly improve.
Embodiment 3:
The preparation of pure polyvinyl alcohol nano film: 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) in the 50mL conical flask, add distilled water, be mixed with the homogeneous transparent solution of 10%wt; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 50 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.005mm/s; Spinning voltage is 30kV, and spinning head is 25cm apart from the distance of receiving pole, receives through 8h and obtains the uniform pure polyvinyl alcohol nano film of thickness; 3, then above-mentioned tunica fibrosa is put into the dry 24h of vacuum drying chamber, fully remove moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 220nm.
Contain the preparation of the polyvinyl alcohol nano film of NaCl (3.0wt%): 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) and put into the 50mL conical flask; Add distilled water; With the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; Then add 3.0% NaCl, continue dissolving and be stirred to homogeneous transparent; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus; Through conduit solution is incorporated into the constant temperature and humidity temperature device for spinning from syringe, maintains the temperature at 30 ℃ and relative humidity 30%, the spinning solution fltting speed is 0.005mm/s; Spinning voltage is 30kV, receives through 8h and obtains the nano fibrous membrane that thickness contains NaCl3.0wt% uniformly; 3, the film for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 285nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.5MPa; The average ultimate tensile strength that contains the polyvinyl alcohol nano film of 3.0wt%NaCl is: 4.2MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 255 ℃; The initial decomposition temperature that contains the polyvinyl alcohol nano film of 3.0wt%NaCl is 297 ℃.Above result shows: the heat endurance and the mechanical property that contain the polyvinyl alcohol nano film of NaCl significantly improve.
Embodiment 4:
The preparation of pure polyvinyl alcohol nano film: 1, take by weighing 1.6g polyvinyl alcohol (alcoholysis degree is 80%) in the 50mL conical flask, add distilled water, be mixed with the homogeneous transparent solution of 8%wt; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, receives through 10h and obtains the uniform pure polyvinyl alcohol nano film of thickness; 3, then above-mentioned tunica fibrosa is put into the dry 24h of vacuum drying chamber, fully remove moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 218nm.
Contain Na
2CO
3The preparation of polyvinyl alcohol nano film (0.3wt%): 1, take by weighing 1.6g polyvinyl alcohol (alcoholysis degree is 80%) and put into the 50mL conical flask, add distilled water, with the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; The Na that then adds 0.3wt%
2CO
3, continue dissolving and be stirred to homogeneous transparent; 2, the solution with above-mentioned preparation adds in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, obtains thickness through 10h and contains Na uniformly
2CO
3The 0.3wt% nano fibrous membrane.3, the tunica fibrosa for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 250nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.3MPa; Contain 0.3wt%Na
2CO
3The average ultimate tensile strength of polyvinyl alcohol nano film be: 4.2MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 245 ℃; Contain 0.3wt% Na
2CO
3The initial decomposition temperature of polyvinyl alcohol nano film be 270 ℃.Above result shows: contain Na
2CO
3The heat endurance and the mechanical property of polyvinyl alcohol nano film significantly improve.
Embodiment 5:
The preparation of pure polyvinyl alcohol nano film: 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) in the 50mL conical flask, add distilled water, be mixed with the homogeneous transparent solution of 10%wt; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, receives through 8h and obtains the uniform pure polyvinyl alcohol nano film of thickness; 3, then above-mentioned tunica fibrosa is put into the dry 24h of vacuum drying chamber, fully remove moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 230nm.
Contain the preparation of the polyvinyl alcohol nano film of KCl (0.3wt%): 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) and put into the 50mL conical flask; Add distilled water; With the stirred in water bath heating 1h of above-mentioned solution, obtain the homogeneous transparent solution of polyvinyl alcohol then at 60 ℃; The KCl that then adds 0.3wt% continues dissolving and is stirred to homogeneous transparent; 2, the solution with above-mentioned preparation adds in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, receives through 8h and obtains the polyvinyl alcohol nano film that thickness contains KCl0.3wt% uniformly.3, the tunica fibrosa for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 280nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.5MPa; The average ultimate tensile strength that contains the polyvinyl alcohol nano film of 0.3wt%KCl is: 4.1MPa.Pure vinal film initial decomposition temperature is 255 ℃; The initial decomposition temperature that contains the polyvinyl alcohol nano film of 0.3wt% KCl is 282 ℃.Above result shows: the heat endurance and the mechanical property that contain the polyvinyl alcohol nano film of KCl significantly improve.
Embodiment 6:
The preparation of pure polyvinyl alcohol nano film: with embodiment 5
Contain Na
2SO
4The preparation of polyvinyl alcohol nano film (0.3wt%): 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) and put into the 50mL conical flask, add distilled water, with the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; The Na that then adds 0.3wt%
2SO
4, continue dissolving and be stirred to homogeneous transparent; 2, the solution with above-mentioned preparation joins in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, and process 8h reception obtains thickness and contains Na uniformly
2SO
4The polyvinyl alcohol nano film of 0.3wt%.3, the tunica fibrosa for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 330nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.5MPa; Contain 0.3wt%Na
2SO
4The average ultimate tensile strength of polyvinyl alcohol nano film be: 4.0MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 255 ℃; Contain 0.3wt% Na
2SO
4The initial decomposition temperature of polyvinyl alcohol nano film be 285 ℃.Above result shows: contain Na
2SO
4The heat endurance and the mechanical property of polyvinyl alcohol nano film significantly improve.
Embodiment 7:
The preparation of pure polyvinyl alcohol nano film: with embodiment 5
Contain NaHCO
3The preparation of polyvinyl alcohol nano film (0.3wt%): 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) and put into the 50mL conical flask, add distilled water, with the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; The NaHCO that then adds 0.3wt%
3, continue dissolving and be stirred to homogeneous transparent; 2, the solution with above-mentioned preparation adds in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, obtains thickness through 8h and contains NaHCO uniformly
3The 0.3wt% nano fibrous membrane.3, the tunica fibrosa for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 315nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.5MPa; Contain 0.3wt% NaHCO
3The average ultimate tensile strength of polyvinyl alcohol nano film be: 3.9MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 255 ℃; Contain 0.3wt% NaHCO
3The initial decomposition temperature of polyvinyl alcohol nano film be 258 ℃.Above result shows: contain NaHCO
3The heat endurance of polyvinyl alcohol nano film obviously do not improve, but mechanical property significantly improves.
Embodiment 8:
The preparation of pure polyvinyl alcohol nano film: with embodiment 5
Contain the preparation of the polyvinyl alcohol nano film of NaOH (0.3wt%): 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) and put into the 50mL conical flask; Add distilled water; With the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; The NaOH that then adds 0.3wt% continues dissolving and is stirred to homogeneous transparent; 2, the solution with above-mentioned preparation adds in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, obtains thickness through 8h and contains the NaOH0.3wt% nano fibrous membrane uniformly.3, the tunica fibrosa for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 308nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.5MPa; The average ultimate tensile strength that contains the polyvinyl alcohol nano film of 0.3wt% NaOH is: 3.8MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 255 ℃; The initial decomposition temperature that contains the polyvinyl alcohol nano film of 0.3wt% NaOH is 280 ℃.Above result shows: the heat endurance and the mechanical property that contain the polyvinyl alcohol nano film of NaOH significantly improve.
Embodiment 9:
The preparation of pure polyvinyl alcohol nano film: with embodiment 5
Contain H
3BO
3The preparation of polyvinyl alcohol nano film (0.3wt%): 1, take by weighing 2g polyvinyl alcohol (alcoholysis degree is 88%) and put into the 50mL conical flask, add distilled water, with the stirred in water bath heating 1h of above-mentioned solution, obtain homogeneous transparent solution then at 60 ℃; The H that then adds 0.3wt%
3BO
3, continue dissolving and be stirred to homogeneous transparent; 2, the solution with above-mentioned preparation adds in the 20mL syringe; Be fixed to then on the propeller of electrostatic spinning apparatus, solution be incorporated into the constant temperature and humidity device for spinning from syringe, maintain the temperature at 30 ℃ and relative humidity 30% through conduit; The spinning solution fltting speed is 0.001mm/s; Spinning voltage is 30kV, and spinning head is 15cm apart from the distance of receiving pole, obtains thickness through 8h and contains H uniformly
3BO
3The 0.3wt% nano fibrous membrane.3, the tunica fibrosa for preparing is put into dry 24h in the vacuum drying chamber, fully removes moisture, and put into drier and deposit subsequent use.Through fibre diameter statistics in the tunica fibrosa stereoscan photograph is learnt that the average diameter of this polyvinyl alcohol nano film is about 356nm.
Tunica fibrosa is carried out extension test and thermogravimetic analysis (TGA): test result shows that the average ultimate tensile strength of pure polyvinyl alcohol nano film is: 2.5MPa; Contain 0.3wt% H
3BO
3The average ultimate tensile strength of polyvinyl alcohol nano film be: 4.1MPa.Pure polyvinyl alcohol nano film initial decomposition temperature is 255 ℃; Contain 0.3wt% H
3BO
3The initial decomposition temperature of polyvinyl alcohol nano film be 290 ℃.Above result shows: contain H
3BO
3The heat endurance and the mechanical property of polyvinyl alcohol nano film significantly improve.
Claims (2)
1. method that improves polyvinyl alcohol electrostatic spinning nano fibrous membrane heat endurance and mechanical property is characterized in that step is following:
The preparation of A, electrostatic spinning solution: adding in the entry PVAC polyvinylalcohol fully, dissolving obtains solution; The concentration of PVA is 8wt% ~ 20wt%; Then sodium chloride, potassium chloride, sodium sulphate, sodium carbonate, sodium acid carbonate, NaOH or boric acid are added above-mentioned solution; Addition is 0.01 wt% ~ 3.0wt%, continues in the interpolation process to stir, and leaves standstill and obtains the homogeneous transparent spinning solution;
B, electrostatic spinning process system film: the spinning solution for preparing is added syringe and is fixed in electrospinning device, carry out spinning; Spinning parameter is: temperature is 20 ~ 50 ℃, and fltting speed is 0.001 ~ 0.005mm/s, and spinning voltage is 10 ~ 45kV, and the spinning syringe needle is 8 ~ 25cm to the distance of dash receiver, receives through 5-10h and obtains thickness uniform fibers film, and is dry under the room temperature.
2. improve the preparation method of polyvinyl alcohol nano film heat endurance and mechanical property according to claim 1, it is characterized in that, the alcoholysis degree scope of used polyvinyl alcohol is 80% ~ 99%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103337338A CN102817178A (en) | 2012-09-10 | 2012-09-10 | Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103337338A CN102817178A (en) | 2012-09-10 | 2012-09-10 | Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102817178A true CN102817178A (en) | 2012-12-12 |
Family
ID=47301601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103337338A Pending CN102817178A (en) | 2012-09-10 | 2012-09-10 | Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102817178A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938366A (en) * | 2014-04-18 | 2014-07-23 | 江南石墨烯研究院 | Method for preparing graphene oxide and polyving akohol composite membrane through electrostatic spinning |
| CN105648653A (en) * | 2016-03-31 | 2016-06-08 | 刘丽娟 | Waterproof polyvinyl alcohol nanofiber membrane and preparation method thereof |
| CN106637492A (en) * | 2016-09-23 | 2017-05-10 | 江西师范大学 | Electrospinning nylon 56/PVA/boric acid composite nanofiber and preparation method thereof |
| CN108169295A (en) * | 2017-10-30 | 2018-06-15 | 上海幂方电子科技有限公司 | Flexible humidity sensor and preparation method thereof |
| CN108560145A (en) * | 2018-03-14 | 2018-09-21 | 上海益好纳米科技有限公司 | A kind of preparation method of sterilization nano fibrous membrane |
| CN108992701A (en) * | 2018-08-17 | 2018-12-14 | 佛山市森昂生物科技有限公司 | A kind of preparation method of nasal packing hemostatic material |
| CN112540074A (en) * | 2019-09-20 | 2021-03-23 | 华南理工大学 | Rapid pesticide residue detection card based on electrostatic spinning method and preparation method and application thereof |
| CN114812661A (en) * | 2021-01-22 | 2022-07-29 | 西安电子科技大学 | Multipoint monitoring optical fiber temperature and humidity sensing probe and preparation method thereof |
| CN115387116A (en) * | 2022-09-02 | 2022-11-25 | 浙江技立新材料股份有限公司 | Biological antibacterial dyeing nanofiber membrane and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921765A (en) * | 1982-07-12 | 1984-02-03 | デイデイエル−ヴエルケ・アクチエンゲゼルシヤフト | Production of fiber blanket needle punched from mineral fiber |
| CN1951987A (en) * | 2006-11-20 | 2007-04-25 | 吉林大学 | Method for preparing low dielectric constant high polymer nanometer fiber membrane using electric spinning method |
| CN101164679A (en) * | 2007-08-10 | 2008-04-23 | 哈尔滨工业大学 | Polyvinylidene fluoride nanometer composite super low pressure ultrafiltering membrane and preparation method thereof |
| CN101892528A (en) * | 2010-06-30 | 2010-11-24 | 苏州大学 | Method for preparing polyvinyl alcohol magnetic film |
| CN102071540A (en) * | 2010-11-17 | 2011-05-25 | 无锡中科光远生物材料有限公司 | Gas sensor fiber membrane and preparation method thereof |
-
2012
- 2012-09-10 CN CN2012103337338A patent/CN102817178A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5921765A (en) * | 1982-07-12 | 1984-02-03 | デイデイエル−ヴエルケ・アクチエンゲゼルシヤフト | Production of fiber blanket needle punched from mineral fiber |
| CN1951987A (en) * | 2006-11-20 | 2007-04-25 | 吉林大学 | Method for preparing low dielectric constant high polymer nanometer fiber membrane using electric spinning method |
| CN101164679A (en) * | 2007-08-10 | 2008-04-23 | 哈尔滨工业大学 | Polyvinylidene fluoride nanometer composite super low pressure ultrafiltering membrane and preparation method thereof |
| CN101892528A (en) * | 2010-06-30 | 2010-11-24 | 苏州大学 | Method for preparing polyvinyl alcohol magnetic film |
| CN102071540A (en) * | 2010-11-17 | 2011-05-25 | 无锡中科光远生物材料有限公司 | Gas sensor fiber membrane and preparation method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103938366A (en) * | 2014-04-18 | 2014-07-23 | 江南石墨烯研究院 | Method for preparing graphene oxide and polyving akohol composite membrane through electrostatic spinning |
| CN105648653A (en) * | 2016-03-31 | 2016-06-08 | 刘丽娟 | Waterproof polyvinyl alcohol nanofiber membrane and preparation method thereof |
| CN105648653B (en) * | 2016-03-31 | 2018-03-13 | 刘丽娟 | A kind of water-resistant polyvinyl alcohol nano fibrous membrane and preparation method thereof |
| CN106637492A (en) * | 2016-09-23 | 2017-05-10 | 江西师范大学 | Electrospinning nylon 56/PVA/boric acid composite nanofiber and preparation method thereof |
| CN106637492B (en) * | 2016-09-23 | 2019-04-16 | 江西师范大学 | Electrospinning nylon 56/PVA/ boric acid composite nano fiber and preparation method thereof |
| CN108169295A (en) * | 2017-10-30 | 2018-06-15 | 上海幂方电子科技有限公司 | Flexible humidity sensor and preparation method thereof |
| CN108560145A (en) * | 2018-03-14 | 2018-09-21 | 上海益好纳米科技有限公司 | A kind of preparation method of sterilization nano fibrous membrane |
| CN108992701A (en) * | 2018-08-17 | 2018-12-14 | 佛山市森昂生物科技有限公司 | A kind of preparation method of nasal packing hemostatic material |
| CN112540074A (en) * | 2019-09-20 | 2021-03-23 | 华南理工大学 | Rapid pesticide residue detection card based on electrostatic spinning method and preparation method and application thereof |
| CN114812661A (en) * | 2021-01-22 | 2022-07-29 | 西安电子科技大学 | Multipoint monitoring optical fiber temperature and humidity sensing probe and preparation method thereof |
| CN115387116A (en) * | 2022-09-02 | 2022-11-25 | 浙江技立新材料股份有限公司 | Biological antibacterial dyeing nanofiber membrane and preparation method thereof |
| CN115387116B (en) * | 2022-09-02 | 2023-08-22 | 浙江技立新材料股份有限公司 | Biological antibacterial dyed nanofiber membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102817178A (en) | Method for improving heat stability and mechanical property of polyvinyl alcohol nanofiber membrane | |
| CN104289042B (en) | A kind of electrostatic spinning nano fiber electret filtering material and preparation method thereof | |
| CN106362601B (en) | A kind of nano fibrous membrane filtering material and preparation method thereof with antibacterial functions | |
| CN109572082B (en) | Composite fiber membrane capable of being used for high-efficiency low-resistance anti-haze mask | |
| CN100376623C (en) | Process for preparing chitosan nano fiber film with stable state | |
| Li et al. | Fabrication and characterization of electrospun wool keratin/poly (vinyl alcohol) blend nanofibers | |
| CN107675359B (en) | A kind of Propiram/sodium alginate composite fiber film and its preparation method and application | |
| CN103483606A (en) | Preparation method of bacterial cellulose composite polymer superfine fiber material | |
| CN103173892A (en) | Preparation method of nano bamboo fiber composite material | |
| Dadol et al. | Solution blow spinning–polyacrylonitrile–assisted cellulose acetate nanofiber membrane | |
| CN104562292A (en) | Preparation method of porous micro-nano PET fibers | |
| CN101003917A (en) | Complex type electrostatic spinning method with positive and negative electrodes in same electric field, and application | |
| CN101838888A (en) | Method for preparing electrospun meta-aramid nano-fiber | |
| CN109438887B (en) | Nanofiber aerogel with photo-thermal conversion, sound insulation, heat insulation and good mechanical recovery and preparation method thereof | |
| CN111020745A (en) | Preparation method of sodium alginate and chitosan composite nanofiber | |
| KR20080075627A (en) | Method for producing cellulose nano fiber | |
| Susanto et al. | Impact of post-treatment on the characteristics of electrospun poly (vinyl alcohol)/chitosan nanofibers | |
| CN104480560A (en) | Electrostatic spinning solution of polyvinylidene fluoride and preparation method of electrostatic spinning solution | |
| CN109232993A (en) | A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball | |
| JP4992024B2 (en) | Chitosan ultrafine fiber and method for producing the same | |
| CN104928789A (en) | Porous nano-fiber prepared by combining electrostatic spinning with anti-solvent technology and preparing method | |
| Htike et al. | The effect of relative humidity on electrospinning ofpoly-(vinyl alcohol) with soluble eggshell membrane | |
| Liu et al. | Properties of hydrophilic chitosan/polysulfone nanofibrous filtration membrane | |
| CN105887228B (en) | The preparation method of porous Diacetate cellulose tow is produced using ultraviolet light auxiliary dry spinning | |
| CN111648044A (en) | Super-absorbent nanofiber membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121212 |