CN104928848A - Macroscopic quantity preparation method for macromolecule-based silver-loaded composite nanofiber membrane - Google Patents
Macroscopic quantity preparation method for macromolecule-based silver-loaded composite nanofiber membrane Download PDFInfo
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Abstract
The invention relates to a macroscopic quantity preparation method for a macromolecule-based silver-loaded composite nanofiber membrane. The method comprises the steps of a spinning solution preparation step, an electrostatic spinning step and precursor reduction. According to the prepared macromolecule-based silver-loaded composite nanofiber membrane, the sizes of silver nanoparticles are stable, obvious agglomeration does not exist, and the distribution is even; the macromolecule-based silver-loaded composite nanofiber membrane has the advantages that the fiber length-diameter ratio is big, and the specific surface area is higher; therefore, the contact ratio of nano-silver and noxious bacteria in fiber is greatly increased, and the antibacterial effect of the nano-silver can be exerted to the maximum extent.
Description
Technical field
The present invention relates to the preparation in macroscopic quantity method of a kind of macromolecule base load silver composite nano-fiber membrane, belong to technical field of nanometer material preparation.
Background technology
Nano-powder material, due to the feature such as skin effect, quantum size effect, makes material itself usually have the special nature totally different with its macroscopic material.All the time, Nano Silver is used as efficacious anti-microbial material because of the chemical stability of its excellence and catalytic activity, has broad-spectrum antiseptic, safety and stability, does not produce the features such as drug resistance.And for macromolecule base load silver composite nano fiber, because nanofiber has, specific area is large, porosity high, thus add the contact ratio of nano particle and harmful bacteria in fiber greatly, farthest can play the antibacterial effect of Nano Silver, the antibacterial ion rate of release of this kind of material can be controlled by the structure adjusting carrier simultaneously, thus make it have long-acting antibacterial effect, thus in the application prospect that the fields such as biochemistry protection, health care, filtration have traditional fibre incomparable.
In recent years, utilize electrostatic spinning technique, metal nanoparticle is incorporated into the method preparing composite nano fiber in macromolecular fibre and receives much concern.At present, electrostatic spinning prepare macromolecule base load silver composite nano fiber method mainly contain Direct dispersion method and local reduction way.Direct dispersion method refers to and is first distributed in Polymer Solution by Nano Silver, what the method again by adding the dispersion of suitable surfactant, high-speed stirred or ultrasonic wave made Nano Silver uniform and stable is dispersed in spinning precursor solution, last electro-spinning, can see Chinese patent document CN104511045A (application number: 201310441908.1) for composite nano fiber.Although this method technique is simple, but nano silver powder need through long-time dispersion, and nano particle has very high specific surface energy usually, therefore in electrostatic spinning process, Nano Silver is easily reunited, dispersion effect is not good in the fibre to make Nano Silver, thus cause it functionally to weaken, even disappear.And in-situ synthesis refers to containing in silver ion and high molecular mixed solution, by functional group specific in macromolecule to the Absorptive complex wave effect of silver ion or macromolecular chain to silver ion move sterically hindered, and the nano level restricted quarter that macromolecule matrix provides, recycling heating or Ultraviolet radiation, sodium borohydride, citric acid etc. carry out in-situ reducing and prepare macromolecule base load silver composite nano fiber, can see Polymer.2008,49,4723-4732; Chinese patent document CN103705969A (application number: 201410001923.9); CN103433035A (application number: 201310298036.8); CN101187111B (application number: 200710171324.1).In the composite nano fiber utilizing in-situ synthesis to prepare, Nano Silver dimensionally stable, is evenly distributed, and is combined well with matrix fiber.But up to now, also do not utilize the method for in-situ synthesis preparation in macroscopic quantity macromolecule base load silver composite nano-fiber membrane to be seen in patent and bibliographical information.
Summary of the invention
For the deficiencies in the prior art, the invention provides one and utilize in-situ synthesis, prepare to magnanimity the method for macromolecule base load silver composite nano-fiber membrane, solve in prior art and carry comparatively large, the easy reunion in silver granuel footpath, skewness, anti-microbial property is unstable, and composite fibre film dynamic performance is poor, cannot the problem of large-scale production.
Technical scheme of the present invention is as follows:
A preparation in macroscopic quantity method for PA/Ag composite nano-fiber membrane, comprises step as follows:
(1) spinning solution preparation
Formic acid solution and glacial acetic acid are mixed, adds nylon (PA) particle under stirring, be stirred to nylon and dissolve completely, then add AgNO
3, lucifuge is stirred to AgNO
3dissolve completely, obtain spinning solution;
In spinning solution, described nylon concentration is 10 ~ 15wt%, and described formic acid concn is 25 ~ 55wt%; Formic acid solution: glacial acetic acid=1:3 ~ 3:1, mass ratio; AgNO
3addition account for 0.3% ~ 2% of nylon quality;
(2) electrostatic spinning
Step (1) gained spinning solution is carried out electrostatic spinning, and condition is: spinning voltage 55 ~ 80kV, electrode distance 100 ~ 220mm, temperature 15 ~ 30 DEG C, and relative humidity 15 ~ 60%, obtains nanofiber film precursor;
(3) presoma reduction
By step (2) gained nanofiber film precursor in 60 ~ 150 DEG C of heating 6 ~ 12h; Or, irradiate 10 ~ 60min under ultraviolet light, obtain PA/Ag composite nano-fiber membrane.
According to the present invention, preferably, the nylon concentration described in step (1) is 12 ~ 14wt%, and described formic acid concn is 25 ~ 50wt%; Formic acid solution: glacial acetic acid=1:2 ~ 2:1, mass ratio; AgNO
3addition account for 0.5% ~ 1.2% of nylon quality;
Preferably, described nylon is nylon 6, and the concentration of described formic acid solution is 88wt%.The spinning solution of step (1) gained can slowly become faint yellow with prolongation standing time, shows AgNO
3partial reduction is Nano Silver.
According to the present invention, preferably, in step (2), electrospinning conditions is: voltage 60 ~ 70kV, electrode distance 150 ~ 180mm, temperature 20 ~ 25 DEG C, relative humidity 30 ~ 45%.
According to the present invention, preferably, in step (3), heating-up temperature is 90 ~ 120 DEG C, and the UV-irradiation time is 20 ~ 40min;
Preferably, the intensity of ultraviolet light is 30 ~ 100w, and wavelength is 190 ~ 260nm.
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
By AgNO
3join in DMF (DMF), stir under lucifuge condition and make AgNO
3dissolve completely, then add PAN (polyacrylonitrile), continue lucifuge and stir 10 ~ 15h, obtain spinning solution;
Described AgNO
3: DMF:PAN=(0.05 ~ 0.8): (8 ~ 9.15): (0.6 ~ 1.2), mass ratio;
(ii) electrostatic spinning
The spinning solution electrostatic spinning that step (i) is obtained, condition is: relative humidity 15 ~ 50%, temperature 15 ~ 30 DEG C, spinning voltage is 15 ~ 25kV, feed rate is 0.4 ~ 1.2mL/h, receiving range between spinning syringe needle and metal plate receiver is 15 ~ 30cm, obtains nanofiber film precursor;
(iii) presoma reduction
By nanofiber film precursor heat treatment 0.5 ~ 4h at the temperature of 60 ~ 200 DEG C obtained in step (ii), naturally cool; Or, irradiate 0.5 ~ 4h under ultraviolet light, obtain PAN/Ag composite nano-fiber membrane.
According to the present invention, preferably, the AgNO described in step (i)
3: DMF:PAN=(0.2 ~ 0.8): (8.2 ~ 9.0): (0.8 ~ 1.0), mass ratio;
Preferably, the relative molecular weight of described PAN is 70,000.
According to the present invention, preferably, in step (ii), electrospinning conditions is: relative humidity 25 ~ 40%, temperature 20 ~ 30 DEG C, spinning voltage is 18 ~ 21kV, receiving range between spinning syringe needle and metal plate receiver is 20 ~ 30cm, and the feed rate of electrostatic spinning is 0.5 ~ 1.2mL/h.
According to the present invention, preferably, in step (iii), heat treatment temperature is 80 ~ 160 DEG C, and the intensity of ultraviolet light is 30 ~ 100w, and wavelength is 190 ~ 260nm.
PA/Ag or the PAN/Ag composite nano-fiber membrane thickness utilizing the inventive method to prepare is homogeneous, and fibre diameter is stablized, and nano-Ag particles particle diameter is less and be evenly distributed, and shows excellent anti-microbial property.
Technical characterstic of the present invention and excellent results as follows:
1, in the macromolecule base load silver composite nano-fiber membrane that prepared by the present invention, nano silver particles dimensionally stable, does not significantly reunite, and is evenly distributed;
2, the macromolecule base load silver composite nano-fiber membrane that prepared by the present invention has that Fiber Aspect Ratio is large, specific area comparatively advantages of higher, thus add the contact ratio of Nano Silver and harmful bacteria in fiber greatly, farthest can play the antibacterial effect of Nano Silver;
3, the present invention utilizes the method for heating or ultraviolet reduction to carry out reduced nano tunica fibrosa presoma, and the simple efficiency of technique is high, can not destroy the original appearance structure of fiber;
4, the macromolecule base load silver composite nano-fiber membrane excellent in mechanical performance prepared of the present invention, Heat stability is good, can carry out preparation in macroscopic quantity.
Accompanying drawing explanation
Fig. 1 is the SEM photo of embodiment 1 gained PA/Ag composite nano-fiber membrane.
Fig. 2 is the SEM photo of embodiment 2 gained PA/Ag composite nano-fiber membrane.
Fig. 3 is the TEM photo of gained nanofiber film precursor in step (2) in embodiment 2.
Fig. 4 is the TEM photo of embodiment 1 gained PA/Ag composite nano-fiber membrane.
Fig. 5 is the TEM photo of embodiment 3 gained PA/Ag composite nano-fiber membrane.
Fig. 6 is the EDS spectrogram of embodiment 5 gained PA/Ag composite nano-fiber membrane.
Fig. 7 is the anti-microbial property optical photograph of embodiment 1 gained PA/Ag composite nano-fiber membrane, and wherein a vibrates after sterilization control sample " 1h " contact time, and b to vibrate for experiment after sterilization sample " 1h " contact time.
Fig. 8 is the TEM photo of embodiment 6 gained PAN/Ag composite nano-fiber membrane.
Fig. 9 is the SEM photo of embodiment 6 gained PAN/Ag composite nano-fiber membrane.
Figure 10 is the XRD spectra of embodiment 6 gained PAN/Ag composite nano-fiber membrane.
Figure 11 is the surperficial Argent grain diameter distribution profile of embodiment 6 gained PAN/Ag composite nano-fiber membrane.
Figure 12 is the TG-DSC curve of embodiment 10 gained PAN/Ag composite nano-fiber membrane.
Figure 13 is the anti-microbial property optical photograph of embodiment 11 gained PAN/Ag composite nano-fiber membrane, and wherein a vibrates after sterilization control sample " 1h " contact time, and b to vibrate for experiment after sterilization sample " 1h " contact time.
Figure 14 is the SEM photo of PAN/Ag composite nano-fiber membrane before and after sterilization of embodiment 12 gained, and wherein a is for before experiment sample vibration sterilization, and b is after testing sterilization of vibrating sample " 1h " contact time.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention will be further described, but be not limited thereto.Raw materials usedly in embodiment be convenient source, device therefor is conventional equipment.
Wherein the anti-microbial property of macromolecule base load silver composite nano-fiber membrane is tested according to GB/T 21510-2008 nano inorganic material bactericidal property detection method Appendix B, and adopts shake-flask method.
Embodiment 1
A preparation in macroscopic quantity method for PA/Ag composite nano-fiber membrane, comprises step as follows:
(1) spinning solution preparation
Be that aqueous formic acid and the 293.4g glacial acetic acid of 88wt% mixes by 146.7g concentration, add 60g nylon 6 particle under stirring, be stirred to nylon 6 and dissolve completely, then add 0.6g AgNO
3rear lucifuge is stirred to AgNO
3dissolve completely, obtain achromaticity and clarification spinning solution;
In spinning solution, the concentration of described nylon 6 is 12wt%, and described formic acid concn is 25.8wt%; Aqueous formic acid: glacial acetic acid=1:2, mass ratio; AgNO
3addition account for 1% of nylon 6 quality;
(2) electrostatic spinning
Use the electrospinning device Nano Spider NS LAB 500 of Elmarco company to carry out electrostatic spinning, the spinning solution of preparation in step (1) is poured in spinning tank, adopt rotating metallic silk electrode to carry out spinning; Electrospinning conditions is: voltage 70kV, electrode distance 170mm, temperature 25 DEG C, relative humidity 40%, and base material translational speed 1.2m/min, obtains nanofiber film precursor;
(3) presoma reduction
Step (2) gained nanofiber film precursor is put into 120 DEG C, baking oven heating 2h, obtain PA/Ag composite nano-fiber membrane.
In heating process, tunica fibrosa slowly becomes yellowish-brown from white, shows the formation of Ag nano particles.As shown in Figure 1, as shown in Figure 1, the uniform diameter of PA/Ag composite nano fiber, average diameter is about 90nm to the SEM photo of gained PA/Ag composite nano fiber.As shown in Figure 4, as shown in Figure 4, in fiber, Ag nano particles is evenly distributed the TEM photo of gained PA/Ag composite nano fiber, and particle diameter is 2 ~ 5nm.
The anti-microbial property of PA/Ag composite nano-fiber membrane is evaluated according to the method for Appendix B in GB/T 21510-2008, take the present embodiment as experiment sample, with the PA tunica fibrosa not containing nanometer Ag for control sample, experiment sample and control sample are carried out sterilization of vibrating " 1h " contact time, the optical photograph of test result as shown in Figure 7, wherein: a is control sample, b is experiment sample.As shown in Figure 7, the bacteriostasis rate 100% of PA/Ag composite nano-fiber membrane that obtains of the present embodiment.
Embodiment 2
As described in Example 1, difference is:
In step (1), concentration is the aqueous formic acid of 88wt% is 145g, glacial acetic acid 290g, aqueous formic acid: glacial acetic acid=1:2, mass ratio, and the quality of nylon 6 is 65g;
In spinning solution, nylon 6 concentration is 13wt%, and formic acid concn is 25.5wt%; AgNO
3quality be 0.65g, account for 1% of nylon 6 quality;
Step (2) is with embodiment 1;
Step (3) is with embodiment 1.
Existing part AgNO in the present embodiment step (2) gained composite nano-fiber membrane presoma
3be reduced to nanometer Ag, as shown in Figure 3.
As shown in Figure 2, as shown in Figure 2, PA/Ag composite nano fiber uniform diameter, average diameter is about 90nm to the present embodiment gained PA/Ag composite nano fiber SEM photo.In fiber, Ag nano particles is evenly distributed, and particle diameter is 2 ~ 5nm.
The bacteriostasis rate 100% of the PA/Ag composite nano-fiber membrane that the present embodiment obtains.
Embodiment 3
As described in Example 1, difference is:
In step (1), concentration is the aqueous formic acid of 88wt% is 145g, glacial acetic acid 290g, aqueous formic acid: glacial acetic acid=1:2, mass ratio, and the quality of nylon 6 is 65g;
In spinning solution, nylon 6 concentration is 13wt%, and formic acid concn is 25.5wt%; AgNO
3quality be 0.78g, account for 1.2% of nylon 6 quality;
Step (2) is with embodiment 1;
By step (2) gained composite nano-fiber membrane presoma UV-irradiation time 1h in step (3), wherein the intensity of ultraviolet light is 30w, and wavelength is 254nm.In irradiation process, tunica fibrosa slowly becomes yellowish-brown from white, shows the formation of Ag nano particles.
The present embodiment gained PA/Ag composite nano fiber uniform diameter, average diameter 90nm.As shown in Figure 5, as shown in Figure 5, in fiber, Ag nano particles is evenly distributed the TEM photo of the PA/Ag composite nano-fiber membrane that the present embodiment obtains, and particle diameter is 2 ~ 5nm.
The bacteriostasis rate 100% of the PA/Ag composite nano-fiber membrane that the present embodiment obtains.
Embodiment 4
As described in Example 1, difference is:
In step (1), concentration is the aqueous formic acid of 88wt% is 217.5g, glacial acetic acid 217.5g, aqueous formic acid: glacial acetic acid=1:1, mass ratio, and the quality of nylon 6 is 65g;
In spinning solution, nylon 6 concentration is 13wt%, and formic acid concn is 38.2wt%; AgNO
3quality be 0.65g, account for 1% of nylon 6 quality;
Step (2) is with embodiment 1;
Step (3) is with embodiment 3.
Gained PA/Ag composite nano fiber uniform diameter, average diameter is about 80nm; In fiber, Ag nano particles is evenly distributed, and particle diameter is 2 ~ 5nm.
The bacteriostasis rate 100% of the PA/Ag composite nano-fiber membrane that the present embodiment obtains.
Embodiment 5
As described in Example 1, difference is:
In step (1), concentration is the aqueous formic acid of 88wt% is 286.7g, glacial acetic acid 143.3g, aqueous formic acid: glacial acetic acid=2:1, mass ratio, and the quality of nylon 6 is 70g;
In spinning solution, nylon 6 concentration is 14wt%, and formic acid concn is 50.4wt%; AgNO
3quality be 0.35g, account for 0.5% of nylon 6 quality;
In step (2), electrospinning conditions is: voltage 60kV, electrode distance 200mm;
Step (3) is with embodiment 1.
Gained PA/Ag composite nano fiber uniform diameter, average diameter is about 100nm; In fiber, Ag nano particles is evenly distributed, and particle diameter is 2 ~ 5nm.
The bacteriostasis rate 100% of the PA/Ag composite nano-fiber membrane that the present embodiment obtains.
The EDS spectrogram of gained PA/Ag composite nano-fiber membrane as shown in Figure 6, as shown in Figure 6, is got at random in EDS spectrogram a little and is shown containing C, N, O, Ag tetra-kinds of elements in fiber, and in spectrogram, Au element is that in sample making course, metal spraying is introduced.
Embodiment 6
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.8g AgNO
3be dissolved in 8.2g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 8%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 30cm, feed rate is 0.5mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3nanofiber film precursor tiling expansion is placed in baking oven, heat treatment 2h at 120 DEG C, and naturally cools, and obtains PAN/Ag composite nano-fiber membrane.
The PAN/AgNO that the present embodiment is obtained
3the TEM photo of composite nano-fiber membrane, as shown in Figure 8; SEM photo as shown in Figure 9.From Fig. 8,9, gained PAN/Ag composite nano fiber uniform diameter, average diameter is 80nm; Fiber morphology is complete, does not have fibrous fracture and tiny slag ball.
As shown in Figure 10, fiber surface Argent grain diameter distribution profile as shown in figure 11 for the XRD spectra of the PAN/Ag composite nano-fiber membrane that the present embodiment obtains.From Figure 10,11, in composite cellulosic membrane, Nano Silver degree of crystallinity is lower, and nano-Ag particles size is less, and fiber surface Argent grain is uniformly dispersed, and average diameter is 5nm.
Embodiment 7
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.1g AgNO
3be dissolved in 8.9g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 1%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 30cm, feed rate is 0.5mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3nanofiber film precursor tiling expansion is placed in baking oven, heat treatment 2h at 120 DEG C, and naturally cools, and obtains PAN/Ag composite nano-fiber membrane.
Embodiment 8
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.2g AgNO
3be dissolved in 8.8g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 2%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 30cm, feed rate is 0.5mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3nanofiber film precursor tiling expansion is placed in baking oven, heat treatment 2h at 120 DEG C, and naturally cools, and obtains PAN/Ag composite nano-fiber membrane.
Embodiment 9
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.4g AgNO
3be dissolved in 8.6g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 4%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 30cm, feed rate is 0.5mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3nanofiber film precursor tiling expansion is placed in baking oven, heat treatment 2h at 120 DEG C, and naturally cools, and obtains PAN/Ag composite nano-fiber membrane.
Embodiment 10
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.6g AgNO
3be dissolved in 8.4g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 6%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 30cm, feed rate is 0.5mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3nanofiber film precursor tiling expansion is placed in baking oven, heat treatment 2h at 120 DEG C, and naturally cools, and obtains PAN/Ag composite nano-fiber membrane.
The TG-DSC curve of the PAN/Ag composite nano-fiber membrane that the present embodiment obtains, as shown in figure 12, the better heat stability of PAN/Ag nano fibrous membrane as shown in Figure 12, can use in the environment of higher temperature.
Embodiment 11
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.8g AgNO
3be dissolved in 8.2g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 8%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 30cm, feed rate is 0.5mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3irradiate 2h under nanofiber film precursor tiling expansion is positioned over uviol lamp, wherein the intensity of ultraviolet light is 30w, and wavelength is 254nm, obtains PAN/Ag composite nano-fiber membrane.
The anti-microbial property of PAN/Ag composite nano-fiber membrane is evaluated according to the method for Appendix B in GB/T 21510-2008, take the present embodiment as experiment sample, with the PAN tunica fibrosa not containing nanometer Ag for control sample, experiment sample and control sample are carried out sterilization of vibrating " 1h " contact time, the optical photograph of test result as shown in figure 13, wherein: a is control sample, b is experiment sample.As shown in Figure 13, the bacteriostasis rate of PAN/Ag nano fibrous membrane is 100%, and this illustrates that the PAN/Ag nano fibrous membrane anti-microbial property of preparation is excellent.
Embodiment 12
A preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
Take 0.8g AgNO
3be dissolved in 8.2g DMF, stir under lucifuge condition and make AgNO
3rapid solution, and then add 1g PAN, continue lucifuge stirring 12h and obtain AgNO
3mass fraction is the spinning solution of 8%;
(ii) electrostatic spinning
Spinning solution obtained for step (i) is joined in the plastic injector of about 10mL, then the relative humidity that controls environment is 30%, temperature is 20 DEG C, adjustment spinning voltage is 20kV, receiving range between spinning syringe needle and metal plate receiver is 25cm, feed rate is 0.8mL/h, and electrospinning obtains PAN/AgNO
3nanofiber film precursor;
(iii) presoma reduction
By PAN/AgNO obtained in step (ii)
3nanofiber film precursor tiling expansion is placed in baking oven, heat treatment 2h at 80 DEG C, and naturally cools, and obtains PAN/Ag composite nano-fiber membrane.
The PAN/Ag composite nano-fiber membrane of the present embodiment gained SEM photo before and after sterilization as shown in figure 14.As shown in Figure 14, scale topography and the structure of nanofiber do not change before and after sterilization, and this illustrates that PAN/Ag nano fibrous membrane has good structural stability and reusability.
Claims (10)
1. a preparation in macroscopic quantity method for PA/Ag composite nano-fiber membrane, comprises step as follows:
(1) spinning solution preparation
Formic acid solution and glacial acetic acid are mixed, adds nylon (PA) particle under stirring, be stirred to nylon and dissolve completely, then add AgNO
3, lucifuge is stirred to AgNO
3dissolve completely, obtain spinning solution;
In spinning solution, described nylon concentration is 10 ~ 15wt%, and described formic acid concn is 25 ~ 55wt%; Formic acid solution: glacial acetic acid=1:3 ~ 3:1, mass ratio; AgNO
3addition account for 0.3% ~ 2% of nylon quality;
(2) electrostatic spinning
Step (1) gained spinning solution is carried out electrostatic spinning, and condition is: spinning voltage 55 ~ 80kV, electrode distance 100 ~ 220mm, temperature 15 ~ 30 DEG C, and relative humidity 15 ~ 60%, obtains nanofiber film precursor;
(3) presoma reduction
By step (2) gained nanofiber film precursor in 60 ~ 150 DEG C of heating 6 ~ 12h; Or, irradiate 10 ~ 60min under ultraviolet light, obtain PA/Ag composite nano-fiber membrane.
2. the preparation in macroscopic quantity method of PA/Ag composite nano-fiber membrane according to claim 1, is characterized in that, the nylon concentration described in step (1) is 12 ~ 14wt%, and described formic acid concn is 25 ~ 50wt%; Formic acid solution: glacial acetic acid=1:2 ~ 2:1, mass ratio; AgNO
3addition account for 0.5% ~ 1.2% of nylon quality.
3. the preparation in macroscopic quantity method of PA/Ag composite nano-fiber membrane according to claim 1, is characterized in that, the nylon described in step (1) is nylon 6, and the concentration of described formic acid solution is 88wt%.
4. the preparation in macroscopic quantity method of PA/Ag composite nano-fiber membrane according to claim 1, it is characterized in that, in step (2), electrospinning conditions is: voltage 60 ~ 70kV, electrode distance 150 ~ 180mm, temperature 20 ~ 25 DEG C, relative humidity 30 ~ 45%.
5. the preparation in macroscopic quantity method of PA/Ag composite nano-fiber membrane according to claim 1, is characterized in that, in step (3), heating-up temperature is 90 ~ 120 DEG C, and the UV-irradiation time is 20 ~ 40min.
6. the preparation in macroscopic quantity method of PA/Ag composite nano-fiber membrane according to claim 1, is characterized in that, the intensity of step (3) medium ultraviolet light is 30 ~ 100w, and wavelength is 190 ~ 260nm.
7. a preparation in macroscopic quantity method for PAN/Ag composite nano-fiber membrane, comprises step as follows:
Prepared by (i) spinning solution
By AgNO
3join in DMF (DMF), stir under lucifuge condition and make AgNO
3dissolve completely, then add PAN (polyacrylonitrile), continue lucifuge and stir 10 ~ 15h, obtain spinning solution;
Described AgNO
3: DMF:PAN=(0.05 ~ 0.8): (8 ~ 9.15): (0.6 ~ 1.2), mass ratio;
(ii) electrostatic spinning
The spinning solution electrostatic spinning that step (i) is obtained, condition is: relative humidity 15 ~ 50%, temperature 15 ~ 30 DEG C, spinning voltage is 15 ~ 25kV, feed rate is 0.4 ~ 1.2mL/h, receiving range between spinning syringe needle and metal plate receiver is 15 ~ 30cm, obtains nanofiber film precursor;
(iii) presoma reduction
By nanofiber film precursor heat treatment 0.5 ~ 4h at the temperature of 60 ~ 200 DEG C obtained in step (ii), naturally cool; Or, irradiate 0.5 ~ 4h under ultraviolet light, obtain PAN/Ag composite nano-fiber membrane.
8. the preparation in macroscopic quantity method of PAN/Ag composite nano-fiber membrane according to claim 7, is characterized in that, the AgNO described in step (i)
3: DMF:PAN=(0.2 ~ 0.8): (8.2 ~ 9.0): (0.8 ~ 1.0), mass ratio;
Preferably, the relative molecular weight of described PAN is 70,000.
9. the preparation in macroscopic quantity method of PAN/Ag composite nano-fiber membrane according to claim 7, it is characterized in that, in step (ii), electrospinning conditions is: relative humidity 25 ~ 40%, temperature 20 ~ 30 DEG C, spinning voltage is 18 ~ 21kV, receiving range between spinning syringe needle and metal plate receiver is 20 ~ 30cm, and feed rate is 0.5 ~ 1.2mL/h.
10. the preparation in macroscopic quantity method of PAN/Ag composite nano-fiber membrane according to claim 7, is characterized in that, in step (iii), heat treatment temperature is 80 ~ 160 DEG C, and the intensity of ultraviolet light is 30 ~ 100w, and wavelength is 190 ~ 260nm.
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