CN104233511B - A kind of coaxial electrostatic spinning prepares the method for electrum fiber - Google Patents
A kind of coaxial electrostatic spinning prepares the method for electrum fiber Download PDFInfo
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- CN104233511B CN104233511B CN201410546060.3A CN201410546060A CN104233511B CN 104233511 B CN104233511 B CN 104233511B CN 201410546060 A CN201410546060 A CN 201410546060A CN 104233511 B CN104233511 B CN 104233511B
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Abstract
A kind of coaxial electrostatic spinning prepares the method for electrum nanofiber, the present invention relates to the preparation method of metal nano fiber, the problem of metallic arrangement defective tightness in the electrum nanofiber that it prepares to solve existing method.Preparation method: one, be dissolved in solvent by polyvinyl alcohol, prepares shell layer spinning solution；Two, during silver nitrate is dissolved in solvent, it is subsequently adding gold chloride, after being heated to boiling, adds reducing agent, dialyse after distillation and concentration, obtain stratum nucleare spinning liquid；Three, with poly-vinyl alcohol solution for outer shaft solution, being interior axle solution with gold-silver alloy nanoparticles solution, regulation spinning parameter carries out coaxial electrostatic spinning；Four, core-shell nano fiber is placed in heating anneal in Muffle furnace process, completes the preparation of electrum nanofiber.The electrum nanofiber surface that the present invention prepares is smooth, gold-silver alloy nanoparticles close-packed arrays.
Description
Technical field
The present invention relates to the preparation method of a kind of alloy fiber, particularly relate to coaxial electrostatic spinning method and prepare electrum fibre
The method of dimension.
Background technology
Nearly ten years, one-dimensional nano structure material such as alloy nano fiber, nanotube, nano belt, nano wire and nano-cable
Deng, they are different from corresponding body material and the novelty of other form nanometer material structure owing to showing at aspects such as electricity, light, magnetic
Feature and they receive much concern in basic research and the important value of high-technology field application aspect, future novel
The nano structure devices such as electricity, magnetic occupy important strategic status.
At present, utilize prepared by electrostatic spinning to have copper nano-wire, cobalt nanowire and SiC/C nano fibrous membrane etc., existing method
As template assisting growth solvent-thermal process and melt spinning and dry spinning etc. are developed for design and synthesizing magnetic nanometer
Structural material, but there is complex process in these preparation methoies, or the nanofiber of preparation is short, metallic arrangement is the tightest
The shortcoming such as close, thus cause the reduction of nanofiber electric conductivity.Coaxial electrostatic spinning is to utilize high polymeric solution or the melt to be
Shell layer spinning solution and alloy nano particle solution are sandwich layer spinning liquid, and its principle is in electro-spinning process, and shell viscosity solution exists
High voltage electric field drive sandwich layer solution to form coaxial jet, this coaxial jet by sandwich layer solution is formed " frictional shearing "
Flow deformation in high-voltage electrostatic field, solidifies through solvent volatilization cooling or melt cooling, thus obtains core-shell nano fiber
A kind of method.
Summary of the invention
The invention aims to solve metallic arrangement defective tightness in the metallic alloy fiber that existing method prepares
Problem, and provide a kind of method that coaxial electrostatic spinning prepares electrum fiber.
Coaxial electrostatic spinning of the present invention is prepared the method for electrum fiber and is followed these steps to realize:
One, being dissolved in solvent a by polyvinyl alcohol, be heated to 50～100 DEG C, stirring obtains shell layer spinning solution to dissolving；
Two, the silver nitrate of 0.0037g～0.0222g is dissolved in the solvent b of 10～60mL, add after fully dissolving 2～
6mL mass concentration is the chlorauric acid solution of 1%, adds solvent b reactant liquor is diluted to 90～540mL after stirring,
Reactant liquor is placed in reaction vessel and is heated to boiling in oil bath pan and keeps 2～10min, is subsequently adding 10～100mL matter
Amount concentration is the reducing agent of 1%, continues to seethe with excitement 30～50min, add 5～20ml mass concentrations be 5%～
After 10%PVA solution, distillation and concentration is to 10～50mL, and concentrated solution dialyses 22～26h with bag filter, repeatedly changes water 3～4 times,
Obtain stratum nucleare spinning liquid；
Three, the shell layer spinning solution that step one obtains is placed in the outer tube of coaxial electrostatic spinning silk device, the core that step 2 is obtained
Layer spinning liquid be placed in the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage be 13～25kv, relative humidity be 10%～
30%, indoor temperature is 15～25 DEG C, and receiving range is 10～25cm, stratum nucleare spinning liquid and shell layer spinning solution fltting speed
Ratio be (1～0.1): 1 carries out coaxial electrostatic spinning, obtains electrum-PVA core-shell nano fiber；
Four, electrum-PVA core-shell nano fiber step 3 obtained is placed in Muffle furnace, is warming up to 300 DEG C and protects
Temperature 6～7h, then proceedes to be warming up to 400～600 DEG C, naturally cools to room temperature with body of heater, obtain gold silver after insulation 1～2h
Alloy nano fiber.
The present invention utilizes coaxial electrostatic spinning method to be prepared for electrum-PVA nuclear fibre, and electrum-PVA nucleocapsid is received
The stratum nucleare of rice fiber is gold-silver alloy nanoparticles solution, and shell is PVA solution, obtains after core-shell nano fiber is fired
Single shaft electrum fiber.The single favorable dispersibility of electrum fiber that the present invention prepares, gold-silver alloy nanoparticles
Close-packed arrays in stratum nucleare, in electrum fiber, the content of gold is higher.This electrum fiber is mainly used in wire device,
Filter barrier material etc..
Accompanying drawing explanation
Fig. 1 is the SEM figure of the gold-silver alloy nanoparticles that embodiment one step 2 obtains；
Fig. 2 is the TEM figure of the electrum-PVA nuclear fibre that embodiment one step 3 obtains；
Fig. 3 is the SEM figure of the electrum-PVA nuclear fibre that embodiment one step 3 obtains；
Fig. 4 is the ultraviolet absorption curve figure of the electrum fiber that embodiment one step 4 obtains；
Fig. 5 is the XRD spectra of the electrum fiber that embodiment one step 4 obtains；
Fig. 6 is that the Ag3d of the electrum fiber XPS that embodiment one step 4 obtains can spectrogram；
Fig. 7 is that the Au4f of the electrum fiber XPS that embodiment one step 4 obtains can spectrogram；
Fig. 8 is the Raman spectrum of the electrum fiber that embodiment one prepares；
Fig. 9 is the scanning electron microscope (SEM) photograph of the electrum fiber that embodiment one prepares.
Detailed description of the invention
Detailed description of the invention one: present embodiment coaxial electrostatic spinning is prepared the method for electrum fiber and followed these steps to reality
Execute:
One, being dissolved in solvent a by polyvinyl alcohol, be heated to 50～100 DEG C, stirring obtains shell layer spinning solution to dissolving；
Two, the silver nitrate of 0.0037g～0.0222g is dissolved in the solvent b of 10～60mL, add after fully dissolving 2～
6mL mass concentration is the chlorauric acid solution of 1%, adds solvent b reactant liquor is diluted to 90～540mL after stirring,
Reactant liquor is placed in reaction vessel and is heated to boiling in oil bath pan and keeps 2～10min, is subsequently adding 10～100mL matter
Amount concentration is the reducing agent of 1%, continues to seethe with excitement 30～50min, add 5～20ml mass concentrations be 5%～
After 10%PVA solution, distillation and concentration is to 10～50mL, and concentrated solution dialyses 22～26h with bag filter, repeatedly changes water 3～4 times,
Obtain stratum nucleare spinning liquid；
Three, the shell layer spinning solution that step one obtains is placed in the outer tube of coaxial electrostatic spinning silk device, the core that step 2 is obtained
Layer spinning liquid be placed in the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage be 13～25kv, relative humidity be 10%～
30%, indoor temperature is 15～25 DEG C, and receiving range is 10～25cm, stratum nucleare spinning liquid and shell layer spinning solution fltting speed
Ratio be (1～0.1): 1 carries out coaxial electrostatic spinning, obtains electrum-PVA nuclear fibre；
Four, electrum-PVA nuclear fibre step 3 obtained is placed in Muffle furnace, be warming up to 300 DEG C and be incubated 6～
7h, then proceedes to be warming up to 400～600 DEG C, naturally cools to room temperature with body of heater, obtain electrum after insulation 1～2h
Fiber.
When present embodiment utilizes coaxial electrostatic spinning to prepare nuclear fibre, the kind of raw material, the molecular weight of chelating polymer template level,
Stratum nucleare and the composition of sandwich layer spinning liquid, stratum nucleare and the velocity ratio of sandwich layer spinning liquid, spinning process parameter and Technology for Heating Processing are to
Pattern and the size of finished product all have a major impact.Present embodiment uses coaxial electrostatic spinning method, with polyvinyl alcohol and going
The mixed liquor of ionized water is shell solution, with the mixed liquor of gold-silver alloy nanoparticles, polyvinyl alcohol and deionized water as sandwich layer
Solution, controls shell and the viscosity of sandwich layer solution, controls stratum nucleare and the velocity ratio of sandwich layer spinning liquid, spinning process parameter
Under excellent spinning condition, prepare electrum-PVA nuclear fibre, then after high-temperature process, obtain electrum fiber.
Detailed description of the invention two: present embodiment unlike detailed description of the invention one the solvent a described in step one for going
Ionized water, dimethyl sulfoxide or N,N-dimethylformamide.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: poly-in present embodiment step one shell layer spinning solution unlike detailed description of the invention one or two
The mass percent of vinyl alcohol is 5%～10%.Other step and parameter are identical with detailed description of the invention one or two.
Present embodiment controls the concentration of shell layer spinning solution, it is to avoid when shell solution concentration is too low, shell viscosity solution is at high pressure
In electric field by stratum nucleare solution formed " frictional shearing " too low and cannot drive stratum nucleare solution formed coaxial jet.Avoid shell
When layer solution concentration is too high, shell solution viscosity is high, and in high voltage electric field, enhanced stretch resistance increases and is difficult to be formed with stratum nucleare solution
Stable coaxial jet.
Detailed description of the invention four: the solvent described in present embodiment step 2 unlike one of detailed description of the invention one to three
B is deionized water, dimethyl sulfoxide or N,N-dimethylformamide.Other step and parameter and detailed description of the invention one to
One of three identical.
Detailed description of the invention five: the reduction described in present embodiment step 2 unlike one of detailed description of the invention one to four
Agent is sodium citrate, sodium borohydride, hydrazine hydrate or formic acid.Other step and parameter and one of detailed description of the invention one to four phase
With.
Detailed description of the invention six: stratum nucleare spinning in present embodiment step 3 unlike one of detailed description of the invention one to five
The fltting speed of liquid is 0.1～5mL/h, and the fltting speed of shell layer spinning solution is 2～10mL/h.Other step and parameter with
One of detailed description of the invention one to five is identical.
Detailed description of the invention seven: present embodiment unlike one of detailed description of the invention one to six step 4 with 1～
The ramp of 6 DEG C/min is to 300 DEG C and is incubated 6～7h, then with the ramp of 1～2 DEG C/min to 400 DEG C, protects
Room temperature is naturally cooled to body of heater after temperature 1～2h.Other step and parameter are identical with one of detailed description of the invention one to six.
Embodiment one: the present embodiment coaxial electrostatic spinning is prepared the method for electrum fiber and followed these steps to implement:
One, 1.2022g polyvinyl alcohol (PVA, n=1750 ± 50) is dissolved in 10.8198ml deionized water, is heated to 90 DEG C
Stirring, to dissolving, obtains shell layer spinning solution；
Two, the silver nitrate of 0.0222g is dissolved in the deionized water of 60mL, after fully dissolving, adds 6mL mass concentration
Being the chlorauric acid solution of 1%, add deionized water reactant liquor is diluted to 540mL after stirring, reactant liquor is placed in instead
Answer and container be heated in oil bath pan boiling and keep 5min, be subsequently adding the sodium citrate that 60mL mass concentration is 1%,
Continue to the 30min that seethes with excitement, add 0.411g mass concentration be after 5%PVA solution distillation and concentration to 30mL, concentrated solution
Dialyse 24h with bag filter, repeatedly change water 3 times, obtain stratum nucleare spinning liquid；
Three, the shell layer spinning solution that step one obtains is placed in the outer tube of coaxial electrostatic spinning silk device, the core that step 2 is obtained
Layer spinning liquid is placed in the inner tube of coaxial electrostatic spinning silk device, and regulation spinning voltage is 18kv, and relative humidity is 30%, room
Interior temperature is 20 DEG C, and receiving range is 18cm, and stratum nucleare spinning liquid fltting speed is 2.5mL/h, and shell layer spinning solution advances speed
Degree carries out coaxial electrostatic spinning for 7.5mL/h, obtains electrum-PVA nuclear fibre；
Four, nuclear fibre is placed in Muffle furnace, to 300 DEG C and is incubated 7h with the ramp of 4 DEG C/min, then with
The ramp of 1.5 DEG C/min, to 400 DEG C, naturally cools to room temperature with body of heater after insulation 1h, obtains electrum fiber.
The average diameter of the electrum fiber that the present embodiment obtains is 50～100nm.
Gold silver nano particle diameter is more uniform as can be seen from Figure 1, and agglomeration is few.By Fig. 2 electrum-PVA nucleocapsid
The TEM figure of fiber understands gold-silver alloy nanoparticles in stratum nucleare arrangement closely, and the SEM figure of Fig. 3 shows that fiber morphology is protected
Hold good continuous fiber structure, single good dispersion, there is bigger specific surface area.
Preparation electrum fiber ultraviolet absorption curve figure as shown in Figure 4, it can be seen that in electrum fiber along with
The increase that the content of gold increases, the ultraviolet absorption peak of electrum fiber moves to long wave direction, it is possible to judge that products therefrom is
Gold-silver alloy nanoparticles rather than golden nanometer particle and the mixture of Nano silver grain.Fig. 5 is XRD spectra, in figure
2 θ=38.2 °, 44.2 °, 64.4 ° and 77.5 °, the most corresponding (111), (200), (220) and (311), demonstrate,prove further
The fiber of real synthesis is electrum fiber；The electrum fiber obtained is carried out x-ray photoelectron spectroscopy analysis,
Electrum fiber XPS figure as shown in Figure 6, Fig. 6 be Ag3d can spectrogram, it can be seen that the two of silver element from figure
Individual peak occurs on the position of 368eV and 374eV, judges that silver is reduced and is present in gold silver conjunction by consulting XPS handbook
In gold fiber, and exist with stable element form；What Fig. 7 represented is Au4f can spectrogram, as we can see from the figure two
Individual peak, respectively on the position of 84eV and 88eV, may determine that as gold according to XPS handbook, it is possible to infer electrum
Containing gold in fiber, this means that gold has been completely reduced and presented in stable.Fig. 8 is electrum fiber
(1) and the surface enhanced raman spectroscopy of PVA-alloy composite fibre (2), it can be seen that electrum fiber Raman phenomenon
Substantially strengthened.
Claims (6)
1. the method that a coaxial electrostatic spinning prepares electrum nanofiber, it is characterised in that be to follow these steps to realize:
One, being dissolved in solvent a by polyvinyl alcohol, be heated to 50～100 DEG C, stirring obtains shell layer spinning solution to dissolving；
Two, being dissolved in the solvent b of 60mL by the silver nitrate of 0.0222g, adding 6mL mass concentration after fully dissolving is 1%
Chlorauric acid solution, add solvent b after stirring and reactant liquor be diluted to 540mL, reactant liquor is placed in reaction vessel
In oil bath pan, it is heated to boiling and keeps 5min, being subsequently adding the reducing agent that 60mL mass concentration is 1%, continue to
Boiling 30min, add 0.411g mass concentration be after 5%PVA solution distillation and concentration to 30mL, concentrated solution bag filter
Dialysis 24h, repeatedly changes water 3 times, obtains stratum nucleare spinning liquid；
Three, the shell layer spinning solution that step one obtains is placed in the outer tube of coaxial electrostatic spinning silk device, the core that step 2 is obtained
Layer spinning liquid be placed in the inner tube of coaxial electrostatic spinning silk device, regulation spinning voltage be 13～25kv, relative humidity be 10%～
30%, indoor temperature is 15～25 DEG C, and receiving range is 10～25cm, stratum nucleare spinning liquid and shell layer spinning solution fltting speed it
Than for (1～0.1): 1 carries out coaxial electrostatic spinning, obtains electrum-PVA core-shell nano fiber；
Four, electrum-PVA core-shell nano fiber step 3 obtained is placed in Muffle furnace, is warming up to 300 DEG C and is incubated
6～7h, then proceed to be warming up to 400～600 DEG C, after insulation 1～2h, naturally cool to room temperature with body of heater, obtain gold silver and close
Gold nano fiber；
Wherein in step one shell layer spinning solution, the mass percent of polyvinyl alcohol is 5%～10%.
The method that a kind of coaxial electrostatic spinning the most according to claim 1 prepares electrum nanofiber, its feature exists
It is deionized water, dimethyl sulfoxide or N,N-dimethylformamide in the solvent a described in step one.
The method that a kind of coaxial electrostatic spinning the most according to claim 1 prepares electrum nanofiber, its feature exists
It is deionized water, dimethyl sulfoxide or N,N-dimethylformamide in the solvent b described in step 2.
The method that a kind of coaxial electrostatic spinning the most according to claim 1 prepares electrum nanofiber, its feature exists
It is sodium citrate, sodium borohydride, hydrazine hydrate or formic acid in the reducing agent described in step 2.
The method that a kind of coaxial electrostatic spinning the most according to claim 1 prepares electrum nanofiber, its feature exists
In step 3, the fltting speed of stratum nucleare spinning liquid is 0.1～5mL/h, and the fltting speed of shell layer spinning solution is 2～10mL/h.
The method that a kind of coaxial electrostatic spinning the most according to claim 1 prepares electrum nanofiber, its feature exists
To 300 DEG C and it is incubated 6～7h, then with the ramp of 1～2 DEG C/min with the ramp of 1～6 DEG C/min in step 4
To 400 DEG C, after insulation 1～2h, naturally cool to room temperature with body of heater.
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| CN110211729B (en) * | 2019-06-24 | 2021-02-26 | 南京邮电大学 | Multi-layer coaxial structure micro-cable and preparation method thereof |
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