CN102191570A - Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable - Google Patents
Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable Download PDFInfo
- Publication number
- CN102191570A CN102191570A CN2011100578997A CN201110057899A CN102191570A CN 102191570 A CN102191570 A CN 102191570A CN 2011100578997 A CN2011100578997 A CN 2011100578997A CN 201110057899 A CN201110057899 A CN 201110057899A CN 102191570 A CN102191570 A CN 102191570A
- Authority
- CN
- China
- Prior art keywords
- pvp
- coaxial
- cable
- spinning solution
- nio
- 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.)
- Granted
Links
Images
Landscapes
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Nonwoven Fabrics (AREA)
Abstract
The invention relates to a method for preparing a NiO@SiO2@TiO2 coaxial three-layer nano cable and belongs to the technical field of preparation of nano materials. The method comprises three steps of: (1) preparing spinning solution, namely adding 4-H2O nickel acetate and polyvinylpyrrolidone (PVP) into N,N-dimethylformamide (DMF) and forming core spinning solution, adding tetraethoxysilane and PVP into ethanol and forming middle spinning solution, and adding tetrabutyl titanate, PVP and glacial acetic acid into the ethanol and forming shell spinning solution; (2) preparing [Ni(CH3COO)2+PVP]@[(C2H5O)4Si+PVP]@[Ti(OC4H9)4+CH3COOH+PVP] precursor compound cable, namely adopting a coaxial electrostatic spinning technology and using a coaxial three-layer spinning nozzle under voltage of 17kV, a curing distance of 15 centimeters, room temperature of 21 to 25 DEG C, relative humidity of 50 to 62 percent; and (3) preparing the NiO@SiO2@TiO2 coaxial three-layer nano cable, namely thermally treating the precursor compound cable at a temperature rising rate of 1 DEG C per minute, preserving the temperature for 8 hours at 800 DEG C, reducing the temperature at the speed of 1 DEG C per minute to 200 DEG C and naturally cooling to room temperature so as to obtain the NiO (core) @SiO2 (middle)@TiO2 (shell) coaxial three-layer nano cable, wherein the diameter of the NiO@SiO2@TiO2 coaxial three-layer nano cable is 200 to 250 nanometers; and the length of the cable is larger than 300 microns.
Description
Technical field
The present invention relates to the inorganic nano material preparing technical field, relate to a kind of NiO@SiO specifically
2@TiO
2The preparation method of coaxial three layers of nano-cable.
Background technology
The preparation of one-dimensional nano structure material and property research are one of forward position focuses of present material science research field.Nano-cable (Nanocables) is because its particular performances, abundant scientific meaning, wide application prospect and the important strategic status of occupying in following nano structure device have caused people's great attention in recent years.The research of coaxial nano cable is started in the mid-90, development later in 2000 is swifter and more violent, and up to the present, people adopt different synthetic methods, different types of material has successfully been prepared hundreds of coaxial nano cable, as: Fe/C, Zn/ZnO, C/C, SiC/C, SiGaN/SiO
xN
yAnd the Fe-C-BN of three-decker and α-Si
3N
4-Si-SiO
2Deng.In more than ten years in the past, people develop many methods that prepare coaxial nano cable on the basis of original preparation quasi-one-dimensional nanometer material, as: hydro-thermal method, sol-gel process, based on nanometer collimation method, vapor growth method, template etc.Continue to explore new synthetic technology, constantly develop and improve the preparation science of coaxial nano cable, obtain high-quality coaxial nano cable, be still the main direction of present coaxial nano cable research.
Because titanium dioxide TiO
2Have excellent photocatalysis, high electricity conversion, superpower chemical stability and good performance such as biocompatibility with nickel oxide NiO, thereby obtain extensive use at aspects such as photocatalysis Decomposition organic matter, photocell electrode, pearlescent material, histoorgan, disinfecting, antimicrobials.SiO
2Be a kind of common resistant to elevated temperatures functional material, be easy to form the construction of cable and obtain paying attention to.Do not see at present by NiO, SiO
2And TiO
2Make up NiO@SiO
2@TiO
2The report of coaxial three layers of nano-cable, @ represents core shell structure, i.e. the construction of cable, this cable is three layers of construction of cable, sandwich layer @ intermediate layer @ shell, sandwich layer is NiO, the intermediate layer is SiO
2, shell is TiO
2, this nano-cable has special structure, uses widely in the hope of obtaining.
The patent No. technical scheme of a relevant electrospinning process (electrospinning) that has been 1975504 U.S. Patent Publication, this method is a kind of effective ways that prepare continuous, as to have macro length micro nanometer fiber, is at first proposed in 1934 by Formhals.This method is mainly used to prepare high polymer nanometer fiber, it is characterized in that making charged Polymer Solution or melt in electrostatic field, to be subjected to the traction of electrostatic force and spray by nozzle, invest the receiving screen on opposite, thereby realization wire drawing, solvent evaporation at normal temperatures then, perhaps melt is cooled to normal temperature and solidifies, and obtains micro nanometer fiber.Over nearly 10 years, occurred adopting electrospinning process to prepare the technical scheme of inorganic compound such as oxidate nano fiber at the inorfil preparing technical field, described oxide comprises TiO
2, ZrO
2, Y
2O
3, Y
2O
3: RE
3+(RE
3+=Eu
3+, Tb
3+, Er
3+, Yb
3+/ Er
3+), NiO, Co
3O
4, Mn
2O
3, Mn
3O
4, CuO, SiO
2, Al
2O
3, V
2O
5, ZnO, Nb
2O
5, MoO
3, CeO
2, LaMO
3(M=Fe, Cr, Mn, Co, Ni, Al), Y
3Al
5O
12, La
2Zr
2O
7Deng metal oxide and composite oxide of metal.Electrostatic spinning technique is improved, adopt coaxial spinning head, spinning solution is injected into respectively in interior pipe and the outer tube, when adding High Level DC Voltage, solution in the inner and outer pipes is pulled out by electric field force simultaneously, solidify the back and form coaxial nano cable, also promptly obtain the coaxial double-layer nano-cable, this technology promptly is a coaxial electrostatic spinning technology.This technology of usefulness such as Wang Ce has prepared silica polymer co-axial nano fiber (SCI, 2005,26 (5): 985-987), @ represents core shell structure, and the material of @ front is a sandwich layer, and the material of @ back is a shell, be sandwich layer @ shell structurre, also be the double-deck construction of cable; Dong Xiangting etc. utilize this technology to prepare TiO
2@SiO
2Sub-micron coaxial cable (chemical journal, 2007,65 (23): 2675-2679), ZnO@SiO
2Coaxial nano cable (Chinese Journal of Inorganic Chemistry, 2010,26 (1), 29-34) and Al
2O
3/ SiO
2Coaxial ultra micro cable (silicate journal, 2009,37 (10): 1712-1717); Han, et al adopt this technology prepared PU (Core)/PC (Shell) composite nano fiber (Polymer Composites, 2006,10:381-386).At present, do not see and utilize coaxial electrostatic spinning technology to prepare NiO@SiO
2@TiO
2The relevant report of coaxial three layers of nano-cable.
When utilizing electrostatic spinning technique to prepare nano material, the structure of the composition of the kind of raw material, the molecular weight of high polymer templates, spinning solution, spinning process parameter, Technology for Heating Processing and spinning head all has material impact to the pattern and the size of final products.The present invention adopts coaxial electrostatic spinning technology, and coaxial three layers of spinning head that spinning head is nested together and is formed by three syringe needles that cut flat different-diameters are with four water acetic acid nickel (CH
3COO)
24H
2O, polyvinylpyrrolidone PVP and N, the mixed liquor of dinethylformamide DMF are the sandwich layer spinning solution, with ethyl orthosilicate (C
2H
5O)
4Si, PVP and absolute ethyl alcohol CH
3CH
2The mixed liquor of OH is the intermediate layer spinning solution, with PVP, CH
3CH
2OH, glacial acetic acid CH
3COOH and butyl titanate Ti (OC
4H
9)
4Mixed liquor be shell layer spinning solution, the viscosity of control spinning solution is most important, under the process conditions of the best, obtains [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable, i.e. sandwich layer @ intermediate layer @ shell structurre composite cable, pass through high-temperature heat treatment again after, obtain the NiO@SiO of novel structure
2@TiO
2Coaxial three layers of nano-cable.
Summary of the invention
The method for preparing coaxial nano cable in background technology has hydro-thermal method, sol-gel process, based on nanometer collimation method, vapor growth method, template etc., what the use coaxial electrostatic spinning technology in the background technology prepared is coaxial double-layer nanometer cables such as inorganic matter inorganic matter, inorganic matter macromolecule and macromolecule high molecular nanometer cable, and the structure of employed raw material, template agent, solvent, spinning head is different with method of the present invention with the final objective product.The present invention uses coaxial electrostatic spinning technology, adopts coaxial three layers of spinning head to prepare the NiO@SiO of novel structure
2@TiO
2Coaxial three layers of nano-cable are sandwich layer with NiO, and diameter is 40-45nm; The intermediate layer is SiO
2, thickness is 40-45nm; Shell is TiO
2, thickness is 45-50nm, the diameter of coaxial three layers of nano-cable is 200-250nm, cable length＞300 μ m.
The present invention is achieved in that and at first prepares the sandwich layer with certain viscosity, intermediate layer and the shell layer spinning solution that is used for coaxial electrostatic spinning technology that the viscosity of control spinning solution is most important.Adopt coaxial three layers of spinning head, application coaxial electrostatic spinning technology to carry out electrostatic spinning, under the process conditions of the best, obtain [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable, promptly @ shell structurre composite cable in sandwich layer @ intermediate layer passes through high-temperature heat treatment, PVP and CH
3Volatilize the Ni (CH in the sandwich layer after the COOH oxidation Decomposition
3COO)
2Oxidation Decomposition generates NiO, constitutes the sandwich layer of the nano-cable that is generated, (the C in the intermediate layer
2H
5O)
4The Si oxidation Decomposition generates SiO
2, the intermediate layer of the nano-cable that formation is generated, the Ti (OC in the shell
4H
9)
4Oxidation Decomposition has generated TiO
2, having constituted the shell of nano-cable, to prepare the coaxial double-layer nano-cable different with employing coaxial electrostatic spinning technology of report in the past for these, finally obtain the NiO@SiO of novel structure
2@TiO
2Coaxial three layers of nano-cable.The steps include:
(1) preparation spinning solution
High polymer templates adopts polyvinylpyrrolidone PVP in the spinning solution, and molecular weight is 90000, and four water acetic acid nickel (CH are used in the nickel source
3COO)
24H
2O, ethyl orthosilicate (C is used in the silicon source
2H
5O)
4Si, butyl titanate Ti (OC is used in the titanium source
4H
9)
4, solvent adopts absolute ethyl alcohol CH
3CH
2OH and N, dinethylformamide DMF, glacial acetic acid CH
3COOH is an additive.With Ni (CH
3COO)
24H
2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the sandwich layer spinning solution, and the mass percent of each material is in the sandwich layer spinning solution: Ni (CH
3COO)
24H
2O is 7%, and PVP is 11%, and DMF is 82%; With (C
2H
5O)
4Si and PVP join CH
3CH
2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the intermediate layer spinning solution, and the mass percent of each material is in the spinning solution of intermediate layer: (C
2H
5O)
4Si is 31%, and PVP is 17%, CH
3CH
2OH is 52%; With Ti (OC
4H
9)
4, PVP and CH
3COOH joins CH
3CH
2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms shell layer spinning solution, and the mass percent of each material is in the shell layer spinning solution: Ti (OC
4H
9)
4Be 20%, PVP is 8%, CH
3COOH is 18%, CH
3CH
2OH is 54%.
(2) preparation [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable
Coaxial three layers of spinning head that spinning head is nested together and is formed by three syringe needles that cut flat different-diameters, the sandwich layer shower nozzle is for cutting the 5# stainless steel syringe needle after putting down, external diameter is 0.5mm, internal diameter is 0.232mm, the intermediate layer shower nozzle is for cutting the 12# stainless steel syringe needle after putting down, external diameter is 1.2mm, internal diameter is 0.790mm, and the shell shower nozzle is for cutting the veterinary syringe syringe needle after putting down, and external diameter is 3.6mm, internal diameter is 2.0mm, the sandwich layer spinning solution for preparing is joined in the interior pipe, and the intermediate layer spinning solution joins in the intervalve, and shell layer spinning solution joins in the outer tube, regulate the sandwich layer shower nozzle, successfully flow out to guarantee each layer spinning solution in the gap of intermediate layer shower nozzle and shell shower nozzle, adopt coaxial electrostatic spinning technology, adopt perpendicular spray mode, shower nozzle is vertical with horizontal plane, applying voltage is 17kV, shower nozzle is 15cm to the curing distance of receiving screen wire netting, 21 ℃～25 ℃ of indoor temperatures, and relative humidity is 50%～62%, along with the volatilization of solvent, on as the wire netting of negative pole, just can collect [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable.
(3) preparation NiO@SiO
2@TiO
2Coaxial three layers of nano-cable
To [Ni (the CH that is obtained
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable heat-treats, and heating rate is 1 ℃/min, at 800 ℃ of insulation 8h, naturally cools to room temperature after reducing to 200 ℃ with the speed of 1 ℃/min then, so far obtains NiO@SiO
2@TiO
2Coaxial three layers of nano-cable.
The NiO@SiO of prepared novel structure in the said process
2@TiO
2Coaxial three layers of nano-cable are sandwich layer with NiO, and diameter is 40-45nm; The intermediate layer is SiO
2, thickness is 40-45nm; Shell is TiO
2, thickness is 45-50nm, the diameter of coaxial three layers of nano-cable is 200-250nm, cable length＞300 μ m.Realized goal of the invention.
Description of drawings
Fig. 1 is NiO@SiO
2@TiO
2The XRD spectra of coaxial three layers of nano-cable.
Fig. 2 is NiO@SiO
2@TiO
2The SEM photo of coaxial three layers of nano-cable.
Fig. 3 is NiO@SiO
2@TiO
2The EDS spectrogram of coaxial three layers of nano-cable.
Fig. 4 is NiO@SiO
2@TiO
2The TEM photo of coaxial three layers of nano-cable, the double accompanying drawing that makes an abstract of this figure.
The specific embodiment
Embodiment: with four water acetic acid nickel (CH
3COO)
24H
2O and polyvinylpyrrolidone PVP (molecular weight is 90000) join N, and among the dinethylformamide DMF, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the sandwich layer spinning solution, and the mass percent of each material is in the sandwich layer spinning solution: Ni (CH
3COO)
24H
2O is 7%, and PVP is 11%, and DMF is 82%; With (C
2H
5O)
4Si and PVP join CH
3CH
2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the intermediate layer spinning solution, and the mass percent of each material is in the spinning solution of intermediate layer: (C
2H
5O)
4Si is 31%, and PVP is 17%, CH
3CH
2OH is 52%; With butyl titanate Ti (OC
4H
9)
4, PVP and glacial acetic acid CH
3COOH joins absolute ethyl alcohol CH
3CH
2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms shell layer spinning solution, and the mass percent of each material is in the shell layer spinning solution: Ti (OC
4H
9)
4Be 20%, PVP is 8%, CH
3COOH is 18%, CH
3CH
2OH is 54%.Adopt coaxial electrostatic spinning technology to spray silk.Coaxial three layers of spinning head that spinning head is nested together and is formed by three syringe needles that cut flat different-diameters, the sandwich layer shower nozzle is for cutting the 5# stainless steel syringe needle after putting down, external diameter is 0.5mm, internal diameter is 0.232mm, the intermediate layer shower nozzle is for cutting the 12# stainless steel syringe needle after putting down, external diameter is 1.2mm, internal diameter is 0.790mm, the shell shower nozzle is for cutting the veterinary syringe syringe needle after putting down, and external diameter is 3.6mm, and internal diameter is 2.0mm, the sandwich layer spinning solution for preparing is joined in the interior pipe, the intermediate layer spinning solution joins in the intervalve, and shell layer spinning solution joins in the outer tube, regulates the sandwich layer shower nozzle, successfully flow out to guarantee each layer spinning solution in the gap of intermediate layer shower nozzle and shell shower nozzle, adopt perpendicular spray mode, shower nozzle is vertical with horizontal plane, and applying voltage is 17kV, and shower nozzle is 15cm to the curing distance of receiving screen wire netting, 21 ℃～25 ℃ of indoor temperatures, relative humidity is 50%～62%, along with the volatilization of solvent, just can collect [Ni (CH on as the wire netting of negative pole
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable.With spun [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable puts into the temperature programmed control stove and heat-treats, and heating rate is 1 ℃/min, at 800 ℃ of insulation 8h, naturally cools to room temperature after reducing to 200 ℃ with the speed of 1 ℃/min then, obtains NiO@SiO
2@TiO
2Coaxial three layers of nano-cable.Prepared NiO@SiO
2@TiO
2Coaxial three layers of nano-cable have good crystal formation, are sandwich layer with NiO, and the intermediate layer is SiO
2, with the TiO of Detitanium-ore-type and rutile-type duplex grain structure
2Be shell, see shown in Figure 1.Prepared NiO@SiO
2@TiO
2Coaxial three layers of nano-cable diameter are 200-250nm, and cable length＞300 μ m is seen shown in Figure 2.NiO@SiO
2@TiO
2Coaxial three layers of nano-cable are formed (the Au conductive layer of surface plating when Au comes from the SEM sample preparation) by Ni, Si, Ti and O element, see shown in Figure 3.Prepared NiO@SiO
2@TiO
2The diameter of the sandwich layer NiO of coaxial three layers of nano-cable is 40-45nm, intermediate layer SiO
2Thickness be 40-45nm; Shell TiO
2Thickness be 45-50nm, see shown in Figure 4.
Polyvinylpyrrolidone, absolute ethyl alcohol, N that the present invention is selected, dinethylformamide, butyl titanate, four water acetic acid nickel, ethyl orthosilicate and glacial acetic acid are commercially available analysis net product.Used glass apparatus and equipment are commonly used in the laboratory.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and distortion according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (2)
1. one kind prepares NiO@SiO
2@TiO
2The method of coaxial three layers of nano-cable is characterized in that, uses coaxial electrostatic spinning technology, coaxial three layers of spinning head that spinning head is nested together and is formed by three syringe needles that cut flat different-diameters, and the preparation product is NiO@SiO
2@TiO
2Coaxial three layers of nano-cable, i.e. sandwich layer @ intermediate layer @ shell structurre, sandwich layer is NiO, the intermediate layer is SiO
2, shell is TiO
2, the steps include:
(1) preparation spinning solution
High polymer templates adopts polyvinylpyrrolidone PVP, and four water acetic acid nickel (CH are used in the nickel source
3COO)
24H
2O, ethyl orthosilicate (C is used in the silicon source
2H
5O)
4Si, butyl titanate Ti (OC is used in the titanium source
4H
9)
4, solvent adopts absolute ethyl alcohol CH
3CH
2OH and N, dinethylformamide DMF, glacial acetic acid CH
3COOH is an additive, with Ni (CH
3COO)
24H
2O and PVP join among the DMF, and the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the sandwich layer spinning solution, and the mass percent of each material is in the sandwich layer spinning solution: Ni (CH
3COO)
24H
2O is 7%, and PVP is 11%, and DMF is 82%, with (C
2H
5O)
4Si and PVP join CH
3CH
2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms the intermediate layer spinning solution, and the mass percent of each material is in the spinning solution of intermediate layer: (C
2H
5O)
4Si is 31%, and PVP is 17%, CH
3CH
2OH is 52%; With Ti (OC
4H
9)
4, PVP and CH
3COOH joins CH
3CH
2Among the OH, the room temperature lower magnetic force stirs 6h, and leaves standstill 3h, promptly forms shell layer spinning solution, and the mass percent of each material is in the shell layer spinning solution: Ti (OC
4H
9)
4Be 20%, PVP is 8%, CH
3COOH is 18%, CH
3CH
2OH is 54%;
(2) preparation [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable
Coaxial three layers of spinning head that spinning head is nested together and is formed by three syringe needles that cut flat different-diameters, the sandwich layer shower nozzle is for cutting the 5# stainless steel syringe needle after putting down, external diameter is 0.5mm, internal diameter is 0.232mm, the intermediate layer shower nozzle is for cutting the 12# stainless steel syringe needle after putting down, external diameter is 1.2mm, internal diameter is 0.790mm, and the shell shower nozzle is for cutting the veterinary syringe syringe needle after putting down, and external diameter is 3.6mm, internal diameter is 2.0mm, the sandwich layer spinning solution for preparing is joined in the interior pipe, and the intermediate layer spinning solution joins in the intervalve, and shell layer spinning solution joins in the outer tube, regulate the sandwich layer shower nozzle, successfully flow out to guarantee each layer spinning solution in the gap of intermediate layer shower nozzle and shell shower nozzle, adopt coaxial electrostatic spinning technology, adopt perpendicular spray mode, shower nozzle is vertical with horizontal plane, applying voltage is 17kV, shower nozzle is 15cm to the curing distance of receiving screen wire netting, 21 ℃～25 ℃ of indoor temperatures, and relative humidity is 50%～62%, along with the volatilization of solvent, on as the wire netting of negative pole, just can collect [Ni (CH
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable;
(3) preparation NiO@SiO
2@TiO
2Coaxial three layers of nano-cable
To [Ni (the CH that is obtained
3COO)
2+ PVP] @[(C
2H
5O)
4Si+PVP] @[Ti (OC
4H
9)
4+ CH
3COOH+PVP] the presoma composite cable heat-treats, and heating rate is 1 ℃/min, at 800 ℃ of insulation 8h, naturally cools to room temperature after reducing to 200 ℃ with the speed of 1 ℃/min then, so far obtains NiO@SiO
2@TiO
2Coaxial three layers of nano-cable.
2. a kind of preparation NiO@SiO according to claim 1
2@TiO
2The method of coaxial three layers of nano-cable is characterized in that, high polymer templates is the polyvinylpyrrolidone of molecular weight Mr=90000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110057899 CN102191570B (en) | 2011-03-11 | 2011-03-11 | Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110057899 CN102191570B (en) | 2011-03-11 | 2011-03-11 | Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102191570A true CN102191570A (en) | 2011-09-21 |
| CN102191570B CN102191570B (en) | 2013-04-24 |
Family
ID=44600406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110057899 Expired - Fee Related CN102191570B (en) | 2011-03-11 | 2011-03-11 | Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102191570B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400249A (en) * | 2011-09-23 | 2012-04-04 | 长春理工大学 | Method for preparing TiO2@SiO2 coaxial nanotube |
| CN102586945A (en) * | 2012-02-21 | 2012-07-18 | 长春理工大学 | Method for preparing SiO2/SnO2/TiO2 three-component parallel nanofiber bundle |
| CN103102067A (en) * | 2011-11-11 | 2013-05-15 | 北京化工大学 | Method of preparing silicon dioxide fiber with rough surfaces through coaxial electrostatic spinning |
| CN103668485A (en) * | 2013-12-03 | 2014-03-26 | 大连海洋大学 | Coaxial three-layer high-activity bio-enzyme-embedded electrostatic spinning nano-fiber membrane and preparation method thereof |
| CN104032406A (en) * | 2014-05-12 | 2014-09-10 | 浙江理工大学 | Preparation method for porous inorganic photocatalytic composite nanometer fiber |
| CN104674377A (en) * | 2014-12-05 | 2015-06-03 | 江苏旷达汽车织物集团股份有限公司 | Preparation method of luminescent low-stretch yarn for inner decorating materials for automobile |
| CN106381532A (en) * | 2016-11-21 | 2017-02-08 | 上海理工大学 | Electric spinning preparation method of nanometer fiber with material gradient distribution features |
| CN106757415A (en) * | 2016-12-08 | 2017-05-31 | 上海理工大学 | A kind of microfluidic control shower nozzle of three-level arrangement, device for spinning and spinning process |
| CN107034550A (en) * | 2017-04-26 | 2017-08-11 | 同济大学 | A kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material |
| CN109208091A (en) * | 2018-08-07 | 2019-01-15 | 黄春梁 | The method that one-step method prepares three layers of composite wave-suction material |
| CN115012125A (en) * | 2022-07-29 | 2022-09-06 | 韩忠 | Moisture-absorbing and quick-drying polyester fabric and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1958890A (en) * | 2006-11-08 | 2007-05-09 | 中国科学院广州化学研究所 | Heat storaging, thermoregulated superfine composite fibre of possessing kernel / shell structure, and preparation method |
| WO2008060675A2 (en) * | 2006-06-01 | 2008-05-22 | Invista Technologies S.A R.L. | Coaxial polycarbonate/polyurethane composite nanofibers |
| JP2009174066A (en) * | 2008-01-21 | 2009-08-06 | Mecc Co Ltd | Spinneret for electrospinning device |
| US7575707B2 (en) * | 2005-03-29 | 2009-08-18 | University Of Washington | Electrospinning of fine hollow fibers |
| CN101763917A (en) * | 2010-03-04 | 2010-06-30 | 长春理工大学 | Method for preparing tin dioxide and titanium dioxide nano cable |
| CN101942711A (en) * | 2010-08-24 | 2011-01-12 | 浙江理工大学 | Electrostatic spinning method of submicron green fluorescent fiber Gd2O3: Tb3+ |
-
2011
- 2011-03-11 CN CN 201110057899 patent/CN102191570B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7575707B2 (en) * | 2005-03-29 | 2009-08-18 | University Of Washington | Electrospinning of fine hollow fibers |
| WO2008060675A2 (en) * | 2006-06-01 | 2008-05-22 | Invista Technologies S.A R.L. | Coaxial polycarbonate/polyurethane composite nanofibers |
| CN1958890A (en) * | 2006-11-08 | 2007-05-09 | 中国科学院广州化学研究所 | Heat storaging, thermoregulated superfine composite fibre of possessing kernel / shell structure, and preparation method |
| JP2009174066A (en) * | 2008-01-21 | 2009-08-06 | Mecc Co Ltd | Spinneret for electrospinning device |
| CN101763917A (en) * | 2010-03-04 | 2010-06-30 | 长春理工大学 | Method for preparing tin dioxide and titanium dioxide nano cable |
| CN101942711A (en) * | 2010-08-24 | 2011-01-12 | 浙江理工大学 | Electrostatic spinning method of submicron green fluorescent fiber Gd2O3: Tb3+ |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400249A (en) * | 2011-09-23 | 2012-04-04 | 长春理工大学 | Method for preparing TiO2@SiO2 coaxial nanotube |
| CN103102067A (en) * | 2011-11-11 | 2013-05-15 | 北京化工大学 | Method of preparing silicon dioxide fiber with rough surfaces through coaxial electrostatic spinning |
| CN102586945A (en) * | 2012-02-21 | 2012-07-18 | 长春理工大学 | Method for preparing SiO2/SnO2/TiO2 three-component parallel nanofiber bundle |
| CN102586945B (en) * | 2012-02-21 | 2014-06-11 | 长春理工大学 | Method for preparing SiO2/SnO2/TiO2 three-component parallel nanofiber bundle |
| CN103668485B (en) * | 2013-12-03 | 2016-03-16 | 大连海洋大学 | The Electrospun nano-fibers film of coaxial three floor height activity embedding biology enzymes and preparation method |
| CN103668485A (en) * | 2013-12-03 | 2014-03-26 | 大连海洋大学 | Coaxial three-layer high-activity bio-enzyme-embedded electrostatic spinning nano-fiber membrane and preparation method thereof |
| CN104032406A (en) * | 2014-05-12 | 2014-09-10 | 浙江理工大学 | Preparation method for porous inorganic photocatalytic composite nanometer fiber |
| CN104674377A (en) * | 2014-12-05 | 2015-06-03 | 江苏旷达汽车织物集团股份有限公司 | Preparation method of luminescent low-stretch yarn for inner decorating materials for automobile |
| CN106381532A (en) * | 2016-11-21 | 2017-02-08 | 上海理工大学 | Electric spinning preparation method of nanometer fiber with material gradient distribution features |
| CN106757415A (en) * | 2016-12-08 | 2017-05-31 | 上海理工大学 | A kind of microfluidic control shower nozzle of three-level arrangement, device for spinning and spinning process |
| CN107034550A (en) * | 2017-04-26 | 2017-08-11 | 同济大学 | A kind of preparation method of one-dimensional monokaryon duplex shell structure dielectric capacitor material |
| CN109208091A (en) * | 2018-08-07 | 2019-01-15 | 黄春梁 | The method that one-step method prepares three layers of composite wave-suction material |
| CN109208091B (en) * | 2018-08-07 | 2021-04-06 | 北京军通新材料科技有限公司 | Method for preparing three-layer composite wave-absorbing material by one-step method |
| CN115012125A (en) * | 2022-07-29 | 2022-09-06 | 韩忠 | Moisture-absorbing and quick-drying polyester fabric and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102191570B (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102191570B (en) | Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable | |
| CN102191571B (en) | Preparation method of coaxial three-layer nano cable NiO@SnO2@TiO2 | |
| CN101763917B (en) | Method for preparing tin dioxide and titanium dioxide nano cable | |
| CN101789288B (en) | Preparation method of nickel titanate at titanium dioxide multi-crystal nanometer cable | |
| CN102400249B (en) | Method for preparing TiO2@SiO2 coaxial nanotube | |
| CN102400248B (en) | Method for preparing parallel polycrystalline nano fiber bundle of stannic oxide and nickel oxide | |
| CN102502874B (en) | Preparation method of ferroferric oxide (Fe3O4) nanobelt in network structure | |
| CN101306839B (en) | Process for preparing titanium dioxide nano-belts | |
| CN102586950B (en) | Method for preparing zinc selenide (ZnSe) nanofiber | |
| CN101694018B (en) | Process for preparing uropium-doped yttrium oxide @ silicon dioxide bean-shaped nano-cables | |
| CN101235556A (en) | Method for preparing perovskite-type rare earth composite oxide ultra-long nano fiber | |
| CN102586945B (en) | Method for preparing SiO2/SnO2/TiO2 three-component parallel nanofiber bundle | |
| CN102592716B (en) | Magnetic and optical dual-function coaxial nano cable and preparation method thereof | |
| CN101786600B (en) | SnO2/ZnO composite polycrystal nanobelt preparation method | |
| CN101786596A (en) | Polycrystalline nano-fiber with europium ion doped with lanthanum aluminate and preparation method thereof | |
| CN102191572A (en) | Method for preparing NiO@ZnTiO3@TiO2 coaxial three-layer nanocable | |
| CN102214505B (en) | Preparation method of Nio@Al2O3@TiO2 coaxial three-layer nano cable | |
| CN102222548B (en) | Method for preparing NiO@SnO2@Zn2TiO4@TiO2 coaxial four-layer nanocable | |
| CN101792170A (en) | Method for preparing cerium dioxide polycrystal nanobelt | |
| CN102605468A (en) | Method for preparing nickel sulfide nano-fibers | |
| CN101789287B (en) | Zinc titanite and titanium dioxide polycrystal nanocable preparation method | |
| CN106381574B (en) | It is a kind of to prepare Bi5O7The method of I nanofibers | |
| CN102277658B (en) | Method for preparing yttrium sulfide nano-fibers | |
| CN102586949B (en) | Method for preparing zinc selenide nanobelt | |
| CN102817106B (en) | Preparation method of cadmium selenide nano-fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130424 Termination date: 20140311 |