CN104746160A - Infrared transmittance/reflectivity variable nano composite fiber and preparation method thereof - Google Patents
Infrared transmittance/reflectivity variable nano composite fiber and preparation method thereof Download PDFInfo
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- CN104746160A CN104746160A CN201310738726.0A CN201310738726A CN104746160A CN 104746160 A CN104746160 A CN 104746160A CN 201310738726 A CN201310738726 A CN 201310738726A CN 104746160 A CN104746160 A CN 104746160A
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Abstract
The invention relates to infrared transmittance/reflectivity variable nano composite fiber and a preparation method thereof. The nano composite fiber comprises an organic polymer and rutile phase vanadium dioxide nano particles composited in the organic polymer, wherein mass fraction of rutile phase vanadium dioxide nano particles is 0.5-50%, and diameter of the nano composite fiber is 100nm-2mum.
Description
Technical field
The present invention relates to nanofiber technology field, particularly a kind of nano-composite fiber containing vanadium dioxide nano particle infrared transmittivity/varying reflectivity, its preparation method and the fibrofelt made thereof.
Background technology
Vanadium dioxide is a kind of material that there is multiple crystal structure, the reversible transition of low temperature monoclinic phase (M phase) semiconductor form to high temperature Tetragonal (R phase) metallic state is there is at 68 DEG C, with this phase in version, optical property and the electrical properties of material are undergone mutation.Based on the change of optical transmittance before and after vanadium dioxide phase transformation, it is applied to smart window material (G.Xu, P.Jin, M.Tazawa, K.Yoshimura, Optimization of antireflection coating for VO
2-basedenergy efficient window, Solar Energy Materials and Solar Cells, 83 (2004) 29-37), when this smart window is below phase transition temperature, holding chamber inside holding is beneficial to infrared light high transmission, more than phase transition temperature, then most of infra-red radiation is blocked in outdoor, in order to practical application, by the method for mixing tungsten, the phase transition temperature of vanadium dioxide smart window can be adjusted to about 30 DEG C.Vanadium dioxide smart window material adopts two kinds of method preparations at present, and a kind of that section of article forwardly provided strictly according to the facts equally uses magnetically controlled sputter method plated film; The another kind of method film forming using chemistry, first prepare the dispersion liquid of precursor solution or vanadium dioxide nano powder, then use spin coating, the methods such as spraying do film.For the preparation of vanadium dioxide M phase nano-powder, directly can be obtained by hydro-thermal reaction (Chinese patent CN102120615A), or the vanadium dioxide nano powder of first Hydrothermal Synthesis B phase or A phase, then be converted into M phase (Chinese patent CN101863511A) by heat treatment.The pattern of vanadium dioxide nano powder can be spherical, bar-shaped, wire, banded.
In infrared reflection coating, there is the transparent conductive oxide of nano-powder film or magnetron sputtering film preparation (TCO) for improving the infrared reflectivity of building glass, also having the coating of containing metal or semiconductor nanoparticle to utilize its infrared absorbance to reach purposes to the low reflection of infrared light.But not yet there is the relevant report of infrared varying reflectivity fabric.
Fabric aspect containing function nano material, relevant report is modal is use the antibiotic fabric (Xu Xiongli containing Nano Silver, Cao Yurong, Zhou Meihua, for medical dressing composite nanometer fiber felt containing nano silver gelatin/chitosan and preparation, Chinese patent CN101187111A), other the fabric containing metal or semiconductor nanoparticle is applied in catalysis and sensor material aspect (Formo, E., Lee, E., Campbell, D., Xia, Y.N.Functionalization ofelectrospun TiO2nanofibers with Pt nanoparticles and nanowires for catalyticapplications.Nano Lett8, 668-672 (2008)), used weaving techniques is generally electrostatic spinning, also report (the Tian Jiemo using melt spinning is had, biologically active nanometer fiber and its products, Chinese patent CN1635201A).The report of the fibrofelt at present not containing vanadium dioxide, does not have the report that textiles regulates and controls for infra-red radiation yet.
Summary of the invention
For prior art Problems existing, we devise a kind of nano-composite fiber and the composite fibrofelt that contain vanadium dioxide nano particle infrared transmittivity/varying reflectivity.
At this, the invention provides the nano-composite fiber of a kind of infrared transmittivity or varying reflectivity, wherein, described nano-composite fiber includes organic polymer and is compounded in the rutile phase hypovanadic oxide nano particle in described organic polymer, the mass fraction of wherein said rutile phase hypovanadic oxide nano particle is 0.5% ~ 50%, and the diameter of described nano-composite fiber is 100nm ~ 2 μm.
Advantage of the present invention is the nano-composite fiber obtaining a kind of infrared transmittivity of not reporting and varying reflectivity, the goods (fibrofelt) prepared by this composite fibre high temperature be in low through with low reflection state, and low temperature is in high transmission and high reverse--bias state, when adopting unadulterated pure rutile phase hypovanadic oxide nano particle, this transition temperature is 68 DEG C, regulates within the specific limits as required transition temperature is reduced or raises by element doping.
In the present invention, described rutile phase hypovanadic oxide nano particle comprises the rutile phase hypovanadic oxide nano particle of pure rutile phase hypovanadic oxide nano particle and/or element doping.
In the present invention, the particle diameter of described rutile phase hypovanadic oxide nano particle is below 100nm.
In the present invention, described organic polymer can be at least one in polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, EVA and polyacrylonitrile.
In the present invention, the preferable range of the mass fraction of described rutile phase hypovanadic oxide nano particle is 5% ~ 40%.
A kind of preparation method of above-mentioned nano-composite fiber is also provided in the present invention, wherein, described nano-composite fiber is prepared by spin processes, wherein spinning solution is mixed to form by described organic polymer, rutile phase hypovanadic oxide nano particle and organic solvent, wherein, in described spinning solution, the mass fraction of rutile phase hypovanadic oxide nano particle is 0.1% ~ 10%.
In the present invention, described spin processes can comprise electrostatic spinning, melt spinning, wet spinning and dry spinning.
Preferably, described spin processes is electrostatic spinning, and spinning voltage can be 8kV ~ 30kV.
Can continuous spinning be carried out, also can spinning discontinuously, at this moment preferably the spinning time is 5 ~ 60 minutes.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the monoclinic phase vanadium dioxide nano particle for electrostatic spinning;
Fig. 2 is be the stereoscan photograph of composite fibre under backscatter mode of 500nm containing vanadium dioxide nano particle diameter, and the organic matter that this spinning uses is PVP;
Fig. 3 is infrared through spectrum under high temperature state and cold state of the fibrofelt of vanadium dioxide nano particle containing different quality mark, and the organic matter that this spinning uses is PVP;
Fig. 4 is the infrared diffuse reflectance spectroscopy of fibrofelt under high temperature state and cold state of the vanadium dioxide nano particle containing different quality mark, and the organic matter that this spinning uses is PVP;
Fig. 5 is be the stereoscan photograph of composite fibrofelt under secondary electron pattern of 1 μm containing vanadium dioxide nano particle diameter, and the organic matter that this spinning uses is PMMA.
Detailed description of the invention
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that accompanying drawing and following embodiment are only for illustration of the present invention, and unrestricted the present invention.
The present invention designs and has prepared a kind of nano-composite fiber felt containing the infrared varying reflectivity of vanadium dioxide nano particle.
The technical solution adopted in the present invention is: monoclinic phase (Rutile Type) vanadium dioxide nano particle is mixed with the organic solution that can be used for electrostatic spinning and ultrasonic disperse evenly after carry out electrostatic spinning, in solution, the mass fraction of vanadium dioxide is 0.5% ~ 8%, and spinning diameter regulates between 150nm ~ 1 μm by organic content in regulation and control solution.Spinning aluminium foil receives, and can completely take off and test Infrared grey image after reaching certain thickness.
Vanadium dioxide nano particle is monoclinic phase (M phase) vanadium dioxide or doping M phase hypovanadic oxide nano particle, and doped chemical is the existing element that can change arbitrarily phase transition temperature of vanadium dioxide, such as Wu, Molybdenum, niobium, tantalum, titanium, chromium, fluorine etc.
Advantage of the present invention is the nano-composite fiber felt obtaining a kind of infrared reflectivity variable do not reported, this material high temperature be in low through or low reflection state, low temperature is in high transmission or high reverse--bias state, when transition temperature does not adulterate be 68 DEG C, regulate within the specific limits by element doping as required and make it reduce or raise.
Take discontinuous spin processes in the present invention, transmitance variable fibrofelt spinning the time be 5 ~ 15 minutes, be preferably 10 minutes, at this moment the difference of high/low temperature infrared transmittivity can reach more than 10%, and increase with the spinning time, fibrofelt thickens, and reduces until its devitrification the transmitance regulating power of light.The fibrofelt of varying reflectivity generally need spin more than 20 minutes to reach certain thickness and intensity, high/low temperature infrared reflectivity difference improves with vanadium dioxide content within the specific limits and improves, maximumly reach more than 30%, in fact after fibrofelt reaches certain thickness, the imitated time does not affect its reflectivity.
This nano-composite fiber structure designed by the present invention, can be used for manufacturing various energy-conservation goods as curtain, tent, clothes, sunshade etc.Its preparation can be not limited to electrospinning process and comprise can be used for industry mass-produced various spinning process as melt spinning, wet spinning, dry spinning etc.
Exemplify embodiment below further to describe the present invention in detail.Should understand equally; following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention.The technological parameters such as the time that following example is concrete, temperature are also only examples in OK range, and namely those skilled in the art can be done in suitable scope by explanation herein and select, and do not really want the concrete numerical value being defined in Examples below.
Embodiment 1
VO
2-PVP composite nanometer fiber felt (VO
2mass fraction about 26%)
By 0.7g PVP(molecular weight 1,300,000) and 9.3g alcohol mix and stir PVP is dissolved, add 0.25g monoclinic phase vanadium dioxide nano particle (phase transition temperature is 40 DEG C, lower with) subsequently, ultrasonic disperse carried out electrostatic spinning after 5 hours.Spinning voltage 15kV, syringe fltting speed is 2.5ml/h, and syringe needle is 15cm to acceptance screen distance.Spinning 10 minutes (testing through spectrum) or 30 minutes (test diffuse reflection spectrum) obtain the composite nanometer fiber felt that fibre diameter is 500nm.Stereoscan photograph is shown in accompanying drawing 2, sees accompanying drawing 3 under high temperature (60 DEG C) and low temperature (20 DEG C) through spectrum, and the infrared diffuse reflectance spectroscopy under high temperature (60 DEG C) and low temperature (20 DEG C) is shown in the dotted line in accompanying drawing 4.
Embodiment 2
VO
2-PVP composite nanometer fiber felt (VO
2mass fraction about 38%)
0.7g PVP and 9.3g alcohol are mixed and stirred makes PVP dissolve, and add 0.5g monoclinic phase vanadium dioxide nano particle subsequently, ultrasonic disperse carried out electrostatic spinning after 5 hours.Spinning voltage 15kV, syringe fltting speed is 2.5ml/h, and syringe needle is 15cm to acceptance screen distance.Spinning obtains the composite nanometer fiber felt that fibre diameter is 500nm for 30 minutes.See accompanying drawing 3 through spectrum under high temperature (60 DEG C) and low temperature (20 DEG C), the infrared diffuse reflectance spectroscopy under high temperature (60 DEG C) and low temperature (20 DEG C) is shown in the dotted line in accompanying drawing 4.
Embodiment 3
VO
2-PMMA composite nanometer fiber felt (VO
2mass fraction about 21%)
By 2.25g PMMA and 7.75g DMF(dimethyl formamide) mix and stir PMMA is dissolved, add 0.6g monoclinic phase vanadium dioxide nano particle subsequently, ultrasonic disperse carried out electrostatic spinning after 5 hours.Spinning voltage 10kV, syringe fltting speed is 1.5ml/h, and syringe needle is 15cm to acceptance screen distance.Spinning obtains the composite nanometer fiber felt that fibre diameter is 1 μm for 30 minutes.Stereoscan photograph is shown in accompanying drawing 5.
Embodiment 4
VO
2-PAN composite nanometer fiber felt (VO
2mass fraction about 17%)
0.5g PAN and 9.5g DMF is mixed and stirred makes PAN dissolve, and add 0.1g monoclinic phase vanadium dioxide nano particle subsequently, ultrasonic disperse carried out electrostatic spinning after 5 hours.Spinning voltage 12kV, syringe fltting speed is 2.5ml/h, and syringe needle is 15cm to acceptance screen distance.Spinning obtains the composite nanometer fiber felt that fibre diameter is 250nm for 30 minutes.
Embodiment 4
VO
2-PEVA composite nanometer fiber felt (VO
2mass fraction about 29%)
1.6g PEVA and 8.4g chloroform are mixed and stirred makes PEVA dissolve, and add 0.25g monoclinic phase vanadium dioxide nano particle subsequently, ultrasonic disperse carried out electrostatic spinning after 5 hours.Spinning voltage 18kV, syringe fltting speed is 2.5ml/h, and syringe needle is 15cm to acceptance screen distance.Spinning obtains the composite nanometer fiber felt that fibre diameter is 500nm for 30 minutes.
Industrial applicability: the nano-composite fiber that the invention provides infrared transmittivity/varying reflectivity, can be used for manufacturing various energy-conservation goods as curtain, tent, clothes, sunshade etc.
Claims (8)
1. the nano-composite fiber of infrared transmittivity/varying reflectivity, it is characterized in that, described nano-composite fiber includes organic polymer and is compounded in the rutile phase hypovanadic oxide nano particle of described organic polymer, the mass fraction of wherein said rutile phase hypovanadic oxide nano particle is 0.5% ~ 50%, and the diameter of described nano-composite fiber is 100nm ~ 2 μm.
2. nano-composite fiber according to claim 1, is characterized in that, described rutile phase hypovanadic oxide nano particle comprises the rutile phase hypovanadic oxide nano particle of pure rutile phase hypovanadic oxide nano particle and/or element doping.
3. nano-composite fiber according to claim 1 and 2, is characterized in that, the particle diameter of described rutile phase hypovanadic oxide nano particle is below 100nm.
4. nano-composite fiber according to any one of claim 1 to 3, is characterized in that, described organic polymer is at least one in polyvinylpyrrolidone, polyvinyl alcohol, polymethyl methacrylate, EVA and polyacrylonitrile.
5. the preparation method of a nano-composite fiber according to any one of claim 1 to 4, it is characterized in that, described nano-composite fiber is prepared by spin processes, wherein spinning solution is mixed to form by described organic polymer, rutile phase hypovanadic oxide nano particle and organic solvent, wherein, in described spinning solution, the mass fraction of rutile phase hypovanadic oxide nano particle is 0.1% ~ 10%.
6. preparation method according to claim 5, is characterized in that, described spin processes comprises electrostatic spinning, melt spinning, wet spinning and dry spinning.
7. the preparation method according to claim 5 or 6, is characterized in that, described spin processes is electrostatic spinning, and spinning voltage is 8kV ~ 30kV.
8. the fibrofelt made of a nano-composite fiber according to any one of claim 1 to 4, it is characterized in that, the infrared transmittivity of described fibrofelt when the phase transition temperature lower than described rutile phase hypovanadic oxide nano particle or reflectivity are higher than the infrared transmittivity of described fibrofelt when the phase transition temperature higher than described rutile phase hypovanadic oxide nano particle or reflectivity.
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Cited By (5)
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| CN105316789A (en) * | 2015-09-30 | 2016-02-10 | 贵州华益能环保科技有限公司 | Preparation method and application of inorganic composite phase-change energy storage filament |
| CN106978671A (en) * | 2017-04-26 | 2017-07-25 | 中国科学院广州能源研究所 | One kind prepares transparent VO using electrostatic spinning technique2The method of thermocolour smart membranes |
| CN107460558A (en) * | 2017-07-28 | 2017-12-12 | 蒋绪川 | Textile, preparation method and applications with regulation infrared transparency energy |
| CN114808170A (en) * | 2021-01-28 | 2022-07-29 | 中国科学院上海硅酸盐研究所 | Light-color fiber with sterilization and heat storage functions, preparation method thereof and fiber product |
| CN114995001A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Variable device of electrogenerated emissivity |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105316789A (en) * | 2015-09-30 | 2016-02-10 | 贵州华益能环保科技有限公司 | Preparation method and application of inorganic composite phase-change energy storage filament |
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| CN114808170A (en) * | 2021-01-28 | 2022-07-29 | 中国科学院上海硅酸盐研究所 | Light-color fiber with sterilization and heat storage functions, preparation method thereof and fiber product |
| CN114808170B (en) * | 2021-01-28 | 2024-04-12 | 中国科学院上海硅酸盐研究所 | Light-colored sterilization heat storage functional fiber, preparation method thereof and fiber product |
| CN114995001A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院上海硅酸盐研究所 | Variable device of electrogenerated emissivity |
| CN114995001B (en) * | 2021-03-01 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Electroluminescence emissivity variable device |
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Application publication date: 20150701 |