CN104804733A - Rare-earth strontium aluminate luminous nanorod and preparation method thereof - Google Patents
Rare-earth strontium aluminate luminous nanorod and preparation method thereof Download PDFInfo
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- CN104804733A CN104804733A CN201510255956.0A CN201510255956A CN104804733A CN 104804733 A CN104804733 A CN 104804733A CN 201510255956 A CN201510255956 A CN 201510255956A CN 104804733 A CN104804733 A CN 104804733A
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Abstract
The invention belongs to the field of a nanometer luminous material, and discloses a rare-earth aluminate luminous material with a one-dimensional nanometer structure and a preparation method thereof. The rare-earth aluminate luminous material is characterized in that SrAl2O4 is used as a substrate, Eu<2+> and Dy<3+> rare-earth ions are used as activating agents, the one-dimensional nanometer rod structure is adopted, the diameter is smaller than 250nm, and the length-diameter ratio is greater than 102. According to the nanometer luminous material, a sol-gel and electrostatic spinning combining method is adopted for preparing precursor fiber; then, the roasting is carried out at a certain temperature and under the weak reduction atmosphere; a target product is obtained; compared with micron-sized coarse crystalline powder, the product has the advantage that the sending peak position generates blue shift. The nanometer luminous material has the advantages and characteristics of no toxicity, no radiation pollution, high material stability and the like, and has application values in the fields of nanometer electronic devices, low-intensity lighting and the like.
Description
Technical field
The present invention relates to luminescent material preparation field, specifically a kind of rare earth aluminic acid strontium Illuminant nanometer rod and preparation method thereof.
Background technology
Long after glow luminous material is the energy-saving material that in numerous luminescent material, a class is important, especially has great advantage in sun power use.Luminescent material is under the irradiation of ambient light, energy-absorbing also stores, after ambient light irradiates stopping, luminescent material discharges the energy deposited in the form of light, so long after glow luminous material has very wide application prospect, be used on the products such as luminous paint, luminous printing ink, luminescent ceramic.Matrix is that the long after glow luminous material because have of aluminate is stablized, acidproof, alkaline-resisting, oxidation-resistance, pollution-free, "dead", the fields such as building decoration, communications and transportation, military installations, fire-fighting emergent, textile decoration can be widely used in.At present, the preparation of rear-earth-doped strontium aluminate luminous material is carried out mainly through solid state reaction, after mixing, calcines in high temperature kiln under reducing atmosphere by chemical feedstocks, then after grinding, obtains luminescent powder.The light-emitting particles obtained by above-mentioned technique is comparatively thick, and generally more than 10 microns, the field higher to fineness requirement at some can not use.
Nano strontium aluminate shows many new different propertiess compared with body material strontium aluminate.Due to the granular of particle size, the sharply increase of specific surface area, Nano strontium aluminate is created and surface effects, small-size effect and the quantum confined effect etc. not available for its body material, thus makes Nano strontium aluminate have the incomparable property of general strontium aluminate product in power, optical, electrical, magnetic, susceptibility etc.In national defence, chemical industry, aviation, light industry, medicine and other fields, there is significant application value.In addition, the performance of nano material except with its size mutually outside the Pass, be also closely related with its shape, 1-dimention nano luminescent material is due to the impact by its nanoscale and one-dimentional structure, the energy band structure of luminescent material is changed, thus shows unique luminosity and rule.At present, the methods such as existing numerous research employing combustion method, sol-gel method, coprecipitation methods have synthesized rare upper doped strontium aluminate nano particle, but have no report about the rare earth aluminic acid strontium luminescent material of one dimension Nano structure and the research of preparation thereof.
Summary of the invention
At the various preparation SrAl that background technology is mentioned
2o
4: Eu
2+, Dy
3+in the method for luminescent material, the shortcoming of high temperature solid-state method is that calcining temperature is high, consuming time, and the luminescent powder particle of preparation is comparatively large, needs grinding, and the luminescent properties after grinding reduces; The shortcoming of sol-gel method is complicated process of preparation, and the luminescent properties of luminescent powder is undesirable; Microwave is sent out with precipitator method preparation technology all immature, also have many technology to have to be solved, and these methods all can not prepare the SrAl with one dimension Nano structure
2o
4: Eu
2+, Dy
3+luminescent material.For this reason, the method that the present invention adopts sol-gel technique and electrostatic spinning technique to combine, prepares europium dysprosium pair and mixes strontium aluminate Illuminant nanometer rod, to expanding the potential range of application of this luminescent material.
The present invention is achieved through the following technical solutions: first, according to stoichiometric ratio Sr
1-x-yal
2o
4: xEu
2+, yDy
3+(x:1-5mol%, y:2-8mol%) makes the presoma spinning colloidal sols with certain viscosity that can be used for electrostatic spinning, under suitable electrostatic spinning process, carry out electrostatic spinning, prepares PVP/ [Sr (NO
3)
2+ Al (NO
3)
3+ Eu (NO
3)
3+ Dy (NO
3)
3] composite nano fiber, put it in high temperature sintering furnace, be greater than 1100 DEG C in temperature, fully calcined for some time under weakly reducing atmosphere, obtain the pure phase SrAl with one-dimentional structure
2o
4: Eu
2+, Dy
3+illuminant nanometer rod.
The invention will be further described below, and concrete steps are as follows:
(1) sol-gel technique is adopted to prepare SrAl
2o
4: Eu
2+, Dy
3+precursor solution.This precursor solution with containing strontium, containing aluminium nitrate for synthesis SrAl
2o
4the raw material of matrix, with rare earth doped europium compound, dysprosium compound for providing Eu
2+, Dy
3+source (mostly be Eu
2o
3and Dy
2o
3), according to stoichiometric ratio SrAl
2o
4: xEu
2+, yDy
3+(x:1-5mol%, y:2-8mol%) takes above-mentioned each raw material, by load weighted Eu
2o
3and Dy
2o
3evaporate excess nitric acid obtain Eu (NO by concentrated nitric acid heating for dissolving
3)
3with Dy (NO
3)
3;
(2) will containing strontium, be dissolved in a small amount of DMF (or dehydrated alcohol) containing the nitrate of aluminium, and with (1) gained Eu (NO
3)
3with Dy (NO
3)
3be uniformly mixed, obtain containing Sr
2+, Al
3+, Eu
3+, Dy
3+nitrate solution;
(3) by the polyvinylpyrrolidone (PVP of 8% ~ 15% massfraction, molecular weight 1,300,000) or polyvinyl alcohol (PVA) or polyacrylonitrile (PAN) add in the DMF (or dehydrated alcohol) of 75 ~ 85% massfractions, airtight more than magnetic agitation 4h at room temperature or 30 ~ 60 DEG C, until form even, water white thick liquid;
(4) (2) gained nitrate solution is slowly poured in the thick liquid of (3), and namely more than Keep agitation 30min obtain the precursor solution being suitable for electrostatic spinning;
(5) get appropriate precursor solution and carry out electrostatic spinning in electrostatic spinning liquid storage pipe.Electrospinning processes is: spinning voltage 8 ~ 20kV volts DS, and spinning solution fltting speed is 0.05 ~ 0.5mL/h, and nozzle inside diameter is less than 1mm, and jet hole is 15 ~ 20cm to the distance of receiving trap, and ambient relative humidity is 30% ~ 60%, and temperature is 10 DEG C ~ 30 DEG C.As the aluminium-foil paper of negative pole being collected PVP/ [Sr (NO
3)
2+ Al (NO
3)
3+ Eu (NO
3)
3+ Dy (NO
3)
3] composite nano fiber.
(6) composite nano fiber of above-mentioned preparation is put into high temperature sintering furnace, at carbon dust or H
2+ N
3calcine under the weakly reducing atmosphere provided.The temperature rise rate of sintering oven is 1 ~ 10 DEG C/min, 1100 DEG C ~ 1300 DEG C calcining at constant temperature 2 ~ 4 hours, then with stove cooling or be down to room temperature with the speed being less than 5 DEG C/min, namely obtains SrAl
2o
1: Eu
2+, Dy
3+illuminant nanometer rod.
With SrAl prepared by aforesaid method
2o
4: Eu
2+, Dy
3+illuminant nanometer material is shown as strontium aluminate pure phase (PDF No.34-0379) by X-ray diffractometer test, sees accompanying drawing 1, belongs to oblique system, there is the bar-shaped structure of 1-dimention nano, diameter < 250nm, diameter Distribution is homogeneous, length-to-diameter ratio > 10
2, see accompanying drawing 2; The excitation spectrum scope of this Illuminant nanometer material is 250 ~ 450nm, can daylight or fluorescence excitation, and this sample launches Eu under 365nm wavelength light excites
2+the 510nm green light of feature, compared with micron-sized coarse-grain powder, there is blue shift in its emission peak positions, and have obvious twilight sunset feature, sees accompanying drawing 3 and Fig. 4.
Accompanying drawing explanation
Fig. 1: prepared sample and standard card (PDF No.34-0379/SrAl
2o
4) XRD spectra;
Fig. 2: the electron scanning micrograph (SEM) of prepared sample;
Fig. 3: the excitation and emission spectra figure of prepared sample;
Fig. 4: prepared sample decay of afterglow curve.
Embodiment
Below in conjunction with embodiment, the present invention is described in more detail, but the present invention is not limited to these embodiments.
Embodiment 1: take 0.053g Eu
2o
3with 0.112g Dy
2o
3put into beaker, add 5ml concentrated nitric acid, and 80 DEG C of heated and stirred, make Eu
2o
3and Dy
2o
3dissolve completely, and continue heating evaporation and fall excess nitric acid, obtain Eu (NO
3)
3with Dy (NO
3)
3; By 7.503g Al (NO
3)
39H
2o, 1.926g Sr (NO
3)
2be dissolved in 20ml DMF, and with Eu (NO
3)
3with Dy (NO
3)
3be mixed to get nitrate colloidal sol; By 2g PVP (M
w=1 300 000) be dissolved in 10g DMF, under normal temperature, airtight magnetic agitation is to dissolving (about 5 ~ 6h) completely, takes out 5g and add from obtained nitrate colloidal sol, continue to stir about 30min obtains can the water white transparency precursor solution of electrospinning; Get the Electrospun liquid storage pipe of 5ml precursor liquid injection with 20G syringe needle, at volts DS 11kV, solidification distance 15cm, fltting speed 0.2mL/h, room temperature 17 DEG C, relative humidity is carry out electrostatic spinning under the condition of 40%, as the aluminium-foil paper of negative pole being collected PVP/ nitrate composite nano fiber.This composite nano fiber is put into retort furnace under 1100 DEG C of carbon reducing agent atmosphere, calcines 4h, temperature rise rate is 2 DEG C/min, with stove cooling after calcining terminates, namely obtains SrAl
2o
4: Eu
2+, Dy
3+illuminant nanometer rod.
Embodiment 2: take 0.141g Eu
2o
3with 0.224g Dy
2o
3put into beaker, add 10ml concentrated nitric acid, and 60 DEG C of heated and stirred, make Eu
2o
3and Dy
2o
3dissolve completely, and continue heating evaporation and fall excess nitric acid, obtain Eu (NO
3)
3with Dy (NO
3)
3; By 15.005g Al (NO
3)
39H
2o, 3.810g Sr (NO
3)
2be dissolved in 40ml dehydrated alcohol, and with Eu (NO
3)
3with Dy (NO
3)
3be mixed to get nitrate solution; Be dissolved in by 2g PAN in 10g dehydrated alcohol, under normal temperature, airtight magnetic agitation is to dissolving completely, adds 5g nitrate colloidal sol, and continue to stir about 30min obtains can the water white transparency precursor solution of electrospinning; Get the Electrospun liquid storage pipe of 10ml precursor liquid injection with 18G syringe needle, apply 15kV volts DS, solidification distance 15cm, fltting speed is 0.5mL/h, room temperature 20 DEG C, relative humidity is carry out electrostatic spinning under 52% condition, as the aluminium-foil paper of negative pole being collected PAN/ nitrate composite nano fiber.This composite nano fiber is put into retort furnace at 1200 DEG C, 5%H
2+ 95%N
2calcine 3h under reducing atmosphere, temperature rise rate is 2 DEG C/min, with stove cooling, namely obtains SrAl
2o
4: Eu
2+, Dy
3+illuminant nanometer rod.
Claims (3)
1. a preparation method for rare-earth-doped strontium aluminate Illuminant nanometer rod, its concrete steps are as follows:
(1) according to formula composition formula Sr
1-x-yal
2o
4: xEu
2+, yDy
3+, wherein 1mol% < x < 5mol%, 2mol% < y < 8mol%, takes each raw material, by load weighted Eu
2o
3and Dy
2o
3evaporate excess nitric acid obtain Eu (NO by concentrated nitric acid heating for dissolving
3)
3with Dy (NO
3)
3; By Al (NO
3)
39H
2o, Sr (NO
3)
2be dissolved in appropriate solvent, and with Eu (NO
3)
3with Dy (NO
3)
3be mixed to get nitrate solution, in this solution, add appropriate viscosity modifier, with plastic film sealing, to be placed on magnetic stirring apparatus to stir at room temperature or 30 ~ 60 DEG C until obtain evenly, water white transparency and have the Static Spinning precursor sol solution of certain viscosity;
(2) get appropriate above-mentioned precursor solution and inject electrostatic spinning syringe, under certain spinning technique, carry out electrostatic spinning, as the aluminium-foil paper of negative pole being collected PVP/ nitrate composite nano fiber.
(3) composite nano fiber collected in step (2) is put into high temperature sintering furnace, 1000 ~ 1400 DEG C, calcining 2 ~ 4 hours under weakly reducing atmosphere, after cooling, obtain the strontium aluminate Illuminant nanometer rod of europium doped, dysprosium.
2. method according to claim 1, is characterized in that the solvent described in step (1) is dehydrated alcohol or DMF (DMF); Described viscosity modifier is PVP or PVA or PAN.
3. method according to claim 1, it is characterized in that the electrostatic spinning process described in step (2) mainly comprises: spinning voltage is 8kV ~ 20kV, solidification distance 10 ~ 20cm, fltting speed is 0.1 ~ 0.5mL/h, spinning environment temperature 10 ~ 30 DEG C, relative humidity is 30% ~ 60%.
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Cited By (5)
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|---|---|---|---|---|
| CN110229657A (en) * | 2019-04-26 | 2019-09-13 | 深圳科尔新材料科技有限公司 | The preparation method of long afterglow mechanoluminescence material |
| CN110317605A (en) * | 2018-03-30 | 2019-10-11 | 中国科学院过程工程研究所 | A kind of preparation method and purposes of the fluorescence probe based on self-assembled micelle |
| CN111155236A (en) * | 2020-01-15 | 2020-05-15 | 华侨大学 | Method for preparing long-afterglow luminescent film material based on electrostatic spinning technology and application |
| CN112663377A (en) * | 2020-12-22 | 2021-04-16 | 阿尔诺维根斯(衢州)特种纸有限公司 | Preparation method of natural flexible transparent paper |
| CN110066653B (en) * | 2019-05-28 | 2021-04-16 | 陕西科技大学 | Preparation method of europium-doped strontium aluminate nanobelt with up-conversion luminescence property |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110317605A (en) * | 2018-03-30 | 2019-10-11 | 中国科学院过程工程研究所 | A kind of preparation method and purposes of the fluorescence probe based on self-assembled micelle |
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| CN110229657B (en) * | 2019-04-26 | 2024-07-26 | 深圳科尔新材料科技有限公司 | Preparation method of long-afterglow luminescent material |
| CN110066653B (en) * | 2019-05-28 | 2021-04-16 | 陕西科技大学 | Preparation method of europium-doped strontium aluminate nanobelt with up-conversion luminescence property |
| CN111155236A (en) * | 2020-01-15 | 2020-05-15 | 华侨大学 | Method for preparing long-afterglow luminescent film material based on electrostatic spinning technology and application |
| CN112663377A (en) * | 2020-12-22 | 2021-04-16 | 阿尔诺维根斯(衢州)特种纸有限公司 | Preparation method of natural flexible transparent paper |
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Application publication date: 20150729 |