CN101942711B - Electrostatic spinning method of submicron green fluorescent fiber Gd2O3: Tb3+ - Google Patents

Electrostatic spinning method of submicron green fluorescent fiber Gd2O3: Tb3+ Download PDF

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CN101942711B
CN101942711B CN2010102652162A CN201010265216A CN101942711B CN 101942711 B CN101942711 B CN 101942711B CN 2010102652162 A CN2010102652162 A CN 2010102652162A CN 201010265216 A CN201010265216 A CN 201010265216A CN 101942711 B CN101942711 B CN 101942711B
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fiber
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CN101942711A (en
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杜平凡
熊杰
宋立新
常怀云
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Zhejiang Sci Tech University ZSTU
Zhejiang University of Science and Technology ZUST
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Abstract

The invention discloses an electrostatic spinning method of submicron green fluorescent fiber Gd2O3: Tb3+. The method comprises the following steps: dissolving two acetate i.e. gadolinium acetate and terbium acetate based on mole ratio in deionized water by ultrasonic processing and magnetic stirring, wherein the total molar concentration of acetate solution is 0.3-0.5 mole/L; then adding polyoxythylene in the solution, wherein the weight of the polyoxythylene is 1-1.2 times of the total weight of the acetates, and stirring at the temperature of 55 DEG C to obtain spinning solution; placing the spinning solution in an injector with a capillary needle tube, applying high voltage between the needle tube and a receiving device, using a micro-injecting pump to control flow rate, jetting trickle and solidifying to form compound fibre which is collected on the receiving device the surface of which is covered with aluminum foil; and transferring the obtained compound fibre to a silicon wafer for roasting, and obtaining the submicron green fluorescent fiber Gd2O3: Tb3+ after the polyoxythylene is completely removed. The invention has simple process, wild preparation conditions, no pollution on environment, low cost and the like.

Description

Sub-micron green fluorescence fiber Gd＜sub〉2＜/sub O＜sub 3＜/sub: Tb＜sup〉3+＜/sup electrospinning process
Technical field
The present invention relates to the ultra-fine inorganic fibre preparation methods, particularly relate to a kind of sub-micron green fluorescence fiber Gd 2O 3: Tb 3+Electrospinning process.
Background technology
The character of submicrometer structure material, preparation and application study have become one of research focus of material science.Electrostatic spinning technique is a kind of effective new method of the accurate one-dimensional sub micrometer structure material of preparation, it prepares superfine fibre by electrostatic force as tractive force, be the schematic diagram of electrostatic spinning process as shown in Figure 1, its principle is as follows: the spinning solution with certain viscosity is encased in the syringe that has the capillary needle tubing, the high pressure of volts up to ten thousand in addition between the receiving system of needle tubing and ground connection, thus a powerful electrostatic field produced.Electric field force puts on the surface of spinning solution and produces electric current, and the characteristic of utilizing like charges to repel each other makes electric field force produce an outside power mutually on the contrary with the surface tension direction of spinning solution.When applied voltage increases and surpass a certain critical value, the suffered electric field force of spinning solution will overcome surface tension and the viscous force and form the injection thread of self.Spray thread drafted thousands of times in a few tens of milliseconds, along unsettled helical trajectory bending motion, along with solvent evaporates, thread solidify to form the superfine fibre of micron to nano grade, is arranged on the gathering-device with unordered shape.
The characteristics of electrostatic spinning are simple, and prepared fiber is even, quasi-continuous, and can reach the length that satisfies the photoelectric device requirement, have been widely used in the preparation high molecular superfine fiber.Recently, people improve this technology again, are used for preparing multiple inorganic ultrafine fiber.Gd 2O 3: Tb 3+As a kind of green fluorescent material of function admirable, can be applicable to aspects such as FPD, an emission, photoelectric functional device.People have adopted several different methods to synthesize Gd 2O 3: Tb 3+Fluorescent powder, and its characteristic studied.If fluorescent material is made submicron order or even nano level fiber, because its special pattern and structure are expected to obtain special nature and application.At present, about green fluorescence fiber Gd 2O 3: Tb 3+Electrostatic spinning preparation do not see open report as yet.
Summary of the invention
The purpose of this invention is to provide a kind of sub-micron green fluorescence fiber Gd 2O 3: Tb 3+Electrospinning process.With polyethylene glycol oxide (PEO), gadolinium acetate (Gd (CH 3COO) 3) and acetic acid terbium (Tb (CH 3COO) 3) be raw material, utilize electrostatic spinning technique to prepare PEO-(Gd (CH 3COO) 3+ Tb (CH 3COO) 3) composite fibre, and composite fibre carried out calcination process, obtained the green fluorescence fiber Gd of submicron order 2O 3: Tb 3+
The technical solution used in the present invention, promptly this preparation method's step is as follows:
1) with mol ratio is 100: 2～100: 6 Gd (CH 3COO) 3And Tb (CH 3COO) 3Two kinds of acetate are dissolved in deionized water through sonicated and magnetic agitation, the total molar concentration of acetate solution is 0.3～0.5 mol, adding quality then in solution is the PEO of 1～1.2 times of acetate gross mass, stirs 4 hours acquisition spinning solutions down at 55 ℃, leaves standstill cooling;
2) spinning solution is encased in the syringe that has the capillary needle tubing, adds high voltage between the receiving system of needle tubing and ground connection, spinning solution overcomes self under the effect of electrostatic field surface tension and viscous force form the injection thread, by micro-injection pump control flow rate; Along with solvent evaporates, spray thread and solidify to form PEO-(Gd (CH 3COO) 3+ Tb (CH 3COO) 3) composite fibre, being collected in surface coverage with disordered state has on the receiving system of aluminium foil;
3) composite fibre that obtains is transferred on the clean silicon chip, after the drying, put into the Muffle furnace roasting, be incubated after 5～7 hours, PEO removes fully, obtains sub-micron green fluorescence fiber Gd 2O 3: Tb 3+
Described step 2) high voltage in is 10～16KV, and flow rate is 0.006～0.01 ml/min, and needle point is 12～20 centimetres to the distance of receiving system.
The heating rate of the selection in the described step 3) is 1 ℃/minute, and sintering temperature is 500～900 ℃.
Prepared Gd 2O 3: Tb 3+Be fibrous, and the diameter of fiber is 400～500nm.
The beneficial effect that the present invention has is:
The present invention has successfully prepared the good sub-micron green fluorescence fiber Gd of luminescent properties 2O 3: Tb 3+, obtained to be different from the unique texture and the pattern of powder luminous material, effectively expanded the type and the purposes of luminescent material.Simultaneously, method of electrostatic spinning have other preparation low-dimensional materials method incomparable advantage, for example technology is simple, preparation condition is gentle, environmentally safe, cost are low etc., and material possesses very high draw ratio, pattern homogeneous, controlled.The present invention is expected in fields such as energy-conserving and environment-protective, photoelectric functional device, advanced micro-nano device acquisition applications well.
Description of drawings
Fig. 1 is the schematic diagram of electrostatic spinning process.Among the figure: 1, spinning solution, 2, the capillary needle tubing, 3, syringe, 4, high voltage source, 5, micro-injection pump, 6, composite fibre, 7, receiving system.
Fig. 2 is the PEO-(Gd (CH of embodiment 1 preparation 3COO) 3+ Tb (CH 3COO) 3) thermogravimetric (TG) curve map of composite fibre sample.
Fig. 3 is X-ray diffraction (XRD) spectrogram of sample after roasting of embodiment 1 preparation.
Fig. 4 is fluorescence (PL) spectrogram of sample after roasting of embodiment 1 preparation.
Fig. 5 is field emission scanning electron microscope (FESEM) photo of sample before and after roasting of embodiment 1 preparation.
The specific embodiment
The invention will be further described below in conjunction with drawings and Examples.
As shown in Figure 1, the step of the inventive method is as follows:
1) with mol ratio is 100: 2～100: 6 Gd (CH 3COO) 3And Tb (CH 3COO) 3Two kinds of acetate are dissolved in deionized water through sonicated and magnetic agitation, the total molar concentration of acetate solution is 0.3～0.5 mol, adding quality then in solution is the PEO of 1～1.2 times of acetate gross mass, stirs 4 hours acquisition spinning solutions 1 down at 55 ℃, leaves standstill cooling;
2) spinning solution 1 is encased in the syringe 3 that has capillary needle tubing 2, between the receiving system of needle tubing and ground connection, add high voltage 4, spinning solution overcomes self under the effect of electrostatic field surface tension and viscous force form the injection thread, by micro-injection pump 5 control flow rates; Along with solvent evaporates, spray thread and solidify to form PEO-(Gd (CH 3COO) 3+ Tb (CH 3COO) 3) composite fibre 6, being collected in surface coverage with disordered state has on the receiving system 7 of aluminium foil;
3) composite fibre 6 that obtains is transferred on the clean silicon chip, after the drying, put into the Muffle furnace roasting, be incubated after 5～7 hours, PEO removes fully, obtains the Gd of crystalline state 2O 3: Tb 3+Fiber.
Described step 2) high voltage in is 10～16KV, and flow rate is 0.006～0.01 ml/min, and needle point is 12～20 centimetres to the distance of receiving system 7.
The heating rate of the selection in the described step 3) is 1 ℃/minute, and sintering temperature is 500～900 ℃.
Embodiment 1:
With 1 gram Gd (CH 3COO) 3With 0.02 gram Tb (CH 3COO) 3Join in 10 ml deionized water, sonicated made two kinds of acetate dissolve fully in 30 minutes through magnetic agitation after 10 minutes again, added 1.02 gram PEO then in solution, stirred down at 55 ℃ and made spinning solution in 4 hours, left standstill cooling; Spinning solution is encased in the syringe, and spinning obtains PEO-(Gd (CH under voltage to be 10KV, flow rate 0.006 ml/min, needle point to the distance of collecting board be 12 centimetres condition 3COO) 3+ Tb (CH 3COO) 3) composite fibre; The composite fibre of collecting on the aluminium foil is transferred on the clean silicon chip, after the drying, put into the Muffle furnace roasting, be warming up to 500 ℃ of roastings, be incubated 5 hours, obtain the sub-micron green fluorescence fiber Gd of crystalline state with 1 ℃/minute speed 2O 3: Tb 3+Fig. 2 is thermogravimetric (TG) curve map of the composite fibre sample of this embodiment preparation, and as can be seen from Figure, temperature needs more than 400 ℃, and PEO could be removed substantially.Fig. 3 is X-ray diffraction (XRD) spectrogram of sample after roasting, with the Gd that is numbered JCPDS No.11-0604 2O 3The standard spectrogram fits like a glove, and what generation was described is with Gd 2O 3Be the inorganic material of matrix, and the small amount of impurities Tb that mixes 3+Do not change Gd 2O 3The original crystal structure of matrix.Fig. 4 is fluorescence (PL) spectrogram of sample after roasting, one group of four groups of emission peak a little less than, its excess-three group is stronger, illustrates that luminescent properties is good, corresponds respectively to as figure 5D 4→ 7F 6, 5D 4→ 7F 5, 5D 4→ 7F 4, 5D 4→ 7F 3Transition between the energy level.Fig. 5 is the pattern photo that sample is taken with field emission scanning electron microscope (FESEM) before and after roasting, can clearly observe Gd 2O 3: Tb 3+The diameter of fiber belongs to submicron order between 400～500nm.
Embodiment 2:
With 1 gram Gd (CH 3COO) 3With 0.04 gram Tb (CH 3COO) 3Join in 8 ml deionized water, sonicated made two kinds of acetate dissolve fully in 30 minutes through magnetic agitation after 10 minutes again, added 1.14 gram PEO then in solution, stirred down at 55 ℃ and made spinning solution in 4 hours, left standstill cooling; Spinning solution is encased in the syringe, and spinning obtains PEO-(Gd (CH under voltage to be 13KV, flow rate 0.008 ml/min, needle point to the distance of collecting board be 16 centimetres condition 3COO) 3+ Tb (CH 3COO) 3) composite fibre; The composite fibre of collecting on the aluminium foil is transferred on the clean silicon chip, after the drying, put into the Muffle furnace roasting, be warming up to 750 ℃ of roastings, be incubated 6 hours, obtain the sub-micron green fluorescence fiber Gd of crystalline state with 1 ℃/minute speed 2O 3: Tb 3+The thermogravimetric of the sample that this embodiment is prepared (TG) curve map, X-ray diffraction (XRD) spectrogram, fluorescence (PL) spectrogram, field emission scanning electron microscope (FESEM) photo are close with embodiment 1.
Embodiment 3:
With 1 gram Gd (CH 3COO) 3With 0.06 gram Tb (CH 3COO) 3Join in 6 ml deionized water, sonicated made two kinds of acetate dissolve fully in 30 minutes through magnetic agitation after 10 minutes again, added 1.27 gram PEO then in solution, stirred down at 55 ℃ and made spinning solution in 4 hours, left standstill cooling; Spinning solution is encased in the syringe, and spinning obtains PEO-(Gd (CH under voltage to be 16KV, flow rate 0.01 ml/min, needle point to the distance of collecting board be 20 centimetres condition 3COO) 3+ Tb (CH 3COO) 3) composite fibre; The composite fibre of collecting on the aluminium foil is transferred on the clean silicon chip, after the drying, put into the Muffle furnace roasting, be warming up to 900 ℃ of roastings, be incubated 7 hours, obtain the sub-micron green fluorescence fiber Gd of crystalline state with 1 ℃/minute speed 2O 3: Tb 3+The thermogravimetric of the sample that this embodiment is prepared (TG) curve map, X-ray diffraction (XRD) spectrogram, fluorescence (PL) spectrogram, field emission scanning electron microscope (FESEM) photo are close with embodiment 1.

Claims (4)

1. sub-micron green fluorescence fiber Gd 2O 3: Tb 3+Electrospinning process, it is characterized in that the step of this method is as follows:
1) with mol ratio is 100: 2～100: 6 Gd (CH 3COO) 3And Tb (CH 3COO) 3Two kinds of acetate are dissolved in deionized water through sonicated and magnetic agitation, the total molar concentration of acetate solution is 0.3～0.5 mol, adding quality then in solution is the PEO of 1～1.2 times of acetate gross mass, stirs 4 hours acquisition spinning solutions (1) down at 55 ℃, leaves standstill cooling;
2) spinning solution (1) is encased in the syringe (3) that has capillary needle tubing (2), between the receiving system of needle tubing and ground connection, add 10～16KV high voltage, spinning solution overcomes self under the effect of electrostatic field surface tension and viscous force form the injection thread, by micro-injection pump (5) control flow rate; Along with solvent evaporates, spray thread and solidify to form PEO-(Gd (CH 3COO) 3+ Tb (CH 3COO) 3) composite fibre (6), being collected in surface coverage with disordered state has on the receiving system (7) of aluminium foil;
3) composite fibre (6) that obtains is transferred on the clean silicon chip, after the drying, put into the Muffle furnace roasting, be incubated after 5～7 hours, PEO removes fully, obtains sub-micron green fluorescence fiber Gd 2O 3: Tb 3+
2. a kind of sub-micron green fluorescence fiber Gd according to claim 1 2O 3: Tb 3+Electrospinning process, it is characterized in that: the flow rate described step 2) is 0.006～0.01 ml/min, needle point is 12～20 centimetres to the distance of receiving system (7).
3. a kind of sub-micron green fluorescence fiber Gd according to claim 1 2O 3: Tb 3+Electrospinning process, it is characterized in that: the heating rate of the selection in the described step 3) is 1 ℃/minute, sintering temperature is 500～900 ℃.
4. a kind of sub-micron green fluorescence fiber Gd according to claim 1 2O 3: Tb 3+Electrospinning process, it is characterized in that: prepared Gd 2O 3: Tb 3+Be fibrous, and the diameter of fiber is 400～500nm.
CN2010102652162A 2010-08-24 2010-08-24 Electrostatic spinning method of submicron green fluorescent fiber Gd2O3: Tb3+ Expired - Fee Related CN101942711B (en)

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CN102191570B (en) * 2011-03-11 2013-04-24 长春理工大学 Method for preparing NiO@SiO2@TiO2 coaxial three-layer nano cable
CN102191572A (en) * 2011-03-11 2011-09-21 长春理工大学 Method for preparing NiO@ZnTiO3@TiO2 coaxial three-layer nanocable
CN102181289A (en) * 2011-03-17 2011-09-14 浙江理工大学 Preparation method of orange red fluorescent nano-fiber membrane, namely SrMoO4: Sm3 plus
CN104808286A (en) * 2015-04-23 2015-07-29 东北大学 Preparation method of polymethyl methacrylate optical fiber grating with adjustable period
CN105568405B (en) * 2016-01-27 2018-04-17 广东工业大学 A kind of magnetic agitation feed flow electrostatic spinning apparatus
CN116180259B (en) * 2022-12-22 2024-01-30 南京航空航天大学 In-situ preparation method of gadolinium-containing carbon nano composite fiber for neutron shielding

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