CN104342851B - A kind of CaSi2O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film - Google Patents

A kind of CaSi2O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film Download PDF

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CN104342851B
CN104342851B CN201410520056.XA CN201410520056A CN104342851B CN 104342851 B CN104342851 B CN 104342851B CN 201410520056 A CN201410520056 A CN 201410520056A CN 104342851 B CN104342851 B CN 104342851B
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fluorescent fiber
fiber film
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casi
spinning
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CN104342851A (en
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王宏志
崔博
李耀刚
张青红
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Donghua University
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Abstract

The present invention relates to a kind of CaSi2O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, including：(1) with europium nitrate, terbium nitrate, cerous nitrate, calcium nitrate, tetraethyl orthosilicate is raw material, is added in the mixed solvent.Polyvinylpyrrolidone is added in uniformly mixed solution, stirs to get transparent spinning solution.(2) the pristine fibre film by the way that the electrostatic spinning time is controlled to be layered.Tunica fibrosa is calcined in air atmosphere, Ca Si O Ce, the Tb/Eu tunica fibrosas being layered.(3) nitrogenized in ammonia atmosphere, obtain the CaSi with layered structure2O2N2:Ce, Tb/Eu fluorescent fiber film.The present invention is purely inorganic fluorescent fiber film, can be suitable for the long-range encapsulation of large power white light LED.The layered structure of different emission fluorescent fiber can reduce the double absorption of transmitting light, so as to improve luminous efficiency.

Description

A kind of CaSi2O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film
Technical field
The invention belongs to large power white light LED fluorescent material field, more particularly to a kind of CaSi2O2N2:Ce, Tb/Eu are more The preparation method of layer multicolor fluorescence tunica fibrosa.
Background technology
As lighting source of new generation, white light LEDs develop to high efficiency and high-power direction.Remotely it is encapsulated into solution Certainly large power white light LED light decay and another feasible way of color drift.LED long-distance fluorescent powder devices are to be attached to fluorescent powder It on substrate (being typically silicon rubber), is separated with blue light LED light source, so as to reduce the heat of chip generation to light-emitting phosphor performance Influence.However, in great power LED, silicon rubber equally exists weather stain phenomenon, and the nitride of high temperature solid-state method synthesis (or oxynitride) reunites serious, hardly possible is uniformly mixed with silicon rubber since grain size is big.
The problem of for above-mentioned silica gel matrix, some scholars propose glass-encapsulated (C.L.Chang et al.J.Micromech.Microeng.,2012,22:105039.) or crystalline ceramics encapsulates (Y.Y.Ding et al.J.Alloys Compd.,2012,521:35.).But the alkali metal ion in the high temperature and glass melt of glass melting Easily the surface of fluorescent powder is damaged, reduces luminous efficiency, and fluorescent powder equally exists the problem of scattered in glass；It is and saturating The preparation of bright ceramics and processing cost are all very high, it is difficult to do thin, and light transmittance is not high, and what is more important can be made at present The fluorescent material system of bright ceramics is seldom, is mostly oxide (such as Al2O3, YAG), it yet there are no the report of nitride transparent ceramics.So And size uniform, the fluorescent fiber film of favorable dispersibility, which shines, is better than simple fluorescent powder grain film (Y.X.Gu et al.J.Mater.Chem.,2011,21:17790).Preparation process is relatively simple simultaneously, and controllability is strong.
The light source of high color rendering index (CRI) is generally required in high-power LED illumination, fluorescence coating used is generally glimmering by two or more Luminescent material mixes.Fluorescent fiber film preparation-shaping is once completed, this is just needed can be to different fluorescence in preparation process The distribution of material, dosage are controllable.There is transmitting light double absorption between a variety of fluorescent materials simultaneously, can cause to emit under light efficiency Drop.This is also one of major issue present in high color rendering index (CRI) light source.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of CaSi2O2N2:Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film Preparation method, by electrostatic spinning technique, by different rare earth ions, layer distributed, fluorescent fiber film shine this method on demand It is adjustable.Tunica fibrosa has multi-layered color structure, and the separation of different emission fluorescent fiber can reduce the secondary suction of transmitting light It receives, so as to improve luminous efficiency.
A kind of CaSi of the present invention2O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, including：
(1) preparation of spinning liquid as precursor：
Using cerous nitrate, terbium nitrate, calcium nitrate, tetraethyl orthosilicate TEOS as raw material, in the mixed solvent is added to；Mixing is equal Polyvinylpyrrolidone PVP is added in even solution, stirs to get transparent spinning solution A；Using europium nitrate, calcium nitrate, TEOS as Raw material is added in the mixed solvent；Polyvinylpyrrolidone PVP is added in uniformly mixed solution, is stirred evenly, is obtained Bright spinning solution B；
(2) electrostatic spinning prepares protofibre film：
At room temperature, above two spinning solution is respectively adopted and carries out electrostatic spinning；
(3) preparation of the precursor fibre film of layering：
The tunica fibrosa obtained in step (2) is placed in and is calcined in air atmosphere, is warming up to 500~600 DEG C, heat preservation 2~4h, presoma Ca-Si-O-Ce, the Tb/Eu tunica fibrosa being layered；
(4) ammonia nitriding prepares multiple-layer polychromatic fluorescent fiber film：
It is cooled to room temperature, the presoma Ca-Si-O-Ce, Tb/Eu with layering that will be obtained after step (3) calcining are fine Film is tieed up in ammonia atmosphere is continually fed into, is warming up to 1200~1300 DEG C, keeps the temperature 1~5h；Obtain that there is layered structure CaSi2O2N2:Ce, Tb/Eu fluorescent fiber film.
In the step (1) in molar ratio, the Ca in spinning solution A:Ce=1:0.001~0.01, Ce:Tb=1:0.5~ Ca in 1, spinning solution B:Eu=1:0.005~0.05, the Ca in spinning solution A, B:Si=1~0.9:2.
Mixed solvent is volume ratio 1~2 in the step (1):8 ultra-pure water and absolute ethyl alcohol, the NO of spinning solution A, B3 - Concentration reaches 0.15mol/L~0.4mol/L.
The PVP that spinning solution A, B are added in the step (1) is divided into two kinds, the first molecular weight is 1300000, is added in The 0.8%~1.2% of solution gross mass, second of molecular weight are 50000, add in the 1.6%~2.4% of solution gross mass.
Spinning technique is voltage 6-12kV in the step (2), and spinning rate 0.2-1.5mL/h receives distance 10- 18cm, humid control is below 30%.
The usage amount of spinning solution A, B are 0.2~2mL in the step (2).
The flow velocity of ammonia is 200-400mL/min in the step (4).
Heating rate is 0.8~1.5 DEG C/min in the step (3), and heating rate is 2~3 DEG C/min in step (4).
Advantageous effect
During first passage control electrostatic spinning of the present invention prepared by the spinning time of different spinning solutions and spinning parameter There is presoma Ca-Si-O-Ce, the Tb/Eu tunica fibrosa of layering；It nitrogenizes to have obtained with layered structure using ammonia CaSi2O2N2:Ce, Tb/Eu fluorescent fiber film.
The layered structure of colorful fiber film so that different emission fluorescent fiber separates, and can reduce the two of transmitting light Secondary absorption, so as to improve luminous efficiency.
Description of the drawings
Fig. 1 are layered electrostatic spinning schematic diagram；
The obtained CaSi with layered structure after Fig. 2 .1300 DEG C nitridations 1h2O2N2:Ce, Tb/Eu fluorescent fiber film SEM photograph；
The emission spectrum and digital photograph of Fig. 3 fluorescent film tow sides, (a) are irradiation CaSi2O2N2:Ce, Tb face, (b) it is irradiation CaSi2O2N2:Eu faces.
Specific embodiment
With reference to specific embodiment, the present invention is further explained.It is to be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Scope.
Embodiment 1
1mL ultra-pure waters and 18mL absolute ethyl alcohols is taken to mix；By 0.009g cerous nitrates, 0.012 terbium nitrate, 0.397g calcium nitrate In the mixed solvent is dissolved in, adds 0.71mL TEOS.After persistently stirring 30min, 0.9g is slowly added under high velocity agitation PVP (molecular weight 1300000) and 2.4g PVP (molecular weight 50000) continues to stir 6h, until solution clear, obtains spinning Liquid A；By 0.019g europium nitrates, 0.402g calcium nitrate is dissolved in the mixed solvent, adds 0.69mL TEOS.Lasting stirring After 30min, 0.9g PVP (molecular weight 1300000) and 2.4g PVP (molecular weight 50000) are slowly added under high velocity agitation, after Continuous stirring 6h, until solution clear, obtains spinning solution B.
Obtained precursor solution is subjected to electrostatic spinning：At room temperature, it is 30% to control humidity, and spinning voltage is set For 6kv, the fltting speed of pump is promoted as 0.2mL/h, and it is 10cm to receive distance.A spinning solutions are subjected to Static Spinning, spinning amount first For 0.2mL, B spinning solutions are changed afterwards, and spinning amount remains as 0.2mL.
Calcine nascent layered fibre obtained above in air atmosphere, heating rate is 0.8 DEG C/min, calcining heat 500 DEG C are, presoma Ca-Si-O-Ce, the Tb/Eu tunica fibrosa that Temperature fall is layered after heat preservation 4h.
Tunica fibrosa after calcining is transferred to tube-type atmosphere furnace, is passed through ammonia, ammonia flow 400mL/min, tubular type gas The heating rate of atmosphere stove is 3 DEG C/min, is warming up to 1200 DEG C, and keeps the temperature 5h, in the case where flowing ammonia, is cooled to room temperature, is had There is the CaSi of layered structure2O2N2:Ce, Tb/Eu fluorescent fiber film.
Embodiment 2
1.5mL ultra-pure waters and 18mL absolute ethyl alcohols is taken to mix；By 0.019g cerous nitrates, 0.022 terbium nitrate, 0.697g nitric acid Calcium is dissolved in the mixed solvent, adds 1.02mL TEOS.After persistently stirring 30min, 1g is slowly added under high velocity agitation PVP (molecular weight 1300000) and 2g PVP (molecular weight 50000) continues to stir 6h, until solution clear, obtains spinning solution A；By 0.03g europium nitrates, 0.613g calcium nitrate is dissolved in the mixed solvent, adds 0.98mL TEOS.Persistently stir 30min Afterwards, 0.9g PVP (molecular weight 1300000) and 2.4g PVP (molecular weight 50000) are slowly added under high velocity agitation, continue to stir 6h is mixed, until solution clear, obtains spinning solution B.
Obtained precursor solution is subjected to electrostatic spinning：At room temperature, it is 30% to control humidity, and spinning voltage is set For 8kv, the fltting speed of pump is promoted as 0.8mL/h, and it is 14cm to receive distance.A spinning solutions are subjected to Static Spinning, spinning amount first For 1mL, B spinning solutions are changed afterwards, and spinning amount remains as 1mL.
Calcine nascent layered fibre obtained above in air atmosphere, heating rate is 1 DEG C/min, calcining heat 550 DEG C it is to keep the temperature presoma Ca-Si-O-Ce, the Tb/Eu tunica fibrosa that Temperature fall after 3h is layered.
Tunica fibrosa after calcining is transferred to tube-type atmosphere furnace, is passed through ammonia, ammonia flow 300mL/min, tubular type gas The heating rate of atmosphere stove is 3 DEG C/min, is warming up to 1250 DEG C, and keeps the temperature 3h, in the case where flowing ammonia, is cooled to room temperature, is had There is the CaSi of layered structure2O2N2:Ce, Tb/Eu fluorescent fiber film.
Embodiment 3
2mL ultra-pure waters and 18mL absolute ethyl alcohols is taken to mix；By 0.015g cerous nitrates, 0.032 terbium nitrate, 0.96g calcium nitrate In the mixed solvent is dissolved in, adds 1.48mL TEOS.After persistently stirring 30min, 1.2g is slowly added under high velocity agitation PVP (molecular weight 1300000) and 1.7g PVP (molecular weight 50000) continues to stir 6h, until solution clear, obtains spinning Liquid A；By 0.05g europium nitrates, 1.102g calcium nitrate is dissolved in the mixed solvent, adds 1.56mL TEOS.Lasting stirring After 30min, 1g PVP (molecular weight 1300000) and 2g PVP (molecular weight 50000) are slowly added under high velocity agitation, continues to stir 6h is mixed, until solution clear, obtains spinning solution B.
Obtained precursor solution is subjected to electrostatic spinning：At room temperature, it is 30% to control humidity, and spinning voltage is set For 12kv, the fltting speed of pump is promoted as 1.5mL/h, and it is 18cm to receive distance.A spinning solutions are subjected to Static Spinning, spinning first It measures as 2mL, changes B spinning solutions afterwards, spinning amount remains as 2mL.
Calcine nascent layered fibre obtained above in air atmosphere, heating rate is 1.5 DEG C/min, calcining heat 600 DEG C are, presoma Ca-Si-O-Ce, the Tb/Eu tunica fibrosa that Temperature fall is layered after heat preservation 2h.
Tunica fibrosa after calcining is transferred to tube-type atmosphere furnace, is passed through ammonia, ammonia flow 200mL/min, tubular type gas The heating rate of atmosphere stove is 3 DEG C/min, is warming up to 1300 DEG C, and keeps the temperature 1h, in the case where flowing ammonia, is cooled to room temperature, is had There is the CaSi of layered structure2O2N2:Ce, Tb/Eu fluorescent fiber film.

Claims (8)

1. a kind of CaSi2O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, including：
(1) using cerous nitrate, terbium nitrate, calcium nitrate, tetraethyl orthosilicate TEOS as raw material, it is added in the mixed solvent；Mixing is equal Polyvinylpyrrolidone PVP is added in even solution, stirs to get transparent spinning solution A；Using europium nitrate, calcium nitrate, TEOS as Raw material is added in the mixed solvent；Polyvinylpyrrolidone PVP is added in uniformly mixed solution, is stirred evenly, is obtained Bright spinning solution B；
(2) at room temperature, above two spinning solution is respectively adopted and carries out electrostatic spinning, obtains protofibre film；
(3) the protofibre film obtained in step (2) is placed in and calcined in air atmosphere, be warming up to 500~600 DEG C, Keep the temperature 2~4h, presoma Ca-Si-O-Ce, the Tb/Eu tunica fibrosa being layered；
(4) it is cooled to room temperature, presoma Ca-Si-O-Ce, the Tb/Eu fiber with layering that will be obtained after step (3) calcining Film is warming up to 1200~1300 DEG C in ammonia atmosphere is continually fed into, and keeps the temperature 1~5h；Obtain that there is layered structure CaSi2O2N2:Ce, Tb/Eu fluorescent fiber film.
2. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：In the step (1) in molar ratio, the Ca in spinning solution A:Ce=1:0.001~0.01, Ce:Tb=1:0.5~ Ca in 1, spinning solution B:Eu=1:0.005~0.05, the Ca in spinning solution A, B:Si=1~0.9:2.
3. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：Mixed solvent is volume ratio 1~2 in the step (1):8 ultra-pure water and absolute ethyl alcohol, the NO of spinning solution A, B3 - Concentration reaches 0.15mol/L~0.4mol/L.
4. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：The PVP that spinning solution A, B are added in the step (1) is divided into two kinds, the first molecular weight is 1300000, is added in The 0.8%~1.2% of solution gross mass, second of molecular weight are 50000, add in the 1.6%~2.4% of solution gross mass.
5. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：Spinning technique is voltage 6-12kV in the step (2), and spinning rate 0.2-1.5mL/h receives distance 10- 18cm, humid control is below 30%.
6. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：The usage amount of spinning solution A, B are 0.2~2mL in the step (2).
7. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：The flow velocity of ammonia is 200-400mL/min in the step (4).
8. a kind of CaSi according to claim 12O2N2:The preparation method of Ce, Tb/Eu multiple-layer polychromatic fluorescent fiber film, It is characterized in that：Heating rate is 0.8~1.5 DEG C/min in the step (3), and heating rate is 2~3 DEG C/min in step (4).
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