CN104927856A - Method for preparing red phosphors of tungstate based on sol-gel combustion method - Google Patents
Method for preparing red phosphors of tungstate based on sol-gel combustion method Download PDFInfo
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Abstract
The invention discloses a method for preparing red phosphors of tungstate based on a sol-gel combustion method. The method comprises the following steps: 1) separately weighing sodium nitrate, magnesium nitrate, gadolinium nitrate, europium nitrate and ammonium tungstate, respectively dissolving the weighed sodium nitrate, the weighed magnesium nitrate, the weighed gadolinium nitrate, the weighed europium nitrate and the weighed ammonium tungstate in deionized water so as to obtain five kinds of saline solutions, and mixing the saline solutions so as to obtain a mixed solution; 2) weighing citric acid, adding the weighed citric acid in the mixed solution obtained in the step 1), and stirring the citric acid and the mixed solution so as to obtain sol; placing the sol in a constant-temperature water bath kettle, and heating the sol in the constant-temperature water bath kettle so as to obtain wet gel; drying the wet gel so as to obtain dry gel; 3) placing the dry gel obtained in the step 2) in a muffle furnace, and calcining the dry gel in the muffle furnace so as to obtain the red phosphors of tungstate NaGd1-xEuxMgWO6. Through the adoption of the method for preparing the red phosphors of the tungstate based on the sol-gel combustion method, which is disclosed by the invention, the red phosphors of the tungstate, which are high in stability, color purity and luminous efficiency, can be prepared, and the red phosphors of the tungstate are very suitable for being applied to white light emitting diodes.
Description
Technical field
The invention belongs to method of manufacturing fluorescent material technical field, be specifically related to a kind of method preparing tungstate red fluorescent powder based on sol-gel combustion method.
Background technology
1993, the appearance of launching the GaN photodiode (LED) of blue light was that lighting field brings a far reaching revolution, subsequently in 1996, by adopting GaN-LED chip and YAG:Ce
3+phosphor combination sends white light, develops first white light LEDs solid light source.Since then, white light LEDs is little with volume, thermal value is low, current consumption is little, the life-span is long, speed of response is fast, environmental protection and can the advantage of planar package arousing great concern, be described as be by surmount incandescent light, luminescent lamp and HID (High Intensity Discharge) lamp the 4th generation lighting source, application prospect is very wide.
At present, realize white light LEDs and mainly contain three kinds of methods: one is that the light that chip and fluorescent material send is mixed to form white light with LED chip luminous excitated fluorescent powder, and namely fluorescent powder coated light changes method; Two is utilize ruddiness, green glow, blue-ray LED to prepare LED white-light devices, i.e. multi-colored led combined method; Three is utilize multiple active coating that LED is directly emitted white light, i.e. Multiple Quantum Well method.Wherein, it is one of main path manufacturing white light LEDs that fluorescent powder coated light changes method, and the business-like product overwhelming majority manufactures in this way at present; In this approach, fluorescent material is vital as the transformational substance role of light, and it directly affects the luminous efficiency of white light LEDs product, work-ing life, the leading indicator such as colour rendering index and colour temperature.Therefore how to prepare and there is the key that luminous efficiency is high, the redness of Heat stability is good, green and blue colour fluorescent powder are raising white light LEDs luminous masses.
For in the research of phosphor for white light LED, all reached the stage of maturity from the luminescent properties etc. that is prepared into of green powder and bloom, but the luminous efficiency of rouge and powder and stability then cannot compared with other powder.All the time, red fluorescent powder for white radiation LED is confined to alkaline earth sulfide series more, the physicochemical property extremely unstable of such fluorescent material, and poor heat stability, light decay is large, the grievous injury quality of white light LEDs product.Therefore, develop high stability, high color purity also can be seemed very important by the red fluorescence material that near ultraviolet and blue light effectively excite.
In recent years, developed many LED new red phosphors successively, as: the red fluorescence powders such as the many aluminates of alkaline-earth metal, silicate, titanate, germanate, arsenate, molybdate, tungstate; Tungstate system red fluorescence powder wherein shows outstanding feature compared with other system: (1) effectively can absorb the exciting light near 400nm; (2) with conventional Y
2o
2s:Eu
3+red fluorescence powder is compared, and relative brightness is higher, is about the former 1.5 times; (3) sinter in atmosphere, sintering temperature (700 DEG C ~ 900 DEG C) is significantly lower than silicate, aluminates system (more than 1200 DEG C); (4) stable in properties, green non-poisonous, can not the toxic gases such as sulfide be produced under uv irradiation; (5) its strongest emission peak is positioned near 615nm, and glow color is pure.
There is as above outstanding feature based on tungstate system red fluorescence powder, more and more receive the concern of people recent years, become the focus of current LED red fluorescence powder research.
Summary of the invention
The object of the present invention is to provide a kind of method preparing tungstate red fluorescent powder based on sol-gel combustion method, the tungstate red fluorescent powder body showing that good stability, purity of color are high and luminous efficiency is high can be prepared, be applicable to very much being applied to white light LEDs.
The technical solution adopted in the present invention is, prepares the method for tungstate red fluorescent powder based on sol-gel combustion method, specifically implements according to following steps:
Step 1, first take SODIUMNITRATE NaNO respectively
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o; Then take five kinds of salt are dissolved in deionized water respectively and are made into five kinds of salts solutions, finally five kinds of salts solutions are mixed formation mixing solutions;
Step 2, first taking citric acid and add in the mixing solutions that step 1 obtains, forming colloidal sol through stirring; Then colloidal sol is placed in thermostat water bath and adds thermosetting wet gel; Xerogel is obtained finally by oven dry;
Step 3, the xerogel obtained is put into retort furnace calcine through step 2, prepare tungstate NaGd
1-xeu
xmgWO
6red fluorescence powder.
Feature of the present invention is also:
Step 1 is specifically implemented according to following steps:
Step 1.1, be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1 ~ 1.2:1 ~ 1.2:0.95 ~ 0.8:0.05 ~ 0.2:0.17 ~ 0.2 takes SODIUMNITRATE NaNO respectively
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o;
Step 1.2, the SODIUMNITRATE NaNO will taken in step 1.1
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively;
Step 1.3, the sodium nitrate solution formed in step 1.2, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution to be mixed, after stirring, be mixed with mixing solutions.
SODIUMNITRATE NaNO in step 1.1
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2the mol ratio of O is preferably n
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1.1:1:0.85:0.15:0.17.
Step 2 is specifically implemented according to following steps:
Step 2.1, take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=1 ~ 2:1;
Step 2.2, the citric acid taken in step 2.1 added the mixing solutions that step 1 prepares, adopt the mode stirred that citric acid is mixed with mixing solutions, the colloidal sol of formation transparence;
Step 2.3, be positioned in the thermostat water bath of 80 DEG C ~ 100 DEG C by the colloidal sol obtained through step 2.2, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 10h ~ 20h, forms wet gel;
Step 2.4, the wet gel obtained through step 2.3 to be placed in baking oven, under 100 DEG C ~ 130 DEG C conditions, carry out aging, drying and processing, after 10h ~ 18h, obtain xerogel.
Step 3 is specifically implemented according to following steps:
Step 3.1, the xerogel obtained through step 2 is positioned in crucible;
Step 3.2, the crucible that xerogel is housed in step 3.1 is put into retort furnace, in 800 DEG C ~ 1000 DEG C temperature ranges, carry out calcination processing, prepare tungstate NaGd
1-xeu
xmgWO
6red fluorescence powder;
Wherein x=0.05,0.10,0.15,0.20; The preferred value of x is 0.15.
Calcination process in step 3.2 is implemented in accordance with the following methods:
First with the ramp to 400 of 2 DEG C/min ~ 5 DEG C/min DEG C ~ 500 DEG C, insulation 1h ~ 3h;
Again with the ramp to 800 of 2 DEG C/min ~ 5 DEG C/min DEG C ~ 1000 DEG C;
Room temperature is cooled to the furnace after being finally incubated 4h ~ 6h.
The invention has the beneficial effects as follows:
(1) prepare in the method for tungstate red fluorescent powder the present invention is based on sol-gel combustion method, sol-gel combustion method is a kind of novel chemical synthesis process, it takes into account the advantage of sol-gel method and low temperature auto-combustion method, is easy to manipulation, not only safe but also rapid; In addition, the tungstate red fluorescent powder (NaGd adopting this method to prepare
1-xeu
xmgWO
6red fluorescence powder) there is good microscopic appearance, namely have that crystalline state is good, granularity is little and uniform feature.
(2) utilize the present invention is based on sol-gel combustion method prepare the method for tungstate red fluorescent powder obtained be that one mixes the novel NaGd of europium
1-xeu
xmgWO
6red fluorescence powder, this red fluorescence powder has perovskite structure, in such an embodiment Eu
3+case shared by ion does not have inversion symmetry, according to transition speed, makes Eu
3+ion is under near ultraviolet (393nm) and blue light (466nm) excite, and luminescent spectrum is based on the electric dipole transition at 616nm place; Additionally by doping and the processing parameter of adjustment rare-earth europium ion, high-purity, that Uniform Doped, granularity are controlled monodisperse spherical powder can be prepared, make it have high stability, high color purity the red fluorescence material that effectively can be excited by near ultraviolet and blue light, the requirement of white light LEDs to red fluorescence powder can be met, the leading indicators such as the luminous efficiency of raising white light LEDs product and colour rendering index, have certain economic and social benefit.
Accompanying drawing explanation
Fig. 1 utilizes the XRD figure that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares;
Fig. 2 utilizes the SEM figure that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares;
Fig. 3 utilizes the exciting light spectrogram that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares;
Fig. 4 utilizes the utilizing emitted light spectrogram that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares;
Fig. 5 utilizes the luminous intensity and Citric Acid Dosage graph of a relation that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares;
Fig. 6 utilizes the luminous intensity and sintering temperature graph of a relation that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares;
Fig. 7 utilizes the luminous intensity and Eu that the present invention is based on the tungstate red fluorescent powder that method that sol-gel combustion method prepares tungstate red fluorescent powder prepares
3+concentration relationship figure.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
The present invention is based on the method that sol-gel combustion method prepares tungstate red fluorescent powder, specifically implement according to following steps:
Step 1, first take SODIUMNITRATE NaNO respectively
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o; Then take five kinds of salt are dissolved in deionized water respectively and are made into five kinds of salts solutions, finally five kinds of salts solutions are mixed formation mixing solutions, specifically implement according to following steps:
Step 1.1, be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1 ~ 1.2:1 ~ 1.2:0.95 ~ 0.8:0.05 ~ 0.2:0.17 ~ 0.2 takes SODIUMNITRATE NaNO respectively
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o;
Wherein, SODIUMNITRATE NaNO
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2the mol ratio of O is preferably n
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1.1:1:0.85:0.15:0.17;
SODIUMNITRATE NaNO
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively;
Step 1.3, the sodium nitrate solution formed in step 1.2, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution to be mixed, after stirring, be mixed with mixing solutions.
Step 2, first taking citric acid and add in the mixing solutions that step 1 obtains, forming colloidal sol through stirring; Then colloidal sol is placed in thermostat water bath and adds thermosetting wet gel; Obtain open-textured lurid xerogel finally by oven dry, specifically implement according to following steps:
Step 2.1, take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=1 ~ 2:1;
Step 2.2, the citric acid taken in step 2.1 added the mixing solutions that step 1 prepares, adopt the mode stirred that citric acid is mixed with mixing solutions, the colloidal sol of formation transparence;
Step 2.3, be positioned in the thermostat water bath of 80 DEG C ~ 100 DEG C by the colloidal sol obtained through step 2.2, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 10h ~ 20h, forms wet gel;
Step 2.4, the wet gel obtained through step 2.3 to be placed in baking oven, under 100 DEG C ~ 130 DEG C conditions, carry out aging, drying and processing, after 10h ~ 18h, obtain open-textured lurid xerogel.
Step 3, the xerogel obtained is put into retort furnace calcine through step 2, prepare tungstate NaGd
1-xeu
xmgWO
6red fluorescence powder, specifically implement according to following steps:
Step 3.1, the xerogel obtained through step 2 is positioned in crucible;
Step 3.2, the crucible that xerogel is housed in step 3.1 is put into retort furnace, in 800 DEG C ~ 1000 DEG C temperature ranges, carry out calcination processing, prepare tungstate NaGd
1-xeu
xmgWO
6red fluorescence powder;
Wherein x=0.05,0.10,0.15,0.20; The preferred value of x is 0.15.
In step 3.2, calcination process is implemented in such a way:
First with the ramp to 400 of 2 DEG C/min ~ 5 DEG C/min DEG C ~ 500 DEG C, insulation 1h ~ 3h; Again with the ramp to 800 of 2 DEG C/min ~ 5 DEG C/min DEG C ~ 1000 DEG C; Room temperature is cooled to the furnace after being finally incubated 4h ~ 6h.
Wherein, NaGd
0.85eu
0.15mgWO
6the XRD figure of red fluorescence powder is composed as shown in Figure 1, as can be seen from Figure 1: NaGd
0.85eu
0.15mgWO
6x-ray diffraction peak and the international standard diffraction card JCPDS 37-0243 of red fluorescence powder are completely the same, do not have the diffraction peak of other any impurity phase, this illustrate prepared by NaGd
0.85eu
0.15mgWO
6red fluorescence powder is single phase perovskite structure, i.e. Eu
3+replace Gd
3+do not change crystalline structure, but define complete solid solution.
NaGd
0.85eu
0.15mgWO
6the SEM of red fluorescence powder schemes as shown in Figure 2, as seen from Figure 2: the NaGd prepared
0.85eu
0.15mgWO
6red fluorescence powder, its powder dispersity is better, and the line of delimitation between particle is comparatively obvious, and particle size distribution range is narrow, and median size is about 1 μm.
Fig. 3 and Fig. 4 is respectively the NaGd measured by spectrophotofluorometer F-7100
0.85eu
0.15mgWO
6the exciting light spectrogram of red fluorescence powder and utilizing emitted light spectrogram.As can be seen from Figure 3: NaGd
0.85eu
0.15mgWO
6there is a series of razor-edge at 360nm ~ 550nm in red fluorescence powder, belongs to Eu
3+4f-4f transition, main peak lay respectively at 393nm (
7f
0→
5l
6) and 466nm (
7f
0→
5d
2), the emmission spectrum of this and the current near ultraviolet LED chip that generally uses and blue-light LED chip coincide, and thus can be used as the red fluorescence powder of near ultraviolet and blue-light excited three primary colors fluorescent powder composing type white light LEDs.As can be seen from Figure 4, NaGd
0.85eu
0.15mgWO
6the emmission spectrum main peak of red fluorescence powder under 393nm excites is positioned at 616nm, belongs to Eu
3+'s
5d
0→
7f
2electric dipole transition.
Find in preparation process, the consumption of citric acid is different, its obtained NaGd
0.85eu
0.15mgWO
6the utilizing emitted light spectrogram of red fluorescence powder is distinguished to some extent, and as shown in Figure 5, although the emmission spectrum main peak under 393nm excites still is positioned at 616nm, when the ratio of citric acid and metal ion is 1:1.5, the emissive porwer of gained sample is the strongest.
In last calcination process, different calcining temperature is to the NaGd obtained
0.85eu
0.15mgWO
6the luminous intensity of red fluorescence powder has impact, as shown in Figure 6 NaGd
0.85eu
0.15mgWO
6luminous intensity along with the rising first increases and then decreases of sintering temperature, its optimal sintering temperature is 950 DEG C.
In addition, respectively to x=0.05,0.1,0.15,0.20 time the NaGd that obtains
1-xeu
xmgWO
6fluorescent material carries out XRD analysis, confirms that each product is target product.The NaGd of different Eu doping
1-xeu
xmgWO
6the relative luminous intensity of each sample is along with Eu
3+the change of doping content, as shown in Figure 7, different Eu
3+the utilizing emitted light spectrogram of the sample of doping content is similar, and under near-ultraviolet light 393nm excites, emission peak main peak is all positioned at 616nm, belongs to
5d
0→
7f
2electric dipole transition.But the emissive porwer of sample is along with Eu
3+the increase of the doping content of ion, first increases and subtracts afterwards, and its optimum doping concentration is x=0.15.
Embodiment 1
Be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1.1:1:0.85:0.15:0.17 takes SODIUMNITRATE, magnesium nitrate, Gadolinium trinitrate, europium nitrate and wolframic acid ammonia respectively; The SODIUMNITRATE NaNO taken
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively; Sodium nitrate solution, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution are mixed, after stirring, is mixed with mixing solutions;
Take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=1.5:1; Citric acid is added mixing solutions, adopts the mode stirred that citric acid is mixed with mixing solutions, form vitreosol; Be positioned over by the colloidal sol obtained in the thermostat water bath of 80 DEG C, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 20h, forms wet gel; Obtained wet gel is placed in baking oven, in 130 DEG C, carries out aging, drying and processing, after 10h, obtain open-textured lurid xerogel;
Xerogel is placed in crucible, the crucible that xerogel is housed is put into retort furnace, in air atmosphere, start to calcine, first with the ramp to 500 DEG C of 2 DEG C/min, insulation 2h; Again with the ramp to 900 DEG C of 2 DEG C/min; Room temperature is cooled to the furnace after being finally incubated 4h; Prepare NaGd
0.85eu
0.15mgWO
6red fluorescence powder.
Embodiment 2
Be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1.2:1.2:0.8:0.2:0.2 takes SODIUMNITRATE, magnesium nitrate, Gadolinium trinitrate, europium nitrate and wolframic acid ammonia respectively; The SODIUMNITRATE NaNO taken
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively; Sodium nitrate solution, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution are mixed, after stirring, is mixed with mixing solutions;
Take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=2:1; Citric acid is added mixing solutions, adopts the mode stirred that citric acid is mixed with mixing solutions, form vitreosol; Be positioned over by the colloidal sol obtained in the thermostat water bath of 85 DEG C, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 15h, forms wet gel; Obtained wet gel is placed in baking oven, in 120 DEG C, carries out aging, drying and processing, after 12h, obtain open-textured lurid xerogel;
Xerogel is placed in crucible, the crucible that xerogel is housed is put into retort furnace, in air atmosphere, start to calcine, first with the ramp to 450 DEG C of 3 DEG C/min, insulation 3h; Again with the ramp to 1000 DEG C of 3 DEG C/min; Room temperature is cooled to the furnace after being finally incubated 5h; Prepare NaGd
0.8eu
0.2mgWO
6red fluorescence powder.
Embodiment 3
Be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1:1:0.9:0.1:0.18 takes SODIUMNITRATE, magnesium nitrate, Gadolinium trinitrate, europium nitrate and wolframic acid ammonia respectively; The SODIUMNITRATE NaNO taken
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively; Sodium nitrate solution, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution are mixed, after stirring, is mixed with mixing solutions;
Take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=1.2:1; Citric acid is added mixing solutions, adopts the mode stirred that citric acid is mixed with mixing solutions, form vitreosol; Be positioned over by the colloidal sol obtained in the thermostat water bath of 90 DEG C, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 15h, forms wet gel; Obtained wet gel is placed in baking oven, in 110 DEG C, carries out aging, drying and processing, after 16h, obtain open-textured lurid xerogel;
Xerogel is placed in crucible, the crucible that xerogel is housed is put into retort furnace, in air atmosphere, start to calcine, first with the ramp to 400 DEG C of 4 DEG C/min, insulation 1h; Again with the ramp to 950 DEG C of 4 DEG C/min; Room temperature is cooled to the furnace after being finally incubated 4.5h; Be prepared into NaGd
0.9eu
0.1mgWO
6red fluorescence powder.
Embodiment 4
Be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1.2:1:0.95:0.05:0.17 takes SODIUMNITRATE, magnesium nitrate, Gadolinium trinitrate, europium nitrate and wolframic acid ammonia respectively; The SODIUMNITRATE NaNO taken
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively; Sodium nitrate solution, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution are mixed, after stirring, is mixed with mixing solutions;
Take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=1.5:1; Citric acid is added mixing solutions, adopts the mode stirred that citric acid is mixed with mixing solutions, form vitreosol; Be positioned over by the colloidal sol obtained in the thermostat water bath of 100 DEG C, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 16h, forms wet gel; Obtained wet gel is placed in baking oven, in 130 DEG C, carries out aging, drying and processing, after 18h, obtain open-textured lurid xerogel;
Xerogel is placed in crucible, the crucible that xerogel is housed is put into retort furnace, in air atmosphere, start to calcine, first with the ramp to 500 DEG C of 5 DEG C/min, insulation 2h; Again with the ramp to 900 DEG C of 5 DEG C/min; Room temperature is cooled to the furnace after being finally incubated 5h; Prepare NaGd
0.95eu
0.05mgWO
6red fluorescence powder.
The present invention is based on the method that sol-gel combustion method prepares tungstate red fluorescent powder, the tungstate red fluorescent material showing that good stability, purity of color are high and luminous efficiency is high can be prepared, be applicable to very much being applied to white light LEDs.
Claims (7)
1. prepare the method for tungstate red fluorescent powder based on sol-gel combustion method, it is characterized in that, specifically implement according to following steps:
Step 1, first take SODIUMNITRATE NaNO respectively
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o; Then take five kinds of salt are dissolved in deionized water respectively and are made into five kinds of salts solutions, finally five kinds of salts solutions are mixed formation mixing solutions;
Step 2, first taking citric acid and add in the mixing solutions that step 1 obtains, forming colloidal sol through stirring; Then colloidal sol is placed in thermostat water bath and adds thermosetting wet gel; Xerogel is obtained finally by oven dry;
Step 3, the xerogel obtained is put into retort furnace calcine through step 2, prepare tungstate NaGd
1-xeu
xmgWO
6red fluorescence powder.
2. the method preparing tungstate red fluorescent powder based on sol-gel combustion method according to claim 1, is characterized in that, described step 1 is specifically implemented according to following steps:
Step 1.1, be n in molar ratio
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1 ~ 1.2:1 ~ 1.2:0.95 ~ 0.8:0.05 ~ 0.2:0.17 ~ 0.2 takes SODIUMNITRATE NaNO respectively
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o;
Step 1.2, the SODIUMNITRATE NaNO will taken in step 1.1
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2o is dissolved in deionized water respectively, forms sodium nitrate solution, the magnesium nitrate solution of 1mol/L, the Gadolinium trinitrate solution of 1mol/L, the europium nitrate solution of 1mol/L, 1mol/L ammonium tungstate solution that molecular volume specific concentration is 1mol/L respectively;
Step 1.3, the sodium nitrate solution formed in step 1.2, magnesium nitrate solution, Gadolinium trinitrate solution, europium nitrate solution and ammonium tungstate solution to be mixed, after stirring, be mixed with mixing solutions.
3. the method preparing tungstate red fluorescent powder based on sol-gel combustion method according to claim 2, is characterized in that, SODIUMNITRATE NaNO in described step 1.1
3, magnesium nitrate Mg (NO
3)
26H
2o, Gadolinium trinitrate Gd (NO
3)
36H
2o, europium nitrate Eu (NO
3)
36H
2o and ammonium tungstate (NH
4)
5h
5[H
2(WO
4)
6] H
2the mol ratio of O is preferably n
naNO3: n
mg (NO3) 26H2O: n
gd (NO3) 36H2O: n
eu (NO3) 36H2O: n
(NH4) 5H5 [H2 (WO4) 6] H2O=1.1:1:0.85:0.15:0.17.
4. the method preparing tungstate red fluorescent powder based on sol-gel combustion method according to claim 1, is characterized in that, described step 2 is specifically implemented according to following steps:
Step 2.1, take citric acid, the mol ratio of citric acid and metal ion is n
citric acid: n
metal ion=1 ~ 2:1;
Step 2.2, the citric acid taken in step 2.1 added the mixing solutions that step 1 prepares, adopt the mode stirred that citric acid is mixed with mixing solutions, the colloidal sol of formation transparence;
Step 2.3, be positioned in the thermostat water bath of 80 DEG C ~ 100 DEG C by the colloidal sol obtained through step 2.2, utilize magnetic stirring apparatus heat colloidal sol and stir, the time is 10h ~ 20h, forms wet gel;
Step 2.4, the wet gel obtained through step 2.3 to be placed in baking oven, under 100 DEG C ~ 130 DEG C conditions, carry out aging, drying and processing, after 10h ~ 18h, obtain xerogel.
5. the method preparing tungstate red fluorescent powder based on sol-gel combustion method according to claim 1, is characterized in that, described step 3 is specifically implemented according to following steps:
Step 3.1, the xerogel obtained through step 2 is positioned in crucible;
Step 3.2, the crucible that xerogel is housed in step 3.1 is put into retort furnace, in 800 DEG C ~ 1000 DEG C temperature ranges, carry out calcination processing, prepare tungstate NaGd
1-xeu
xmgWO
6red fluorescence powder.
6. the method preparing tungstate red fluorescent powder based on sol-gel combustion method according to claim 5, is characterized in that, the tungstate NaGd obtained of preparation in described step 3.2
1-xeu
xmgWO
6red fluorescence powder, its x=0.05,0.10,0.15,0.20;
The preferred value of x is 0.15.
7. the method preparing tungstate red fluorescent powder based on sol-gel combustion method according to claim 5, is characterized in that, the calcination process in described step 3.2 is implemented in accordance with the following methods:
First with the ramp to 400 of 2 DEG C/min ~ 5 DEG C/min DEG C ~ 500 DEG C, insulation 1h ~ 3h;
Again with the ramp to 800 of 2 DEG C/min ~ 5 DEG C/min DEG C ~ 1000 DEG C;
Room temperature is cooled to the furnace after being finally incubated 4h ~ 6h.
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