CN106497559B - A method of white light LEDs Ca- α-SiAlON:Eu fluorescent powder is synthesized using slag of coal gasification - Google Patents
A method of white light LEDs Ca- α-SiAlON:Eu fluorescent powder is synthesized using slag of coal gasification Download PDFInfo
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Abstract
The invention discloses a kind of methods using slag of coal gasification synthesis white light LEDs Ca- α-SiAlON:Eu fluorescent powder, use slag of coal gasification for raw material, after clinker is mixed with europium oxide, high-purity Ca- α-SiAlON:Eu fluorescent powder is obtained by carbothermal reduction-nitridation reaction bonded postprocessing working procedures.Nitriding temperature and soaking time in the additive amount and nitriding process that invention passes through regulation europium oxide, high-purity Ca- α-SiAlON:Eu fluorescent powder is obtained with lower cost, its purity reaches 95wt.% or more, simultaneously, used slag of coal gasification provides the source Ca, Si, Al, O and C of carbothermal reduction-nitridation synthesis Ca- α-SiAlON, and reaction is without being added additional reducing agent；In addition, the C ingredient in gasifier slag provides reducing atmosphere for reaction, and under the effect, Eu3+Eu can be reduced into2+, to realize the biggish Eu of radius2+Doping in Ca- α-SiAlON obtains Ca- α-SiAlON:Eu fluorescent powder, finally realizes application of the slag of coal gasification on SiAlON functional material.
Description
Technical field
The present invention relates to functional material preparation technical fields, in particular, provide a kind of utilization slag of coal gasification synthesis white light
The method of LED Ca- α-SiAlON:Eu fluorescent powder.
Background technique
White light emitting diode (lighting emitting diode, LED) is a kind of with the new of energy-saving and emission-reduction effect
The all solid state lighting source of type, compared with incandescent lamp and fluorescent lamp, it has, and low energy consumption, light efficiency is high, the service life is long, small in size, response
Fastly, advantages of environment protection.Fluorescent material is the essential component part of white light LEDs, it directly influences shining for white light
The performances such as efficiency, colour rendering, colour temperature, service life.Fluorescent material is made of matrix and activator, in recent years, to match grand (SiAlON)
It is used as a kind of novel fluorescent material matrix for the nitrogen oxides of representative, by the close attention of people, according to its structure difference
It is broadly divided into α-SiAlON and two kinds of β-SiAlON.
In fluorescent powder, at present about rare earth ion doped SiAlON fluorescent powder synthetic method mainly have gas pressure sintering method,
Gas reduction nitriding, CRN method, wherein gas pressure sintering method is suitble to produce in enormous quantities, but nitride raw material price is high
Expensive, simultaneously because nitride has very strong covalent bond, reactivity is low, thus needs higher synthesis temperature, wants to equipment
Ask higher；Gas reduction nitriding synthesis temperature is low compared with gas pressure sintering method, and shortcoming is NH3-CH4Gas is relatively hazardous and toxic
Property；CRN method synthesis temperature is low, and synthetic powder particle diameter distribution is narrow, but disadvantage is that residual carbon remains in fluorescent powder
It will affect its luminescent properties.
In the above several method, CRN method because the prices of raw materials are cheap, reaction temperature is low, obtain without group
Poly- powder is conducive to the advantages such as the LED encapsulation of fluorescent powder, becomes the optimal path for reducing fluorescent powder synthesis cost.When SiAlON makees
When for white light LEDs fluorescent matrix material, the luminescent properties of fluorescent material to the purity and crystallinity of SiAlON propose compared with
High requirement, at present other than the report of above-mentioned pure-oxide carbothermal reduction-nitridation synthesis SiAlON fluorescent powder, with natural minerals
Or solid waste is very few for the research of raw material.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of utilization slag of coal gasification synthesis white light
The LED method of Ca- α-SiAlON:Eu fluorescent powder, realizes the integrated application of slag of coal gasification, reduces costs simultaneously.
In order to solve the above-mentioned technical problem, the present invention is realised by adopting the following technical scheme:
A method of using slag of coal gasification synthesize white light LEDs Ca- α-SiAlON:Eu fluorescent powder, specifically include with
Lower step:
Step 1: slag of coal gasification and europium oxide are mixed according to the ratio that mass percent is 100:3~6.
Step 2: the mixture that step 1 is obtained is placed in ball mill, 6~10h of wet ball grinding, mixed after obtaining ball milling
Close slurry；
Step 3: it after mixed slurry is carried out rotary evaporation on a rotary evaporator, places into baking oven and is dried, obtain
Powder after drying is placed in mold and is pressed into sample by the powder after to drying.
Step 4: sample is put into crucible, and crucible is placed in atmosphere furnace, is passed through the nitrogen of flowing, with 5~7 DEG C/min
Heating rate be heated to 800~1000 DEG C, then be heated to 1200~1300 DEG C with the heating rate of 3~5 DEG C/min, then with 1
The heating rate of~3 DEG C/min is heated to 1420~1460 DEG C, then keeps the temperature 6~9h, obtains nitridation product.
Step 5: will nitridation product be put into moderate oven, be heated in air atmosphere 700~900 DEG C and keep the temperature 6~
9h；
Step 6: it will be cleaned multiple times in the dilute hydrochloric acid of 20~25wt.% except the product after carbon, until upper layer filtrate
Clarification, filters out filtrate, by filter residue after filtering drying, obtains Ca- α-SiAlON:Eu fluorescent powder.
There are also following distinguishing features by the present invention:
Further, the flow of the nitrogen is 0.5L/min.
Further, the crucible is corundum crucible.
Further, rotating evaporation temperature is 50~80 DEG C, and drying temperature is 50~100 DEG C.
Further, ball-milling medium is ethyl alcohol, grinding ball material Al2O3, revolving speed is 200~500r/min.
Further, the europium oxide is the powder that purity is 98.5%~99.5%, partial size is 1~100 μm.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention by regulation europium oxide additive amount and nitriding process in nitriding temperature and soaking time, with compared with
Low cost obtains high-purity Ca- α-SiAlON:Eu fluorescent powder, and purity reaches 95wt.% or more.
(2) the C ingredient in slag of coal gasification provides reducing atmosphere for reaction, under the effect, is dissolved originally into α-
The trivalent Eu of SiAlON host lattice3+It is reduced to divalent Eu2+, realize the biggish Eu of radius2+(0.117nm) is in α-SiAlON
In doping；In addition, in stabilizing ion Ca2+Under the action of, Eu2+Ion can steadily be present between α-SiAlON host lattice
The centre of luminescence is served as in gap position, and then realizes application of the slag of coal gasification on SiAlON functional material.
(3) slag of coal gasification provides the source Ca, Si, Al, O and C of carbothermal reduction-nitridation synthesis Ca- α-SiAlON, reaction
It is not necessary that additional reducing agent is added, so that it is made full use of waste resource, reduce costs.
Detailed description of the invention
Fig. 1 is the XRD spectrum of comparative example of the present invention product obtained.
Fig. 2 is the XRD spectrum for the Ca- α-SiAlON:Eu fluorescent powder that the present invention synthesizes.In figure, (a) is the XRD of embodiment 1
As a result, (b) being the XRD of embodiment 2 as a result, (c) being the XRD of embodiment 3 as a result, (d) being the XRD of embodiment 4 as a result, (e) being
The XRD result of embodiment 5.
Fig. 3 is the SEM photograph and XRD analysis result for the Ca- α-SiAlON:Eu fluorescent powder that the present invention synthesizes, wherein Fig. 3
(a) SEM photograph of the Ca- α-SiAlON:Eu fluorescent powder synthesized for the embodiment of the present invention 1；Fig. 3 (b) is the conjunction of the embodiment of the present invention 2
At Ca- α-SiAlON:Eu fluorescent powder SEM photograph；Fig. 3 (c) is that the Ca- α-SiAlON:Eu that the embodiment of the present invention 3 synthesizes is glimmering
The SEM photograph of light powder；Fig. 3 (d) is the SEM photograph for the Ca- α-SiAlON:Eu fluorescent powder that the embodiment of the present invention 4 synthesizes；Fig. 3 (e)
For the EDS analysis result for the Ca- α-SiAlON:Eu fluorescent powder that the embodiment of the present invention 1 synthesizes；Fig. 3 (f) is the embodiment of the present invention 4
The EDS of the Ca- α-SiAlON:Eu fluorescent powder of synthesis analyzes result.
Fig. 4 is the fluorescence spectra for the Ca- α-SiAlON:Eu fluorescent powder that the present invention synthesizes.
Fig. 5 is Eu in the intensity of emission spectra and raw material for the Ca- α-SiAlON:Eu fluorescent powder that the present invention synthesizes2O3Additive amount
Between relationship.
Explanation is further explained in detail to particular content of the invention with reference to embodiments.
Specific embodiment
Solid waste --- slag of coal gasification utilizes carbothermal reduction-nitridation synthesis Ca- α-SiAlON powder and preparation Ca-
Although α-SiAlON ceramics have had certain Research foundation,.In actual research process, based on slag of coal gasification
Raw material is wanted, Ca- α-SiAlON:Eu fluorescent powder is synthesized by carbothermal reduction-nitridation, encounters many actual difficulties.Pass through research
It was found that the addition of europium oxide is affected to slag of coal gasification addition on reduction nitridation process, if the addition underexercise of europium oxide is not only
It will affect the luminescent properties of synthetizing phosphor powder, or even cannot get high pure phosphor.The present invention is anti-with slag of coal gasification to europium oxide
During answering synthetizing phosphor powder, it is deep to carry out system for nitriding temperature and soaking time in the additive amount and nitriding process of europium oxide
Research, to obtain the Ca- α-SiAlON:Eu fluorescent powder of purity is high, morphological rules and good luminescence property as overall study mesh
Mark.
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to implement in detail below
Example, all equivalent transformations made on the basis of the technical solutions of the present application each fall within protection scope of the present invention.
The invention proposes a kind of sides using slag of coal gasification synthesis white light LEDs Ca- α-SiAlON:Eu fluorescent powder
Method, specifically includes the following steps:
Step 1: slag of coal gasification and europium oxide are mixed according to the ratio that mass percent is 100:3~6, wherein oxygen
Changing europium is the powder that purity is 98.5%~99.5%, partial size is 1~100 μm.
Step 2: the mixture that step 1 is obtained is placed in ball mill, grinding ball material Al2O3, using dehydrated alcohol as
Ball-milling medium, 6~10h of wet ball grinding in the case where revolving speed is 300r/min, the mixed slurry after obtaining ball milling；
Step 3: after mixed slurry is carried out rotary evaporation at 50~80 DEG C on a rotary evaporator, baking oven is placed into
In dried, drying temperature be 50~100 DEG C, the powder after drying is placed in mold and suppresses by the powder after being dried
At sample.
Step 4: sample being put into, sample be put into corundum crucible, due to having alumina composition in raw material, uses oxidation
The crucible of aluminium will not pollute raw material, and cost is relatively low, and corundum crucible is placed in atmosphere furnace, be passed through the nitrogen of flowing, nitrogen
Flow is 0.5L/min, is heated to 800~1000 DEG C with the heating rate of 5~7 DEG C/min, then with the heating speed of 3~5 DEG C/min
Degree is heated to 1200~1300 DEG C, then is heated to 1420~1460 DEG C with the heating rate of 1~3 DEG C/min, then keep the temperature 6~
9h obtains nitridation product.
Step 5: will nitridation product be put into moderate oven, be heated in air atmosphere 700~900 DEG C and keep the temperature 6~
9h；
Step 6: it will be cleaned multiple times in the dilute hydrochloric acid of 20~25wt.% except the product after carbon, until upper layer filtrate
Clarification, filters out filtrate, by filter residue after filtering drying, obtains Ca- α-SiAlON:Eu fluorescent powder.
Slag of coal gasification according to the present invention selects chemical industry Co., Ltd of Shenmu County, chemical composition are as follows: CaO 7
~10wt.%, SiO235~42wt.%, Al2O310~15wt.%, MgO 1~1.5wt.%, K21~1.5wt.% of O,
Na2O 1~1.5wt.%, Fe2O320~25wt.% of 4~8wt.%, C, other: surplus.
Comparative example:
The method of this comparative example slag of coal gasification and cerium oxide synthetizing phosphor powder, specific as follows:
10g slag of coal gasification is weighed, 0.3g cerium oxide mixes the two, wherein cerium oxide purity is 98.5%, partial size
For 1 μm of powder；Mixture is placed in ball mill, the wet ball grinding 8h in the case where revolving speed is 400r/min, the mixing slurry that will be obtained
After material carries out rotary evaporation on a rotary evaporator at 50 DEG C, places into baking oven and dried at 60 DEG C, after drying
Powder be placed in the mold of Ф 10mm, be pressed into sample by the way that hand is molded；In a nitrogen atmosphere in high temperature controllable type atmosphere
Carbothermal reduction-nitridation reaction is carried out in furnace, is heated to 800 DEG C with the heating rate of 5 DEG C/min, then with the heating rate of 4 DEG C/min
1200 DEG C are heated to, then is heated to 1450 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 9h at 1450 DEG C, the nitridation that will be obtained
Product is put into moderate oven, and 700 DEG C are heated in air atmosphere and keeps the temperature 9h；Then by obtained product 20wt.%'s
It is cleaned multiple times in dilute hydrochloric acid, until upper layer filtrate is clarified, filters out filtrate, by filter residue after filtering drying, obtained final
Product.
Material phase analysis (i.e. XRD analysis) discovery is carried out by the object phase composition of the final product to acquisition, as shown in Figure 1,
Synthesizing in product does not have Ca- α-SiAlON phase, illustrates that cerium oxide can impact the synthesis of Ca- α-SiAlON phase, in turn
It cannot obtain fluorescent material.
Embodiment 1:
10g slag of coal gasification is weighed, 0.3g europium oxide mixes the two, wherein europium oxide purity is 98.5%, partial size
For 1 μm of powder；Mixture is placed in ball mill, the wet ball grinding 8h in the case where revolving speed is 400r/min, the mixing slurry that will be obtained
After material carries out rotary evaporation on a rotary evaporator at 50 DEG C, places into baking oven and dried at 60 DEG C, after drying
Powder be placed in the mold of Ф 10mm, be pressed into sample by the way that hand is molded；In a nitrogen atmosphere in high temperature controllable type atmosphere
Carbothermal reduction-nitridation reaction is carried out in furnace, is heated to 800 DEG C with the heating rate of 5 DEG C/min, then with the heating rate of 4 DEG C/min
1200 DEG C are heated to, then is heated to 1450 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 9h at 1450 DEG C；The nitridation that will be obtained
Product is put into moderate oven, and 700 DEG C are heated in air atmosphere and keeps the temperature 9h；Then by obtained product 20wt.%'s
It is cleaned multiple times in dilute hydrochloric acid, until upper layer filtrate is clarified, filters out filtrate, by filter residue after filtering drying, obtained final
Product.The final product obtained it can be seen from the XRD diagram in Fig. 2 (a) is single Ca- α-SiAlON phase；By in Fig. 3 (a)
SEM photograph can be seen that the Ca- α-SiAlON of synthesis is mutually in elongation column pattern, and Fig. 3 (e) gives EDS in Fig. 3 (a) and analyzes
(spot scan) as a result, knowing that Eu ion has been dissolved into the lattice of Ca- α-SiAlON.To Ca- α-SiAlON:Eu fluorescent powder
Fluorescence spectrum detection is carried out, as shown in Fig. 4 (a), the excitation spectrum of fluorescent powder shows as a very wide band, and there are two peak values point
Not at~300nm and~420nm, caused by first excitation peak is the absorption as Ca- α-SiAlON host lattice, and second
Excitation peak is by Eu2+4f in ion7→4f6Caused by the absorption of 5d.Under 420nm excitation, broadband hair is presented in emission spectrum
It penetrates, peak wavelength 568nm, this is by Eu2+4f in ion65d→4f7Transition caused by, which can be used as white light
LED yellow fluorescent powder.
Embodiment 2:
10g slag of coal gasification is weighed, 0.4g europium oxide mixes the two, wherein europium oxide purity is 98.5%, partial size
For 1 μm of powder；Mixture is placed in ball mill, the wet ball grinding 6h in the case where revolving speed is 500r/min, the mixing slurry that will be obtained
After material carries out rotary evaporation on a rotary evaporator at 70 DEG C, places into baking oven and dried at 50 DEG C, after drying
Powder be placed in the mold of Ф 10mm, be pressed into sample by the way that hand is molded；In a nitrogen atmosphere in high temperature controllable type atmosphere
Carbothermal reduction-nitridation reaction is carried out in furnace, is heated to 900 DEG C with the heating rate of 6 DEG C/min, then with the heating rate of 3 DEG C/min
1200 DEG C are heated to, then is heated to 1420 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 6h at 1420 DEG C；The nitridation that will be obtained
Product is put into moderate oven, and 700 DEG C are heated in air atmosphere and keeps the temperature 8h；Then by obtained product 20wt.%'s
It is cleaned multiple times in dilute hydrochloric acid, until upper layer filtrate is clarified, filters out filtrate, by filter residue after filtering drying, obtain Ca- α-
SiAlON:Eu fluorescent powder.It can be seen that by the XRD spectrum of synthetizing phosphor powder in Fig. 2 (b), final product is single Ca- α-SiAlON
Phase；Fig. 3 (b) can be seen that the Ca- α-SiAlON that the present embodiment synthesizes mutually is in elongation column pattern；It is detected by fluorescence spectrum
It learns: can be seen that from Fig. 4 (b), under 420nm excitation, broadband emission, peak wavelength 569nm is presented in emission spectrum.In addition,
From figure 5 it can be seen that the luminous intensity of the fluorescent powder is compared with Eu2O3High when additive amount is 3wt.%, which can be used as white light
LED yellow fluorescent powder.
Embodiment 3:
10g slag of coal gasification is weighed, 0.5g europium oxide mixes the two, wherein europium oxide purity is 99.5%, partial size
For 100 μm of powder；Mixture is placed in ball mill, the wet ball grinding 10h in the case where revolving speed is 200r/min, the mixing that will be obtained
It after slurry carries out rotary evaporation on a rotary evaporator at 60 DEG C, places into baking oven and is dried at 80 DEG C, will dry
Powder afterwards is placed in the mold of Ф 10mm, is pressed into sample by the way that hand is molded；In a nitrogen atmosphere in high temperature controllable type gas
Carbothermal reduction-nitridation reaction is carried out in atmosphere furnace, is heated to 800 DEG C with the heating rate of 7 DEG C/min, then with the heating speed of 5 DEG C/min
Degree is heated to 1300 DEG C, then is heated to 1460 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 7h at 1460 DEG C；The nitrogen that will be obtained
Change product to be put into moderate oven, 800 DEG C are heated in air atmosphere and keeps the temperature 7h；Then by obtained product in 22wt.%
Dilute hydrochloric acid in be cleaned multiple times, until upper layer filtrate is clarified, filter out filtrate, by filter residue filtered it is dry after, obtain Ca-
α-SiAlON:Eu fluorescent powder.By Fig. 2 (c) as it can be seen that the final product of the present embodiment is single Ca- α-SiAlON phase；By Fig. 3 (c)
As can be seen that the Ca- α-SiAlON that the present embodiment synthesizes mutually is in elongation column pattern；It is learnt by fluorescence spectrum detection: such as
Shown in Fig. 4 (c), under 420nm excitation, broadband emission, peak wavelength 571nm, in addition, can from Fig. 5 is presented in emission spectrum
To find out, the luminous intensity of the fluorescent powder is compared with Eu2O3High when additive amount is 4wt.%, which can be used as white light LEDs yellow
Fluorescent powder.
Embodiment 4:
10g slag of coal gasification is weighed, 0.6g europium oxide mixes the two, wherein europium oxide purity is 99.5%, partial size
For 100 μm of powder；Mixture is placed in ball mill, the wet ball grinding 9h in the case where revolving speed is 300r/min, the mixing that will be obtained
It after slurry carries out rotary evaporation on a rotary evaporator at 80 DEG C, places into baking oven and is dried at 100 DEG C, will dry
Powder afterwards is placed in the mold of Ф 10mm, is pressed into sample by the way that hand is molded；In a nitrogen atmosphere in high temperature controllable type gas
Carbothermal reduction-nitridation reaction is carried out in atmosphere furnace, is heated to 1000 DEG C with the heating rate of 7 DEG C/min, then with the heating of 4 DEG C/min
Speed is heated to 1300 DEG C, then is heated to 1450 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 8h at 1450 DEG C；By what is obtained
Nitridation product is put into moderate oven, and 900 DEG C are heated in air atmosphere and keeps the temperature 6h；Then obtained product is existed
It is cleaned multiple times in the dilute hydrochloric acid of 25wt.%, until upper layer filtrate is clarified, filters out filtrate, by filter residue after filtering drying,
Obtain Ca- α-SiAlON:Eu fluorescent powder.From Fig. 2 (d) as can be seen that the final product that the present embodiment obtains mutually is single Ca- α-
SiAlON phase；By Fig. 3 (d) with 3 (f) it is found that the Ca- α-SiAlON that synthesizes of the present embodiment is mutually in elongation column pattern, and Eu from
Son has been dissolved into the lattice of Ca- α-SiAlON；It is learnt by fluorescence spectrum detection: as shown in Fig. 4 (d), being excited in 420nm
Under, broadband emission, peak wavelength 576nm is presented in emission spectrum；In addition, figure 4, it is seen that the strong light of the fluorescent powder
Degree is compared with Eu2O3High when additive amount is 5wt.%, which can be used as Yellow fluorescent powder used by white light LED.
Embodiment 5
10g slag of coal gasification is weighed, 0.7g europium oxide mixes the two, wherein europium oxide purity is 99.5%, partial size
For 100 μm of powder；Mixture is placed in ball mill, the wet ball grinding 9h in the case where revolving speed is 400r/min, the mixing that will be obtained
It after slurry carries out rotary evaporation on a rotary evaporator at 70 DEG C, places into baking oven and is dried at 100 DEG C, will dry
Powder afterwards is placed in the mold of Ф 10mm, is pressed into sample by the way that hand is molded；In a nitrogen atmosphere in high temperature controllable type gas
Carbothermal reduction-nitridation reaction is carried out in atmosphere furnace, is heated to 1000 DEG C with the heating rate of 6 DEG C/min, then with the heating of 4 DEG C/min
Speed is heated to 1300 DEG C, then is heated to 1450 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 9h at 1450 DEG C；By what is obtained
Nitridation product is put into moderate oven, and 700 DEG C are heated in air atmosphere and keeps the temperature 9h；Then obtained product is existed
It is cleaned multiple times in the dilute hydrochloric acid of 20wt.%, until upper layer filtrate is clarified, filters out filtrate, by filter residue after filtering drying,
Obtain Ca- α-SiAlON:Eu fluorescent powder.From Fig. 2 (e) as can be seen that the obtained final product of the present embodiment is in addition to Ca- α-
Outside SiAlON phase, submellite phase (Ca is also detected2Al2SiO7) diffraction maximum, illustrate the adding too much of europium oxide at this time,
Cause to nitrogenize in product and other impurity phases occur, reduces the phase purity of synthetizing phosphor powder body, and then cannot get required
High pure phosphor.
It is found by carrying out analysis to the final product of acquisition, the slag of coal gasification carbothermal reduction-nitridation for adding europium oxide closes
At the reaction mechanism of Ca- α-SiAlON:Eu fluorescent powder are as follows:
Ca-Si-Al-O glass phase and europium oxide in initial reaction stage (~1200 DEG C), gasifier slag form Ca-Si-
Al-Eu-O liquid phase:
Ca-Si-Al-O+Eu2O3→ Ca-Si-Al-Eu-O (liquid phase)
(~1300 DEG C) as the temperature rises, Ca-Si-Al-Eu-O liquid phase occur carbothermal reduction-nitridation reaction and generate richness
The SiAlON phase (O-SiAlON) of oxygen:
Ca-Si-Al-Eu-O (liquid phase)+C+N2→O-SiAlON
With penetrating further into for nitrogen, oxygen-enriched SiAlON phase is gradually changed into the SiAlON phase (β-SiAlON of rich nitrogen
With α-SiAlON), β-SiAlON can also be further transformed to α-SiAlON:
O-SiAlON→β-SiAlON
O-SiAlON→α-SiAlON
β-SiAlON→α-SiAlON
Finally, calcium ion (Ca2+) and trivalent europium ion (Eu3+) be dissolved into the lattice of α-SiAlON, in reproducibility gas
Under atmosphere, Eu3+Further it is reduced into Eu2+, ultimately form Ca- α-SiAlON:Eu fluorescent powder.
When the additive amount of europium oxide excessive (such as embodiment 5), high-purity fluorescent powder can not be obtained, this is because a side
Face original Ca-Si-Al-O system becomes Ca-Eu-Si-Al-O system, and the formation temperature of liquid phase, liquid phase are formed and glued in reaction process
Degree changes correspondingly, to influence the formation temperature and shape characteristic of final Ca- α-SiAlON；On the other hand, due to europium oxide with
The interaction of reducing agent consumes part carbon so that participate in carbothermal reduction-nitridation synthesis Ca- α-SiAlON reaction in CaO,
Al2O3、SiO2It changes with the relative amount of C, this change may result in final nitridation product other impurities phase (such as
Ca2Al2SiO7, SiC etc.) generation, influence the phase purity of synthetizing phosphor powder, and then its luminescent properties；In addition, Eu2O3Additive amount
Doping concentration of the Eu ion in host lattice in synthesis Ca- α-SiAlON:Eu fluorescent powder is also determined, it equally also can be to photism
It can have an impact.
In conclusion the present invention uses slag of coal gasification for raw material, by adding suitable europium oxide, pass through carbon thermal reduction
Nitridation reaction combination postprocessing working procedures, by adjusting nitriding temperature and soaking time, available high-purity Ca- α-SiAlON:
Eu fluorescent powder, purity reach 95wt.% or more.
Claims (5)
1. a kind of method using slag of coal gasification synthesis white light LEDs Ca- α-SiAlON:Eu fluorescent powder, which is characterized in that tool
Body the following steps are included:
Step 1: slag of coal gasification and europium oxide are mixed according to the ratio that mass percent is 100:3~6；The oxidation
Europium is the powder that purity is 98.5%~99.5%, partial size is 1~100 μm.
Step 2: the mixture that step 1 is obtained is placed in ball mill, 6~10h of wet ball grinding, the mixing slurry after obtaining ball milling
Material；
Step 3: it after mixed slurry is carried out rotary evaporation on a rotary evaporator, places into baking oven and is dried, dried
Powder after dry, the powder after drying is placed in mold and is pressed into sample；
Step 4: sample is put into crucible, and crucible is placed in atmosphere furnace, is passed through the nitrogen of flowing, with the liter of 5~7 DEG C/min
Warm speed is heated to 800~1000 DEG C, then is heated to 1200~1300 DEG C with the heating rate of 3~5 DEG C/min, then with 1~3
DEG C/heating rate of min is heated to 1420~1460 DEG C, 6~9h is then kept the temperature, nitridation product is obtained；
Step 5: nitridation product is put into moderate oven, and 700~900 DEG C are heated in air atmosphere and keeps the temperature 6~9h；
Step 6: it will be cleaned multiple times in the dilute hydrochloric acid of 20~25wt.% except the product after carbon, until upper layer filtrate is clear
Clearly, filtrate is filtered out, by filter residue after filtering drying, obtains Ca- α-SiAlON:Eu fluorescent powder.
2. the method for synthesizing white light LEDs Ca- α-SiAlON:Eu fluorescent powder using slag of coal gasification as described in claim 1,
It is characterized in that, the flow of the nitrogen is 0.5L/min.
3. the method for synthesizing white light LEDs Ca- α-SiAlON:Eu fluorescent powder using slag of coal gasification as described in claim 1,
It is characterized in that, the crucible is corundum crucible.
4. the method for synthesizing white light LEDs Ca- α-SiAlON:Eu fluorescent powder using slag of coal gasification as described in claim 1,
It is characterized in that, the rotating evaporation temperature is 50~80 DEG C, and drying temperature is 50~100 DEG C.
5. the method for synthesizing white light LEDs Ca- α-SiAlON:Eu fluorescent powder using slag of coal gasification as described in claim 1,
It is characterized in that, the ball-milling medium is ethyl alcohol, grinding ball material Al2O3, revolving speed is 200~500r/min.
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| CN101607821A (en) * | 2009-07-13 | 2009-12-23 | 西安建筑科技大学 | A kind of method of utilizing gasifier slag to synthesize Ca-alpha-Sialon |
| CN101864311A (en) * | 2010-06-18 | 2010-10-20 | 上海应用技术学院 | Rare-earth ion doped superfine alpha-sialon fluorescent powder and synthesis method thereof |
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| EP1555307A2 (en) * | 2003-12-01 | 2005-07-20 | Ube Industries, Ltd. | Production method of sialon-based phosphor, and sialon-based phosphor |
| CN101607821A (en) * | 2009-07-13 | 2009-12-23 | 西安建筑科技大学 | A kind of method of utilizing gasifier slag to synthesize Ca-alpha-Sialon |
| CN101864311A (en) * | 2010-06-18 | 2010-10-20 | 上海应用技术学院 | Rare-earth ion doped superfine alpha-sialon fluorescent powder and synthesis method thereof |
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