CN1297629C - Cerium, gadolinium activated yttrium aluminium garnet fluorescent powder and preparation method - Google Patents
Cerium, gadolinium activated yttrium aluminium garnet fluorescent powder and preparation method Download PDFInfo
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- CN1297629C CN1297629C CNB2005100127889A CN200510012788A CN1297629C CN 1297629 C CN1297629 C CN 1297629C CN B2005100127889 A CNB2005100127889 A CN B2005100127889A CN 200510012788 A CN200510012788 A CN 200510012788A CN 1297629 C CN1297629 C CN 1297629C
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Abstract
The present invention relates to yttrium aluminium garnet fluorescent powder activated by cerium and gadolinium, and a preparation method thereof. Yttrium oxide, alumina, cerium oxide, gadolinium oxide, boric acid, barium fluoride, carbon powder and anhydrous alcohol are used as raw materials, wherein the cerium oxide and the gadolinium oxide are used as activating agents, the boric acid and the barium fluoride are used as fusing agents, the anhydrous alcohol is used as a ball milling medium, and the carbon powder is used as a reducing agent. After the raw materials are processed by the following steps of mixing, grinding, ball milling through a ball mill, calcination through a high-temperature tubular furnace, cooling, fine grinding, sieving, detection, packing and storing, the yttrium aluminum garnet fluorescent powder which is yellow and has high purify is obtained. The yttrium aluminium garnet fluorescent powder granules are in a sphere shape and are fine and uniform to form a single yttrium aluminum garnet YAG phase with good luminous performance, so that the single yttrium aluminum garnet YAG phase can be particularly used as fluorescent powder for a white-light diode. The preparation method has the advantages of less equipment, simple process, abundant sources of the raw materials, low preparation cost, high product yield (the yield can reach 95%), and good purity (the purity can reach 98%). Thereby, the preparation method is a very ideal method for preparing the yttrium aluminum garnet fluorescent powder.
Description
Technical field
The present invention relates to the preparation method of a kind of cerium, gadolinium activated yttrium aluminium garnet fluorescent powder, belong to the technical field of rare earth aluminate fluorescent material preparation method.
Background technology
Yttrium aluminum garnet (being called for short YAG) is by yttrium oxide and a kind of rare earth aluminate garnet of aluminum oxide reaction synthetic, belong to isometric system, it is the crystal that a kind of hardness is very big, fusing point is very high, have excellent mechanical intensity, chemical stability, thermal conductivity, be a kind of monocrystal material of excellent property, because the radius and the Y of trivalent rare earth ions
3+Radius (rY
3+=0.096nm) close, be easy to mix and replace Y
3+Ion and obtain the luminous of different colours, thereby be widely used as laser and luminous substrate material.
With cerium-ion activated yttrium aluminum garnet (YAG:Ce
3+) be often used as ultrashort afterglow flying-spot scanner fluorescent material, green light under cathode-ray exciting; Earlier 1990s, after Japan Ri Ya company succeeds in developing efficient blue LED (LEDs), make LEDs form the integral framework of red, green, blue three primary colours, thereby LEDs efficient, less energy-consumption becomes a kind of very promising pollution-free green solid general lighting light source, caused great attention, the making method of white light LEDs s is normally used efficient gallium nitride-based material: the blue led s chip of InGaN (InGaN) preparation excites yellow YAG:Ce
3+Fluorescent material forms white light LEDs s; The blue light that InGaN sends partly is used to excite YAG:Ce
3+, YAG:Ce
3+Be excited, the gold-tinted that sends forms white light with the residue blue light.
With blue chip and yellow YAG:Ce
3+The white light LEDs s of fluorescent material preparation, because the redness in the shortage red, green, blue three primary colours causes the colour temperature of white light LEDs s higher, decay is serious, is difficult to meet various lighting requirements; Studies show that, at yellow YAG:Ce
3+Add gadolinium ion in the fluorescent material, can make the red shift of fluorescent material emission wavelength effectively, send orange coloured light, thereby reduce the colour temperature of white light LEDs s, improve the performance of white light LEDs s.
At present, the method for producing yttrium aluminium garnet fluorescent powder mainly contains high-temperature solid phase reaction method, sol-gel method, the precipitator method, combustion method, microwave exposure method etc., and these methods respectively possess some good points, but also have many weak points.
For example: high-temperature solid phase reaction method is a kind of traditional synthetic method, technical process simply, does not need complex apparatus, is beneficial to suitability for industrialized production, but the synthesis temperature height, more than 1500 ℃, long reaction time, more than 10 hours, production unit is fragile, and fluorescent powder grain is thick, easily caking, dephasign is many, is difficult to obtain monophasic cube of garnet structure.
For example: sol-gel method, generally adopting the organo-metallic alkoxide is raw material, by steps such as hydrolysis, polycondensation, drying, sintering, can obtain the granularity smaller particles, need not to grind, but technical process be long, moisture wraps in the colloid, be difficult for losing, metal alkoxide is a raw material, the cost height, toxic, pollution is arranged, harmful, influence the luminosity of luminescent powder.
For example: the precipitator method, divide sluggish precipitation, coprecipitation method again, sluggish precipitation is slowly to generate precipitation when metal salt solution and precipitant solution mixing, coprecipitation method is to be used for synthetic two or more the composite oxides of metallic element, the precipitator method have solved the deficiency of sol-gel method, and the raw materials used inorganics that is, cost is low, easily dry, no Prevent Carbon Contamination, but, can not realize the homogeneity that microcosmic is formed because precipitation produces between the component concentration and sedimentation speed there are differences, and synthetic product is reunited more serious, and luminous efficiency is low.
For example: combustion method, it is the thermopositive reaction between organic-fuel and the metal salt solution, reaction system can be warming up to 1600 ℃, produce a large amount of gases, be swift in response, entire reaction course only must tens seconds, the product granularity is little, size distribution is even, but introduces carbon easily in combustion processes, and product purity is reduced.
For example: the microwave exposure method, be a kind of method of new rise, adopt microwave exposure forced hydrolysis or the pyrolysis of microwave exposure precursor, can make various single or composite oxides ultrafine powders, make system can be in very short time even heating, in washing, dry, 900 ℃ of calcinings, obtain single yttrium aluminum garnet, but most of raw material is few oxide compound that absorbs microwave, must take certain measure, just can effectively utilize microwave method, the synthetic method difficulty is big, still is in exploratory development period.
Summary of the invention
Goal of the invention
The objective of the invention is at disadvantages of background technology, a kind of brand-new preparation method of making the yttrium aluminium garnet fluorescent powder of activator of cerium ion, gadolinium ion is provided, adopt new reparation technology flow process and equipment, adopt new chemical substance to add and proportioning, the method that adopts mechanical mill and high-temperature calcination, combination reaction to combine, finally obtain highly purified yttrium aluminium garnet fluorescent powder, make the required yellow fluorescent powder of white light-emitting diodes to be applicable to, and be complementary with the InGaN light-emitting diode chip for backlight unit of blue light.
Technical scheme
The chemical substance that the present invention uses is: yttrium oxide, cerium oxide, aluminum oxide, gadolinium sesquioxide, boric acid, barium fluoride, carbon dust, dehydrated alcohol, its combination matching is: with gram, milliliter is measure unit
Yttrium oxide: Y
2O
32.5746 gram ± 0.0005 gram
Cerium oxide: CeO
20.2066 gram ± 0.0005 gram
Aluminum oxide: Al
2O
35.098 gram ± 0.0005 gram
Gadolinium sesquioxide: Gd
2O
36.525 gram ± 0.0005 gram
Boric acid: H
3BO
30.072 gram ± 0.0005 gram
Barium fluoride: BaF
20.072 gram ± 0.0005 gram
Carbon dust: C 14.5482 grams ± 0.003 gram
Dehydrated alcohol: CH
3CH
210 milliliters ± 1 milliliter of OH
Metallic element mol ratio: yttrium Y: cerium Ce: gadolinium Gd: aluminium Al=1.14: 0.06: 0.18: 5
Preparation method of the present invention is as follows:
1) selected chemical substance
To carry out selectedly to the required chemical substance of proportioning, and carry out control of purity:
Yttrium oxide: 99.99%
Cerium oxide: 99.99%
Aluminum oxide: 99%
Gadolinium sesquioxide: 99.99%
Boric acid: 99.5%
Barium fluoride: 99%
Carbon dust: 99%
Dehydrated alcohol: 99.7%
2) raw material mixes
The chemical substance that proportioning is required places mixing vessel, mixes;
3) grind
The chemical substance that mixes is placed agate mortar, grind, milling time 30 minutes with grinding rod;
4) ball milling
Fine powder after grinding is placed agate jar, add agate ball, the raw material fine powder is 1: 3 with the amount ratio of agate ball, add 10 milliliters ± 1 milliliter of ball-milling medium dehydrated alcohol, place planetary ball mill to carry out ball milling agate jar then, 300 rev/mins of ball milling speed, become micropowders behind the raw material fine powder ball milling at 3 hours ball milling time;
5) oven dry
Raw material micropowders behind the ball milling is placed stainless steel or glassware, put into drying baker then and dry, bake out temperature is 100 ℃ ± 3 ℃, and drying time is 2 hours;
6) carbon dust grinds
To restrain with carbon dust 14.5482 grams ± 0.003 of the same weight of required chemical substance, in agate mortar, grind, sieve, grind again, become fine powder;
7) the raw material fine powder mixes with carbon dust
Raw material micropowders after the ball milling oven dry is placed mixing vessel, add carbon powder of reducing agent 14.5482 grams ± 0.003 gram of identical weight then, mixing and stirring becomes mixing fine powders, and mixing fine powders is placed corundum product boat;
8) high-temperature calcination
The corundum product boat that the raw material mixing fine powders is housed is placed high temperature process furnances, open High Temperature Furnaces Heating Apparatus then and carry out heat temperature raising, rate of heating is 7 ℃/minute, and be 183 minutes heat-up time, is heated to 1300 ℃ ± 5 ℃, stops heating; This temperature constant temperature insulation 540 minutes, product was with high temperature process furnances cooling cooling then, and be 256 minutes cooling time, and speed of cooling is 5 ℃/minute, is cooled to 20 ℃ ± 3 ℃, and fusing assistant boric acid, barium fluoride are fluxed;
Combination reaction
In the high-temperature calcination process, its chemical substance will be carried out combination reaction, and the combination reaction formula is as follows:
Cerium ion, gadolinium ion activate and reaction;
9) pulverize, grind
Cooled product powder places agate mortar, pulverizes, fine grinding the yellowly powder;
10) sieve
Product powder behind the fine grinding sieves with 400 purpose screen clothes, grinds repeatedly, sieves repeatedly, obtains final product-yttrium aluminium garnet fluorescent powder yellow powder;
11) collect product
Grinding, the yttrium aluminium garnet fluorescent powder yellow powder that obtains that sieves are placed brown transparent Glass Containers, the airtight preservation of lucifuge;
12) detect, analyze, contrast
Purity, form, pattern, particle size, structure, luminescent properties to the yttrium aluminium garnet fluorescent powder yellow powder detect, analyze, contrast, carry out the analysis that compares of crystalline structure, thing with the X-ray diffraction analysis instrument, carry out fluorescent powder grain pattern, size comparative analysis with field emission scanning electron microscope, carry out the luminescent properties analysis with fluorescence spectrophotometer;
13) packing and storing
Yttrium aluminium garnet fluorescent powder yellow powder to producing places brown glass container, and lucifuge is airtight to be stored in drying, cool place, the clean environment, and storing temp is 20 ℃ ± 3 ℃, strict waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode.
The calcining of described cerium, gadolinium ion activated yttrium aluminium garnet fluorescent powder, in high temperature process furnances, carry out, calcining temperature is 1300 ℃ ± 5 ℃, and heat temperature raising speed is 7 ℃/minute, and the heating-up time is 183 minutes, the constant temperature soaking time is 540 minutes, after the calcining, product is with stove cooling cooling, and cooling rate is 5 ℃/minute, temperature fall time is 256 minutes, is cooled to 20 ℃ ± 3 ℃ of normal temperature.
Ce elements in the described chemical substance cerium oxide and the gadolinium element in the gadolinium sesquioxide are the active element of yttrium aluminium garnet fluorescent powder, the doping of cerium oxide is 0.2066 gram ± 0.0005 gram, the doping of gadolinium sesquioxide is 6.525 grams ± 0.0005 grams, and yttrium (Y): cerium (Ce): gadolinium (Gd): the mol ratio of aluminium (Al) element is Y: Ce: Gd: Al=1.14: 0.06: 0.18: 5.
Producing of described cerium, gadolinium ion activated yttrium aluminium garnet fluorescent powder is with yttrium oxide Y
2O
3, aluminium oxide Al
2O
3Be raw material, with cerium oxide CeO
2, gadolinium sesquioxide Gd
2O
3Being activator, is reductive agent with carbon dust C, with boric acid H
3BO
3, barium fluoride BaF
2Be fusing assistant, with dehydrated alcohol CH
3CH
2OH is a ball-milling medium.
The pattern of described cerium, gadolinium ion activated yttrium aluminium garnet fluorescent powder is a form of spherical particles, and its particle size is 3-5 μ m.
Effect
The present invention compares with background technology has tangible advance, adopted rational chemical substance selected, proportioning, fusing assistant adds, mix, grind, ball milling, oven dry, calcining, heat up, constant temperature, insulation, cooling, grind, sieve, the check and analysis contrast, with yttrium oxide, aluminum oxide is a raw material, with cerium oxide, gadolinium sesquioxide is an activator, with the carbon dust is reductive agent, with boric acid, barium fluoride is a fusing assistant, with the dehydrated alcohol is ball-milling medium, finally obtain yttrium aluminium garnet fluorescent powder yellow powder product, the product even particle distribution, the pattern subglobular, form single yttrium aluminium garnet YAG phase, luminescent properties is good, this patent is produced the synthetic yttrium aluminium garnet fluorescent powder and can be complementary with the InGaN chip of blue light, the utmost point is applicable to makes the required yellow fluorescent powder of white light-emitting diodes, this preparation method uses equipment few, technical process is simple, it is low to produce cost, the product yield height, production yield rate can reach 95%, purity is good, and purity can reach 98%, is the preparation method of the required yttrium aluminum garnet yellow fluorescent powder of very good making white light-emitting diodes.
Description of drawings
Fig. 1 is for producing the yttrium aluminium garnet fluorescent powder process flow sheet
Fig. 2 heats up, is incubated, cools off the coordinate graph of a relation for the high temperature process furnances calcining
Fig. 3 is the fluorescent powder product X ray diffracting spectrum
Fig. 4 is the excitation spectrum comparison diagram of different cerium doping fluorescent powder product
Fig. 5 is the emmission spectrum comparison diagram of different cerium doping fluorescent powder product
Fig. 6 is the emmission spectrum comparison diagram of different gadolinium doping fluorescent powder product
Fig. 7 is the fluorescent powder product excitation spectrum
Fig. 8 is the fluorescent powder product emmission spectrum
Fig. 9 is the following 5000 times of microscopic appearance figure of fluorescent powder product field emission scanning electron microscope
Embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, to produce yttrium aluminium garnet fluorescent powder and will carry out in strict accordance with process flow sheet, each production parameter is wanted strict control, operation according to the order of sequence.
To producing required chemical substance material: yttrium oxide, cerium oxide, aluminum oxide, gadolinium sesquioxide, boric acid, barium fluoride, carbon dust, dehydrated alcohol want strict selected, and carry out control of purity, can not have impurity to get involved, and prevent to generate by product.
To must not exceed minimum and maximum scope in strict accordance with the proportioning Weighting and Controlling to required chemical substance.
Employed chemical substance is to be raw material with yttrium oxide, aluminum oxide, is activator with cerium oxide, gadolinium sesquioxide, is fusing assistant with boric acid, barium fluoride, is reductive agent with the carbon dust, is ball-milling medium with the dehydrated alcohol.
Behind the cerium-ion activated yttrium aluminium garnet fluorescent powder of activator cerium oxide, can send gold-tinted, and form white light with the residue blue light;
Behind the gadolinium ion activated yttrium aluminum garnet phosphor powder of activator gadolinium sesquioxide, can effectively make the red shift of fluorescent material emission wavelength, send orange coloured light, reduce the colour temperature of product white light-emitting diodes, improve the performance of product.
The mixing of desired raw material is wanted evenly, and grinding will be ground in agate mortar in refinement, must not be less than 30 minutes.
Fine powder after the grinding will place agate jar to carry out ball milling with ball mill, and raw material is advisable with 1: 3 with the amount ratio of ball, and adds 10 milliliters ± 1 milliliter of ball-milling medium dehydrated alcohol, and ball milling speed is good with 300 rev/mins, and the ball milling time is 3 hours.
Will dry processing behind the ball milling, carry out in drying baker, bake out temperature is 100 ℃ ± 3 ℃, and drying time is 2 hours.
Take by weighing carbon dust 14.5482 gram ± 0.003 gram with the same weight of required chemical substance, in agate mortar, grind, become fine powder.
Raw material fine powder after the oven dry will add carbon dust 14.5482 grams ± 0.003 gram of same weight, and mixes and stir, and becomes mixing fine powders, places corundum product boat then, waits for calcining.
Calcining is carried out in high temperature process furnances, corundum product boat is placed High Temperature Furnaces Heating Apparatus together with the raw material mixing fine powders, heat temperature raising then, heat-up rate is 7 ℃/minute, during to 1300 ℃, constant temperature insulation 540 minutes, and carry out combination reaction, activator cerium ion, gadolinium ion carry out activating reaction.
Behind constant temperature insulation, combination reaction, the activating reaction, the cooling cooling, speed of cooling is 5 ℃/minute, corundum product boat with the High Temperature Furnaces Heating Apparatus cooling, to 20 ℃ ± 3 ℃ of normal temperature, takes out product boat and product together with product.
To pulverize, grind, sieve after the product calcining, after sieving with 400 eye mesh screens, promptly obtain final product-yttrium aluminium garnet fluorescent powder yellow powder.
The yellow powder of producing will be collected in airtight preservation in the brown glass container, carries out check and analysis then and contrasts its pattern, color and luster, structure, performance etc.
To producing required equipment: container, agate mortar, ball mill, agate jar, corundum product boat, glass stirring rod, grinding rod, drying baker, high temperature process furnances, screen cloth, detecting instrument etc. will keep clean, and pollution must not be arranged.
Each preparation apparatus is in quasi-operating status;
Selected by proportioning, take by weighing 10 milliliters of yttrium oxide 2.5746 grams, cerium oxide 0.2066 gram, aluminum oxide 5.098 grams, gadolinium sesquioxide 6.525 grams, boric acid 0.072 gram, barium fluoride 0.072 gram, carbon dust 14.5482 grams, dehydrated alcohol;
Place mixing vessel to mix chemical substance yttrium oxide, cerium oxide, aluminum oxide, gadolinium sesquioxide, boric acid, barium fluoride;
Place agate mortar to grind 30 minutes the blended chemical substance, become fine powder;
Fine powder after grinding is placed agate jar, add agate ball, the raw material fine powder is 1: 3 with agate ball amount ratio, add 10 milliliters of ball-milling medium dehydrated alcohols, open planetary ball mill and carry out ball milling, 300 rev/mins of ball mill revolutions, 3 hours ball milling time, the raw material fine powder becomes micropowders behind the ball milling;
Micropowders behind the ball milling is collected in stainless steel or the Glass Containers, places drying baker to dry, 100 ℃ ± 3 ℃ of bake out temperatures, drying time 2 hours;
Take by weighing and equiponderant carbon dust 14.5482 grams of required chemical substance, in agate mortar, grind, become fine powder;
Raw material micropowders after the oven dry is added carbon dust 14.5482 grams, carbon dust weight=raw material micropowders weight, mixing and stirring becomes mixing fine powders;
Mixing fine powders is placed corundum product boat;
Place high temperature process furnances to calcine together with mixing fine powders in corundum product boat;
Open High Temperature Furnaces Heating Apparatus, the heating that heats up, heat-up rate is 7 ℃/minute, the constant temperature insulation is 540 minutes during to 1300 ℃ ± 5 ℃, in the time of 1300 ℃ ± 5 ℃, combination reaction takes place;
Fusing assistant boric acid, barium fluoride are fluxed, and activator cerium ion, gadolinium ion activate and reaction;
After calcining finishes, the cooling cooling, speed of cooling is 5 ℃/minute, corundum product boat cools off with High Temperature Furnaces Heating Apparatus together with product, to 20 ℃ ± 3 ℃ of normal temperature;
Cooled yellow powder product places agate mortar to grind; Sieve with 400 purpose screen clothes then, grind, sieve and carry out by turns repeatedly, finally obtain product-yttrium aluminium garnet fluorescent powder yellow powder;
The yttrium aluminium garnet fluorescent powder yellow powder is collected in the brown glass container, and lucifuge, airtight preservation are in order to detecting, analyze, contrasting; Thereby finished the whole process of producing.
Shown in Figure 2, be that high temperature process furnances calcining heats up, constant temperature insulation, cooling coordinate graph of a relation, when the temperature of high temperature process furnances is warming up to 1300 ℃ ± 5 ℃, 7 ℃/minute of heat-up rates from 20 ℃ ± 3 ℃, take 183 minutes, intersect at the A point, constant temperature, soaking time 540 minutes, the insulation period is the A-B section, constant temperature insulation back is the cooling period, promptly reduce to 20 ℃ ± 3 ℃ of normal temperature from the B point, cooling rate is 5 ℃/minute, and be 256 minutes cooling time.
Shown in Figure 3, be the fluorescent powder product X ray diffracting spectrum, ordinate zou is a diffraction peak intensity, and X-coordinate is 2 times of diffraction angle, and the crystal indices of three strongest ones' peak correspondence of product are respectively (420), (211), (640).
Shown in Figure 4, it is the excitation spectrum comparison diagram of the fluorescent powder product of different cerium ion-doped amounts, ordinate zou is the relative intensity index, X-coordinate is a nano wave length, find out among the figure, when the molar fraction of cerium ion is b-x=0.06, blue-light excited the strongest by the 460nm wavelength, take second place during c-x=0.08, minimum during a-x=0.04.
Shown in Figure 5, it is the emmission spectrum comparison diagram of the fluorescent powder product of different cerium ion-doped amounts, ordinate zou is the relative intensity index, X-coordinate is a nano wave length, find out among the figure that when the molar fraction of cerium ion was b-x=0.06, emissive porwer was the strongest, take second place during c-x=0.08, minimum during a-x=0.04.
The cerium ion-doped amount of the activator that is adopted, be to draw through a large amount of experimental summaries, optimization, the molar fraction x=0.06 of cerium ion, the molecular weight of cerium oxide are 172.13, the amount of substance of cerium oxide is 0.0012mol, is 0.2066 gram so can draw the consumption of cerium oxide.
Shown in Figure 6, it is the emmission spectrum comparison diagram of the fluorescent powder product of different gadolinium ion dopings, ordinate zou is the relative intensity index, and X-coordinate is a nano wave length, finds out among the figure, when the molar fraction of gadolinium ion is f-y=0.18, fluorescent material emission wavelength red shift maximum is 560nm, helps making the moderate white light-emitting diodes of colour temperature, emission wavelength is 531nm during d-y=0.06, and emission wavelength is 543nm during e-y=0.12.
The activator gadolinium ion doping that is adopted, be to draw through a large amount of experimental summaries, optimization, the molar fraction y=0.18 of gadolinium ion, the molecular weight of gadolinium sesquioxide are 362.5, the amount of substance of gadolinium sesquioxide is 0.018mol, is 6.525 grams so can draw the consumption of gadolinium sesquioxide.
Shown in Figure 7, be the exciting light spectrogram of fluorescent powder product, ordinate zou is the relative intensity index, and X-coordinate is a nano wave length, and product can effectively be excited by the blue light of 460nm wavelength.
Shown in Figure 8, be the emmission spectrum figure of fluorescent powder product, ordinate zou is the relative intensity index, and X-coordinate is a nano wave length, and maximum emission peak is 560nm, is the yellow emission wave band.
Shown in Figure 9, be fluorescent powder product microscopic appearance figure of 5000 times under field emission scanning electron microscope, the fluorescent powder product even particle distribution, spherical in shape substantially, particle size is 3-5 μ m.
In producing the process of yttrium aluminium garnet fluorescent powder, owing to grinding, ball milling, sieve, dry, calcine, cool off, also can make the fluorescent powder grain pattern produced and size that trace takes place and change, but not influence the luminescent properties of fluorescent material.
The chemical substance proportioning of producing yttrium aluminium garnet fluorescent powder is what to determine in a numerical range that sets in advance, is measure unit with gram, milliliter, when carrying out industrialization and produce, with kilogram, be upgraded to measure unit.
Claims (5)
1, the preparation method of a kind of cerium, gadolinium activated yttrium aluminium garnet fluorescent powder, it is characterized in that: the chemical substance that the present invention uses is: yttrium oxide, cerium oxide, aluminum oxide, gadolinium sesquioxide, boric acid, barium fluoride, carbon dust, dehydrated alcohol, its combination matching is: with gram, milliliter is measure unit
Yttrium oxide: Y
2O
32.5746 gram ± 0.0005 gram
Cerium oxide: CeO
20.2066 gram ± 0.0005 gram
Aluminum oxide: Al
2O
35.098 gram ± 0.0005 gram
Gadolinium sesquioxide: Gd
2O
36.525 gram ± 0.0005 gram
Boric acid: H
3BO
30.072 gram ± 0.0005 gram
Barium fluoride: BaF
20.072 gram ± 0.0005 gram
Carbon dust: C 14.5482 grams ± 0.003 gram
Dehydrated alcohol: CH
3CH
210 milliliters ± 1 milliliter of OH
Metallic element mol ratio: yttrium Y: cerium Ce: gadolinium Gd: aluminium Al=1.14: 0.06: 0.18: 5
Preparation method of the present invention is as follows:
1) selected chemical substance
To carry out selectedly to the required chemical substance of proportioning, and carry out control of purity:
Yttrium oxide: 99.99%
Cerium oxide: 99.99%
Aluminum oxide: 99%
Gadolinium sesquioxide: 99.99%
Boric acid: 99.5%
Barium fluoride: 99%
Carbon dust: 99%
Dehydrated alcohol: 99.7%
2) raw material mixes
The chemical substance that proportioning is required places mixing vessel, mixes;
3) grind
The chemical substance that mixes is placed agate mortar, grind, milling time 30 minutes with grinding rod;
4) ball milling
Fine powder after grinding is placed agate jar, add agate ball, the ratio of raw material fine powder and agate ball is 1: 3, add 10 milliliters ± 1 milliliter of ball-milling medium dehydrated alcohol, place planetary ball mill to carry out ball milling agate jar then, 300 rev/mins of ball milling speed, become micropowders behind the raw material fine powder ball milling at 3 hours ball milling time;
5) oven dry
Raw material micropowders behind the ball milling is placed stainless steel or glassware, put into drying baker then and dry, bake out temperature is 100 ℃ ± 3 ℃, and drying time is 2 hours;
6) carbon dust grinds
To restrain with carbon dust 14.5482 grams ± 0.003 of the same weight of required chemical substance, in agate mortar, grind, sieve, grind again, become fine powder;
7) the raw material fine powder mixes with carbon dust
Raw material micropowders after the ball milling oven dry is placed mixing vessel, add carbon powder of reducing agent 14.5482 grams ± 0.003 gram of identical weight then, mixing and stirring becomes mixing fine powders, and mixing fine powders is placed corundum product boat;
8) high-temperature calcination
The corundum product boat that the raw material mixing fine powders is housed is placed high temperature process furnances, open High Temperature Furnaces Heating Apparatus then and carry out heat temperature raising, rate of heating is 7 ℃/minute, and be 183 minutes heat-up time, be heated to 1300 ℃ ± 5 ℃, stop heating, this temperature constant temperature insulation 540 minutes, product was with high temperature process furnances cooling cooling then, speed of cooling is 5 ℃/minute, be 256 minutes cooling time, is cooled to 20 ℃ ± 3 ℃, and fusing assistant boric acid, barium fluoride are fluxed;
Combination reaction
In the high-temperature calcination process, its chemical substance will be carried out combination reaction, and the combination reaction formula is as follows:
Cerium ion, gadolinium ion activate and reaction;
9) pulverize, grind
Cooled product powder places agate mortar, pulverizes, fine grinding the yellowly powder;
10) sieve
Product powder behind the fine grinding sieves with 400 purpose screen clothes, grinds repeatedly, sieves repeatedly, obtains final product-yttrium aluminium garnet fluorescent powder yellow powder;
11) collect product
Grinding, the yttrium aluminium garnet fluorescent powder yellow powder that obtains that sieves are placed brown transparent Glass Containers, the airtight preservation of lucifuge;
12) detect, analyze, contrast
Purity, form, pattern, particle size, structure, luminescent properties to the yttrium aluminium garnet fluorescent powder yellow powder detect, analyze, contrast, carry out the analysis that compares of crystalline structure, thing with the X-ray diffraction analysis instrument, carry out fluorescent powder grain pattern, size comparative analysis with field emission scanning electron microscope, carry out the luminescent properties analysis with fluorescence spectrophotometer;
13) packing and storing
Yttrium aluminium garnet fluorescent powder yellow powder to producing places brown glass container, and lucifuge is airtight to be stored in drying, cool place, the clean environment, and storing temp is 20 ℃ ± 3 ℃, strict waterproof, protection against the tide, fire prevention, sun-proof, anti-soda acid to corrode.
2, the preparation method of a kind of cerium according to claim 1, gadolinium activated yttrium aluminium garnet fluorescent powder, it is characterized in that: the calcining of described yttrium aluminium garnet fluorescent powder, in high temperature process furnances, to carry out, calcining temperature is 1300 ℃ ± 5 ℃, heat temperature raising speed is 7 ℃/minute, heating-up time is 183 minutes, and the constant temperature soaking time is 540 minutes, after the calcining, product is with stove cooling cooling, cooling rate is 5 ℃/minute, and temperature fall time is 256 minutes, is cooled to 20 ℃ ± 3 ℃ of normal temperature.
3, the preparation method of a kind of cerium according to claim 1, gadolinium activated yttrium aluminium garnet fluorescent powder, it is characterized in that: Ce elements in the described chemical substance cerium oxide and the gadolinium element in the gadolinium sesquioxide are the active element of yttrium aluminium garnet fluorescent powder, the doping of cerium oxide is 0.2066 gram ± 0.0005 gram, the doping of gadolinium sesquioxide is 6.525 grams ± 0.0005 grams, and yttrium (Y): cerium (Ce): gadolinium (Gd): the mol ratio of aluminium (Al) element is Y: Ce: Gd: Al=1.14: 0.06: 0.18: 5.
4, the preparation method of a kind of cerium according to claim 1, gadolinium activated yttrium aluminium garnet fluorescent powder, it is characterized in that: producing of described yttrium aluminium garnet fluorescent powder is with yttrium oxide Y
2O
3, aluminium oxide Al
2O
3Be raw material, with cerium oxide CeO
2, gadolinium sesquioxide Gd
2O
3Being activator, is reductive agent with carbon dust C, with boric acid H
3BO
3, barium fluoride BaF
2Be fusing assistant, with dehydrated alcohol CH
3CH
2OH is a ball-milling medium.
5, the preparation method of a kind of cerium according to claim 1, gadolinium activated yttrium aluminium garnet fluorescent powder, it is characterized in that: the pattern of described yttrium aluminium garnet fluorescent powder is a form of spherical particles, its particle size is 3-5 μ m.
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