A kind of manufacture method of superfine fluorescent powder
Technical field
The present invention relates to the manufacture method of superfine fluorescent powder.Specific implementation process comprises: the preparation feed liquid, add inorganic salt and incendiary material, and cause making incendiary material that fluffyization, burning take place under certain condition, under certain sintering condition, forming fluorescent powder crystal again, processes such as impurity are removed in the fluorescent material in washing.
Background technology
Superfine fluorescent powder is meant near the fluorescent material nanometer-submicron-scale, is a class has the important application prospect at demonstration and lighting field fluorescent material.Because physical influences such as the quantum confined effect of nanometer-submicron particle itself, small-size effect, surface state effect influence, it is many peculiar and have a characteristic of using value to make this class fluorescent material have at aspects such as physics, photochemistry.Nanometer-submicron fluorescent material can be used for comprising: a plurality of fields such as illumination, demonstration, optical information storage, optical information transfer, opto-electronic conversion, scintillator, biological mark have especially begun to present good scientific research and have used trend in demonstration and lighting field.
The preparation method of the superfine fluorescent powder of report mainly contains sol-gel method, combustion method, hydrothermal method, homogeneous precipitation method, microemulsion method or the like at present.Have combustion method and salt that property wherein related to the present invention is bigger help the aerosol decomposition method, below these two kinds of methods are simply set forth respectively.
Combustion method has begun to be applied to the preparation research of nano luminescent material through improving and development.The preparation process of this method is: by adding an amount of incendiary material and reaction promoter in the metal-nitrate solutions, low temperature causes combustion reactions, and the system temperature of reaction reached about 1000 ℃ in moment, react rapidly, and moment finished.Compare characteristics (Mater.Res.Bull.1997,32 (5): 501.) such as combustion method has shortened product crystalline growth time greatly, and it is fast to have speed of response, energy-conservation with the fluorescent material preparation method of routine.The material of combustion method preparation simultaneously has many advantages: as narrow particle size distribution, by regulating the content and the concentration may command particle size of incendiary material.Shortcoming is that tangible agglomeration is arranged between the powder, and powder is network-like, and luminous intensity is not ideal enough.
People such as calendar year 2001 Bin xia propose a kind of salt and help aerosol decomposition method (Adv.Mater. (2001), 13 (20): 1579), people such as K.Okuyama had carried out elaborating (Chem.Engineer.Sci.58 (2003): 537-547) in 2003 to this method afterwards, this method is by adding inorganic salt in the aerosol precursor body, inorganic salt become fused salt and form a kind of solvent environment during pyroprocessing, avoid the particulate reunion, can prepare dispersing property nano particle preferably.What but this method decomposition course used is the spray pyrolysis method, and its luminous intensity is unsatisfactory, also inadvisable at aspects such as throughput, cost, yields.
The preparation method of comprehensive above several superfine fluorescent powders as can be seen, is not fit to suitability for industrialized production at present and has the preparation method of the superfine fluorescent powder of excellent luminescent properties.
Summary of the invention
The object of the present invention is to provide a kind of superfine fluorescent powder manufacture method, this method implementation process is simple, with low cost.
To achieve these goals, the present invention takes following technical scheme:
A kind of superfine fluorescent powder manufacture method comprises four main characterization step simultaneously: make presoma, add incendiary material and alkali-metal muriate in the presoma preparation process, this mixture heating up is ignited, pass through high-temperature heat treatment then.
This superfine fluorescent powder manufacture method specifically comprises the steps:
1) gets Chemical Composition corresponding metal salt and/or oxide compound in the target superfine fluorescent powder, through being made into the aqueous solution after the dissolving respectively; According to target the stoichiometric ratio of superfine fluorescent powder is mixed these solution, obtains mixing solutions; Concentration to this mixing solutions is specifically unqualified, but will guarantee that this mixing solutions can also can dissolve incendiary material and alkali-metal muriate in the complete following step fully;
2) in the mixing solutions that step 1) obtains, add target fluorescent material weight 1-10 incendiary material doubly, stir and make it dissolving;
3) in step 2) add target fluorescent material weight 1-10 alkali-metal muriate doubly in the mixing solutions that obtains, stir mixed;
4) mixture that step 3) is obtained places High Temperature Furnaces Heating Apparatus, adds the thermal initiation combustion reactions, and is incubated;
5) place High Temperature Furnaces Heating Apparatus with obtaining product in the step 4), obtain fluorescent material through roasting;
6) add water washing with obtaining product in the step 5), more after filtration, oven dry is ground, and sieves and promptly gets superfine fluorescent powder product of the present invention.
Can make material precursor that fluffyization and incendiary incendiary material take place by in system, adding, to utilize its institute's heat of emitting and, thereby to stop crystalline to be grown up at a large amount of bubbles of product intermediate formation.The present invention simultaneously also adopts inorganic salt (being alkali-metal muriate) as barrier material, further prevent the reunion of product, the product list is disperseed, and the crystal structure of the fluorescent material of growing in this inorganic salt (the being alkali-metal muriate) environment is complete simultaneously, and pattern is better.
In superfine fluorescent powder manufacture method of the present invention, in described step 1), described corresponding metal salt is the metal ion that comprised of target fluorescent material or the salt of non-metallic element, described corresponding oxide compound is the oxide compound that target fluorescent material is comprised, and the state of described corresponding metal salt, oxide compound is solid-state, the liquid state or the aqueous solution; In the target superfine fluorescent powder, contain under the situation of boron, in described step 1), also add 103-108% doubly to the boric acid of corresponding chemical metering ratio.
In superfine fluorescent powder manufacture method of the present invention, in described step 2) in, described incendiary material comprises at least a in urea, citric acid and the glycine.
In superfine fluorescent powder manufacture method of the present invention, in described step 2) in, described alkali-metal muriate is at least a among NaCl, KCl and the LiCl.
In superfine fluorescent powder manufacture method of the present invention, in described step 4), the temperature of described heating is 450-1200 ℃, and the time of insulation is 10 minutes-2 hours.Wherein, soaking time changes with the amount that adds incendiary material.
In superfine fluorescent powder manufacture method of the present invention, in described step 5), described maturing temperature is at 800-1600 ℃, and soaking time was at 10 minutes-24 hours, and calcination atmosphere is air or hydrogenous reducing atmosphere.This maturing temperature is different and slightly different with the composition of target fluorescent material with soaking time.
In superfine fluorescent powder manufacture method of the present invention, in described step 6), described adding in the water washing,, when the resultant specific conductivity of washing surplus solution of this fluorescent material of washing≤10 μ S/cm, washing finishes.
Characteristics of the present invention are:
1, the superfine fluorescent powder particle size of the present invention's preparation is less, between 20nm-2 μ m, can adjust with the need; The pattern rule, homogeneity is good.2, the superfine fluorescent powder luminous intensity height of the present invention's preparation.3, implementation method of the present invention is simple, and cost of equipment is cheap, and treatment capacity is higher, is suitable for various high-end demonstrations or the illumination preparation with superfine fluorescent powder.
Description of drawings
Fig. 1 is the TEM photo that embodiment 1,2,3 obtains product among the present invention, and wherein, Fig. 1 a is the TEM photo that the embodiment of the invention 1 obtains product; Fig. 1 b is the TEM photo that the embodiment of the invention 2 obtains product; Fig. 1 c is the TEM photo that the embodiment of the invention 3 obtains product.
Fig. 2 obtains the XRD figure spectrum of product for embodiment 1 among the present invention.
Fig. 3 obtains the SEM photo of product for comparing embodiment 1 among the present invention.
Fig. 4 compares for emmission spectrum and comparing embodiment 1 emmission spectrum that embodiment 1 among the present invention obtains product.
Embodiment
Embodiment
Embodiment 1: utilize method of the present invention to prepare 1kg nanometer (Y, Gd) BO
3: the embodiment of Eu fluorescent material.Specific implementation process is as follows:
1) dissolves Y respectively with 1: 1 nitric acid
2O
3, Gd
2O
3, Eu
2O
3Obtain rare earth nitrate solution, make indicator with the dimethyl phenol orange, EDTA is its concentration of titration respectively.
2) measure the rare earth nitrate solution of respective volume respectively according to stoichiometric ratio, mixing adds 105% times of boric acid to corresponding chemical metering ratio, stirs to make it to be dissolved in the mixed rare earth nitrates solution.
3) in above slurries, add the 2kg citric acid as incendiary material, fully mixing.
4) add 1kgNaCl in the slurries of step 3, stirring and dissolving in the crucible of packing into, places High Temperature Furnaces Heating Apparatus to cause combustion reactions down for 500 ℃.Treat after combustion reactions is finished system temperature to be increased to 1200 ℃, be incubated 2 hours.Product is ground, reload in the crucible, at N
2: H
2Be under the reducing atmosphere of 25: 75 (volume ratio), 1000 ℃ of roastings 10 hours.
5) the product of roasting washing adds a certain amount of BaSiO to the specific conductivity of washing surplus solution=10 μ S/cm in powder
3Surface treatment agent carries out surface treatment and promptly obtains the inventive method prepared (Y, Gd) BO
3: Eu fluorescent material.
Comparing embodiment 1: high temperature solid-state method prepares 1kg (Y, Gd) BO
3: the comparing embodiment of Eu fluorescent material.Specific implementation process is as follows:
The oxide compound of the Y of uniform mixing stoichiometric ratio, Gd, Eu and boric acid, then 1200 ℃ of roastings 4 hours, fragmentation, grinding, surface treatment obtain (Y, Gd) BO
3: Eu fluorescent material.
Embodiment 2: utilize method of the present invention to prepare 1kg (Gd, Ce) BO
3: the embodiment of Tb fluorescent material.Specific implementation process is similar to Example 1, and its implementation process is as follows:
1) dissolves CeO respectively with 1: 1 nitric acid
2, Gd
2O
3, Tb
4O
7Obtain rare earth nitrate solution, make indicator with the dimethyl phenol orange, EDTA is its concentration of titration respectively.
2) measure the rare earth nitrate solution of respective volume respectively according to stoichiometric ratio, mixing adds 105% times of boric acid to corresponding chemical metering ratio, stirs to make it to be dissolved in the mixed rare earth nitrates solution.
3) add 10kg urea as incendiary material in above slurries, abundant mixing is in the crucible of packing into.
4) add 10kgKCl in the slurries of step 3, stirring and dissolving in the crucible of packing into, places High Temperature Furnaces Heating Apparatus to cause combustion reactions down for 500 ℃.Treat after combustion reactions is finished system temperature to be increased to 800 ℃, be incubated 2 hours.Product is ground, reload in the crucible, at N
2: H
2Be under the reducing atmosphere of 25: 75 (volume ratio), 1300 ℃ of roastings 4 hours.
5) product of roasting washs to specific conductivity=10 μ S/cm, adds a certain amount of surface treatment agent and carries out surface treatment and promptly obtain the inventive method prepared (Gd, Ce) BO
3: Tb fluorescent material.
TEM shows that the particle size of this powder is 500nm, the pattern rule.The luminescent properties of this powder of luminescent properties test shows has reached the level of corresponding reference.
Embodiment 3: utilize method of the present invention to prepare 1kg nanometer Y
2O
3: the embodiment of Eu fluorescent material.Specific implementation process is as follows:
1) dissolves Y respectively with 1: 1 nitric acid
2O
3, Eu
2O
3Obtain rare earth nitrate solution, make indicator with the dimethyl phenol orange, EDTA is its concentration of titration respectively.
2) measure the rare earth nitrate solution of respective volume respectively according to stoichiometric ratio, mixing.
3) in above slurries, add the 5kg citric acid as incendiary material, fully mixing.
4) add 1kgLiCl in the slurries of step 3, stirring and dissolving in the crucible of packing into, places High Temperature Furnaces Heating Apparatus to cause combustion reactions down for 700 ℃.Treat after combustion reactions is finished system temperature to be increased to 1200 ℃, be incubated 2 hours.Product is ground, reload in the crucible, at N
2: H
2Be under the reducing atmosphere of 25: 75 (volume ratio), 1600 ℃ of roastings 10 minutes.
5) product of roasting washing is to the specific conductivity of washing surplus solution=9 μ S/cm, adds a certain amount of surface treatment agent and carry out surface treatment and promptly obtain the prepared nanometer Y of the inventive method in powder
2O
3: Eu fluorescent material.
A in the accompanying drawing 1, b, c have shown the TEM photo of embodiment 1,2,3 gained superfine fluorescent powders respectively, and as can be seen, this method prepares the less and size homogeneous of particle size of luminescent material, granule-morphology rule, good dispersion property.
Accompanying drawing 2 has provided the XRD figure spectrum of embodiment 1 gained superfine fluorescent powder, and this collection of illustrative plates proof adopts prepared (Y, Gd) BO of method of the present invention
3: Eu fluorescent material is hexagonal system YBO
3N-type waferN has a small amount of dephasign to occur.
Accompanying drawing 3 is the SEM photo that comparing embodiment 1 obtains product in this specification sheets, and the particle size of this fluorescent material is 3-5 μ m as can be seen, and pattern is irregular, the size distribution broad.
Accompanying drawing 4 compares for emmission spectrum and comparing embodiment 1 emmission spectrum that embodiment 1 in this specification sheets obtains product.Solid line is embodiment 1 among Fig. 4, and dotted line is a comparing embodiment 1.As can be seen from Figure 4, adopt method of the present invention prepared (Y, Gd) BO
3: the strongest emission peak of Eu fluorescent material is 611nm, rather than 593nm.The emission peak that is positioned at about 625nm has had tangible broadening, and near the emission peak the 700nm also is significantly improved, because the red shift and the broadening of spectrum main peak, the purity of color of this powder can improve.
Tabulate down and 1 shown the embodiment that mentioned among the present invention and the performance of comparing embodiment.As can be seen, the particle size of the superfine fluorescent powder that method of the present invention is prepared is less, and luminescent properties is better.
Table 1: the embodiment among the present invention and the performance of comparing embodiment are relatively.
Sample | CIEx | CIEy | Relative brightness (with reference to the company standard sample) | Particle diameter/nm |
Embodiment |
1 | 0.6417 | 0.3581 | 91 (172nmVUV excites) | 100 |
Comparing embodiment 1 | 0.6415 | 0.3579 | 100 (172nmVUV excites) | 3100 |
Embodiment 2 | 0.3306 | 0.5828 | 105 (254nmUV excites) | 320 |
Embodiment 3 | 0.3305 | 0.5826 | 100 (254nmUV excites) | 60 |