CN112143488B - Reaction method for protecting molten medium and preparation method of stress luminescent fluorescent powder - Google Patents
Reaction method for protecting molten medium and preparation method of stress luminescent fluorescent powder Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 201
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000003223 protective agent Substances 0.000 claims abstract description 54
- 239000007787 solid Substances 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 150000004820 halides Chemical class 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 150000002910 rare earth metals Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 2
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 230000001681 protective effect Effects 0.000 abstract description 7
- 229910052950 sphalerite Inorganic materials 0.000 description 33
- 229910052984 zinc sulfide Inorganic materials 0.000 description 33
- 229910052593 corundum Inorganic materials 0.000 description 25
- 239000010431 corundum Substances 0.000 description 25
- 239000012467 final product Substances 0.000 description 25
- 229910052748 manganese Inorganic materials 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 23
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 22
- 238000000227 grinding Methods 0.000 description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 18
- 238000011068 loading method Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000000047 product Substances 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- 239000011780 sodium chloride Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000004020 luminiscence type Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052745 lead Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
- C09K11/572—Chalcogenides
- C09K11/574—Chalcogenides with zinc or cadmium
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
- C09K11/572—Chalcogenides
- C09K11/576—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
- C09K11/582—Chalcogenides
- C09K11/584—Chalcogenides with zinc or cadmium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/661—Chalcogenides
- C09K11/663—Chalcogenides with alkaline earth metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7729—Chalcogenides
- C09K11/7731—Chalcogenides with alkaline earth metals
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention relates to the field of material preparation, in particular to a reaction method for protecting a molten medium and a preparation method of stress luminescent fluorescent powder. The invention adds the solid protective agent with the melting point lower than the reaction temperature and the boiling point not lower than the reaction temperature into the reaction system, so that the whole reaction system is immersed into a melting medium formed by the protective agent, thereby isolating the reaction system from the outside, and being particularly suitable for the reaction sensitive to atmosphere such as air. Because operations such as vacuumizing or introducing protective gas are not needed, the operation is simple, and the requirements on equipment are low, the production efficiency is improved, and the production cost is reduced.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a reaction method for protecting a molten medium and a preparation method of stress luminescent fluorescent powder.
Background
Stress luminescence is the luminescence response of a material under the action of mechanical forces. Stress luminescent materials are novel optical functional materials which have been developed for decades and which can convert mechanical energy into optical energy. The stress luminescent material with self-recovery characteristic is represented by rare earth or transition metal ion doped sulfide and oxysulfide system, and has application potential in the fields of pressure sensing, biological imaging, building structure detection and the like. Such materials are usually prepared by a traditional high-temperature solid-phase reaction method and are subjected to technological processes of batching, mixing, calcining, grinding, screening and the like, however, sulfides and sulfur oxides in the materials are easily oxidized by oxygen in the air, so that the materials are very sensitive to the reaction atmosphere.
The traditional reaction system which is sensitive to the reaction atmosphere generally adopts the reaction under the protection atmosphere of nitrogen or inert gas, so that the requirement on the gas atmosphere is high, the corresponding preparation cost and the complexity of the process flow are improved, and the large-scale popularization and production are not facilitated.
Disclosure of Invention
Based on this, it is necessary to provide a reaction method for protecting a molten medium and a method for producing a stress-emitting phosphor, which can simplify the production process and reduce the cost.
In one aspect, the invention provides a molten medium protected reaction process comprising the steps of:
adding solid reaction raw materials and solid protective agents into a reaction container, wherein the protective agents do not participate in the reaction and the addition amount of the protective agents is enough to completely submerge a reaction system in a molten state;
heating to the reaction temperature of the reaction raw materials for reaction, wherein the boiling point of the reaction raw materials and the boiling point of a reaction product are not lower than the reaction temperature, the melting point of the protective agent is lower than the reaction temperature and the boiling point of the protective agent is not lower than the reaction temperature, and the density of the protective agent in a molten state is lower than that of the reaction raw materials and the reaction product in a solid state or a molten state;
the reaction product was collected after the reaction.
In one embodiment, the reaction materials are plural.
In one embodiment, the adding solid reaction materials and solid protectant to the reaction vessel comprises:
mixing the reaction raw materials and part of the protective agent, and adding the mixture into the reaction container;
and continuing to add the rest of the protective agent into the reaction vessel so as to cover the upper layer.
In one embodiment, the adding solid reaction materials and solid protectant to the reaction vessel comprises:
firstly, adding the reaction raw materials into the reaction container;
the protective agent is added to the reaction vessel so as to cover the upper layer.
In one embodiment, the reaction is carried out under an air atmosphere.
In one embodiment, the protectant is an inorganic salt.
In one embodiment, the reaction raw materials include a host raw material and a dopant, and at least one of the host raw materials.
The invention also provides a preparation method of the stress luminescent fluorescent powder, which uses the reaction method protected by the molten medium to treat the reaction raw materials of the stress luminescent fluorescent powder to prepare the stress luminescent fluorescent powder.
In one embodiment, the reaction feed contains ZnS.
In one embodiment, the reaction raw materials further contain one or more of MgO, caO, srO and BaO.
In one embodiment, the reaction raw material further contains an element for doping, wherein the element for doping is one or more of transition metal, rare earth metal and main group metal elements.
In one embodiment, the elements for doping are present in the form of one or more of halides, nitrates and sulfates.
In one embodiment, the material for doping in the reaction raw materials accounts for 0.01% -10% of the mole ratio of the main raw materials.
In one embodiment, the protecting agent is one or more of an alkali metal or alkaline earth metal halide, carbonate, sulfate, and phosphate.
In one embodiment, the heating rate of the reaction is 1-20 ℃/min when the temperature is raised to the reaction temperature of the reaction raw materials.
In one embodiment, the reaction temperature is 600 to 1100 ℃.
In one embodiment, the reaction time for the reaction by raising the temperature to the reaction temperature of the reaction raw material is 0.5 to 10 hours.
According to the reaction method, the solid protective agent is added into the reaction system, and the melting point of the protective agent is lower than the reaction temperature and the boiling point of the protective agent is not lower than the reaction temperature, so that after the temperature is raised to the reaction temperature, the solid protective agent is melted to become a melting medium, the density of the melting medium is smaller, the whole reaction system can be completely immersed to be isolated from the outside, and the whole reaction system is in the melting medium and is not affected even in reactions sensitive to atmosphere such as air. The reaction method is particularly suitable for air-sensitive reaction without preparing a special protective gas atmosphere, and in the specific reaction, only a solid protective agent meeting the conditions is added, complicated operations such as vacuumizing or filling protective gas are not needed, and the reaction conditions have low requirements on equipment, so that the production efficiency is improved, and the production cost is reduced.
Furthermore, for a reaction system in which the reaction raw material and the reaction product are both solid phases, a protective agent is introduced into the reaction system to form a molten medium at the reaction temperature, so that the reaction system is completely immersed in the molten medium formed by the protective agent, the reaction raw material and the reaction product can be relatively uniformly dispersed in the molten medium, and the solid of the reaction raw material and the solid of the reaction product are not easy to agglomerate and adhere, thereby being beneficial to obtaining the reaction product with uniform shape and particle size.
Drawings
FIG. 1 is an X-ray diffraction analysis (XRD) of a partially stressed lumiphor synthesized by the method of the present invention, wherein Theta (Degre) is the diffraction angle (°).
Fig. 2 (a) and (b) are Scanning Electron Microscope (SEM) photographs of the stress luminescent phosphors synthesized in example 1 and comparative example 1, respectively.
In fig. 3, (a), (b), (c), (d), (e) and (f) are stress luminescence spectra of the synthesized stress luminescence phosphors of examples 1, 4 to 6, 11 and 8 in this order, wherein the abscissa Wavelength is the Wavelength, the ordinate ML Intensity is the fluorescence Intensity of the stress luminescence, and counts is the number of photons received at the time of fluorescence spectrum measurement.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The invention provides a reaction method for protecting a molten medium, which comprises the following steps:
step S1: adding solid reaction raw materials and solid protective agents into a reaction container, wherein the protective agents do not participate in the reaction, and the addition amount is enough to completely submerge a reaction system in a molten state;
step S2: heating to the reaction temperature of the reaction raw material to perform a reaction, wherein the boiling point of the reaction raw material and the boiling point of the reaction product are not lower than the reaction temperature, the melting point of the protective agent is lower than the reaction temperature and the boiling point is not lower than the reaction temperature, and the density of the protective agent in a molten state is lower than that of the reaction raw material and the reaction product in a solid state or a molten state;
step S3: the reaction product was collected after the reaction.
In a specific example, there are a plurality of reaction materials, and solid phase contact reaction is performed between the plurality of reaction materials. It will be appreciated that in other examples, the reaction feed may be melted to a liquid state at the reaction temperature, however, the density of the liquid reaction feed is greater than the density of the protecting agent in the molten state and thus will be below the protecting agent in the molten state in the reaction vessel.
In one specific example, adding solid reaction raw materials and solid protecting agents to a reaction vessel comprises:
mixing the reaction raw materials and part of the protective agent, and adding the mixture into a reaction container;
the remaining protecting agent is continuously added into the reaction vessel so as to cover the upper layer.
Alternatively, adding solid reaction materials and solid protectants to the reaction vessel includes:
firstly, adding reaction raw materials into a reaction container;
a protective agent is added to the reaction vessel to cover the upper layer.
The mode of adding the protective agent can depend on the types and the amounts of the reaction raw materials, for example, when only a single reaction raw material is in a solid state at the reaction temperature, the reaction raw material and part of the protective agent are mixed and added, and then the rest of the protective agent is added, so that a product with relatively small size and uniform particles is obtained; when more than one reaction raw material is in solid state at the reaction temperature, the reaction raw material is added into the reaction container, and then the protective agent is added into the reaction container, so that the completeness of the solid-phase reaction is improved. According to the reaction method, the solid protective agent is added into the reaction system, after the temperature is raised to the reaction temperature, the solid protective agent is melted to become a molten medium, and the whole reaction system is completely immersed to be isolated from the outside, so that the whole reaction system is in the isolated protection of the molten medium, and no special protective gas atmosphere is needed to be prepared. In one specific example, the reaction is carried out under an air atmosphere.
Further, in one embodiment, the protectant is an inorganic salt.
Still further, the reaction raw materials include a host raw material and a dopant, at least one of the host raw materials. Preferably, the constituent element of the protective agent is the same as at least one element among other elements in the dopant other than the element for doping.
The invention also provides a preparation method of the stress luminescent fluorescent powder, which uses the reaction method protected by the molten medium to treat the reaction raw materials of the stress luminescent fluorescent powder to prepare the stress luminescent fluorescent powder.
For stress-emitting phosphors, in some examples, the reaction raw material contains ZnS. Optionally, the reaction raw materials further contain one or more of MgO, caO, srO and BaO. Accordingly, the synthesis target is ZnS, caZnOS, srZnOS, baZnOS or SrZn 2 S 2 O, etc. and different proportions of the two-phase heterojunction stressed luminescent material ZnS-MZnOS (m= Mg, ca, sr, ba).
Optionally, the reaction raw material further contains an element for doping, and the element for doping may be one or more of transition metal (Mn, cu, ag, etc.), rare earth metal (Pr, nd, sm, eu, tb, dy, ho, er or Yb, etc.), and main group metal element (Sn, pb, sb, bi, etc.). In some specific examples, the elements used for doping are present in one or more of halides, nitrates, and sulfates.
Further, for the stress luminescent phosphor, the material for doping in the reaction raw material may be 0.01% to 10% by mole, for example, 0.1% to 10%, 1% to 5% or 2% to 4% by mole, and for example, 0.05%, 1%, 2%, 3%, 4%, 5%, 6% and 8% by mole based on the main raw material.
The protecting agent is one or more of halide, carbonate, sulfate and phosphate of alkali metal or alkaline earth metal. The protecting agent is generally selected from the group consisting of halides (F, cl, br), carbonates, sulphates, phosphates of alkali metals (Li, na, K, cs) and alkaline earth metals (Mg, ca, sr, ba).
The stress luminescence color of the material can be regulated and controlled in a large range by utilizing the combination of different doping matrixes and doping agents so as to meet the actual application requirements; besides affecting the melting temperature of the system, the protectant component can introduce different defects into the system, so as to regulate and control the material performance, and also play a role in regulating and controlling the morphology and size of the final product particles. Referring to fig. 1, the stress luminescent phosphor synthesized by the method of the present invention includes ZnS, caZnOS, and two-phase heterojunction products thereof, wherein ZnS can control phase transition between sphalerite (s-ZnS) and wurtzite (w-ZnS) by adjusting reaction temperature.
For the stress luminescent phosphor, the temperature rising rate can be 1-20 ℃ per minute during temperature rising, for example, can be 2-18 ℃ per minute, 5-15 ℃ per minute or 8-12 ℃ per minute, and can be 1 ℃ per minute, 2 ℃ per minute, 3 ℃ per minute, 4 ℃ per minute, 6 ℃ per minute, 7 ℃ per minute, 9 ℃ per minute, 10 ℃ per minute, 11 ℃ per minute, 13 ℃ per minute, 14 ℃ per minute, 16 ℃ per minute, 17 ℃ per minute or 19 ℃ per minute. The reaction temperature is 600 to 1200 ℃, for example, 650 to 750 ℃, 850 to 900 ℃, 900 to 1000 ℃ or 1000 to 1200 ℃, and for example, 700 ℃, 855 ℃, 890 ℃, 1050 ℃, 1100 ℃, 1150 ℃ or 1190 ℃. The reaction time for the reaction at the temperature raised to the reaction temperature of the reaction raw material is 0.5 to 10 hours, and may be, for example, 0.5 to 8 hours, 2 to 8 hours or 3 to 6 hours, and may be, for example, 1 hour, 2.5 hours, 4 hours, 5 hours, 7 hours or 9 hours. Specifically, if the oxidation reaction temperature of the reaction raw material is lower than the melting point of the protective agent, a higher temperature rising rate is preferable. The reaction temperature and the reaction time can influence the phase and the shape and the size of the final product within a certain range.
Further, for the stress luminescent fluorescent powder, after the reaction is finished, the stress luminescent fluorescent powder can be collected by cooling, simply washing with clear water and drying.
According to the reaction method, the solid protective agent is added into the reaction system, and the melting point of the protective agent is lower than the reaction temperature and the boiling point of the protective agent is not lower than the reaction temperature, so that after the temperature is raised to the reaction temperature, the solid protective agent becomes a molten medium, the density of the molten medium is smaller, the whole reaction system can be completely immersed, and therefore, the whole reaction system is in the molten medium, and even the reaction sensitive to atmosphere such as air is not affected. The reaction method does not need special protective gas atmosphere, is particularly suitable for air-sensitive reaction, does not need complicated operations such as vacuumizing or filling protective gas in the specific reaction, has low equipment requirements, and is beneficial to improving the production efficiency and reducing the production cost.
The reaction method for protecting a molten medium according to the present invention will be described in further detail with reference to specific examples. The following examples are mainly directed to the preparation of stress luminescent phosphors, and it is understood that in other embodiments, the reaction method of the present invention for protecting a molten medium is not limited to stress luminescent phosphors, but may be other high temperature solid phase or liquid phase reactions, particularly reactions that are relatively sensitive to air and require a protective gas atmosphere such as nitrogen or inert gas.
In the following specific examples, the nominal composition means a composition of a compound calculated from the ratio of the raw materials to be charged, and in actual cases, the actual composition of the reaction product is slightly lower than the nominal composition because the reaction cannot proceed by 100%.
Example 1
ZnS:2% Mn phosphor.
Firstly, accurately weighing 10g of ZnS raw material, 10g of NaCl and 0.406g of MnCl 2 ·4H 2 O (molar ratio to ZnS: 2%) was ground for 10min and then charged into a corundum crucible. Then weighing 20g of NaCl salt again, grinding for 10min, loading into the same corundum crucible, and putting into a box-type reaction furnace. Heating to 1020 ℃ at the heating rate of 10 ℃/min, and naturally cooling to room temperature after reacting for 2 hours.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt by using clear water, washing for a plurality of times, and drying to obtain the final product of which the nominal composition is ZnS and 2% Mn.
Referring to FIG. 3 (a), the ZnS:2% Mn phosphor obtained in this example exhibited a broad-peak emission of orange light.
Example 2
ZnS:3% Mn phosphor.
Firstly, accurately weighing 10g ZnS raw material and 10g CaCl 2 0.61g MnCl 2 ·4H 2 O (molar ratio to ZnS: 2%) was ground for 10min and then charged into a corundum crucible. Subsequently, 20g CaCl was weighed again 2 Grinding salt for 10min, loading into the same corundum crucible, and placing into a box-type reaction furnace. Heating to 950 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt with clear water, washing with water for several times, and drying to obtain the final product with the nominal composition ZnS and 3% Mn.
Example 3
ZnS 0.05% Cu fluorescent powder.
Firstly, accurately weighing 10g of ZnS raw material, 10g of NaCl and 0.0087g of CuCl 2 ·2H 2 O (molar ratio to ZnS 0.05%) was ground for 10min and then charged into a corundum crucible. Then weighing 20g of NaCl salt again, grinding for 10min, loading into the same corundum crucible, and putting into a box-type reaction furnace. Heating to 1000 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt by using clear water, washing for a plurality of times, and drying to obtain the final product with the nominal composition ZnS of 0.05% Cu.
Example 4
CaZnOS 2% Mn fluorescent powder.
5g ZnS,2.877g CaO (stoichiometric ratio 1:1) and 0.203g MnCl were first accurately weighed 2 ·4H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Then weighing 20g of NaCl, grinding, loading into the same corundum crucible, and then placing into a box-type reaction furnace. Heating to 1000 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt by using clear water, washing for a plurality of times, and drying to obtain the final product with the nominal composition of CaZnOS and 2% Mn.
Referring to FIG. 3 (b), the CaZnOS:2% Mn phosphor obtained in this example exhibits a broad peak emission of red light.
Example 5
CaZnOS 1% Pb fluorescent powder.
5g ZnS,2.877g CaO (stoichiometric ratio 1:1) and 0.143g PbCl were first accurately weighed 2 Grinding for 10minLoading into corundum crucible and compacting. Subsequently, 20g CaCl was weighed out 2 Grinding, loading into a corundum crucible, and placing into a box-type reaction furnace. Heating to 1000 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt by using clear water, washing for a plurality of times, and drying to obtain a final product with the nominal composition of CaZnOS and 1% Pb.
Referring to FIG. 3 (c), the CaZnOS 1% Pb phosphor obtained in this example exhibited a broad peak emission of blue-violet light.
Example 6
CaZnOS 1% Eu fluorescent powder.
5g ZnS,2.877g CaO (stoichiometric ratio 1:1) and 0.188g EuCl were first accurately weighed 3 ·6H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Subsequently, 20g CaCl was weighed out 2 Grinding, loading into a corundum crucible, and placing into a box-type reaction furnace. Heating to 1000 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt by using clear water, washing for a plurality of times, and drying to obtain the final product with the nominal composition of CaZnOS and 1% Eu.
Referring to FIG. 3 (d), the CaZnOS:1% Eu phosphor obtained in this example exhibits linear red light emission.
Example 7
ZnS-CaZnOS, 2% Mn fluorescent powder.
5g ZnS,1.438g CaO (molar ratio 2:1) and 0.203g MnCl were first accurately weighed 2 ·4H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Then 6.9g NaCl and 13.1g CaCl were weighed out 2 Grinding, loading into a corundum crucible, and placing into a box-type reaction furnace. Heating to 1000 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt with clear water, washing with water for a plurality of times, and drying to obtain the ZnS-CaZnOS:2%Mn heterojunction fluorescent powder final product.
Example 8
3ZnS-2CaZnOS, 0.2% Mn,1% Pr fluorescent powder.
5g ZnS,1.151g CaO (molar ratio 5:2) and 0.0041g MnCl were first accurately weighed 2 ·4H 2 O and 0.0365g0.192g PrCl 3 ·6H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Then weighing 20g of NaCl, grinding, loading into the same corundum crucible, and then placing into a box-type reaction furnace. Heating to 1000 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt with clear water, washing with water for several times, and drying to obtain the 3ZnS-2CaZnOS, 0.5% Mn and 1% Pr heterojunction fluorescent powder final product.
Referring to FIG. 3 (f), the 3ZnS-2CaZnOS, 0.2% Mn,1% Pr phosphor obtained in this example exhibited a linear spectrum.
Example 9
SrZnOS 2% Mn fluorescent powder.
First, 5g ZnS,4.290SrO (stoichiometric ratio 1:1), and 0.203g MnCl were accurately weighed out 2 ·4H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Then weighing 20g of NaCl, grinding, loading into the same corundum crucible, and then placing into a box-type reaction furnace. Heating to 900 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt with clear water, washing with water for several times, and drying to obtain the final product with the nominal composition SrZnOS and 2% Mn.
Example 10
BaZnOS 2% Mn fluorescent powder.
First, 5g ZnS,7.866BaO (stoichiometric ratio 1:1), and 0.203g MnCl were accurately weighed out 2 ·4H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Then weighing 20g of NaCl, grinding, loading into the same corundum crucible, and then placing into a box-type reaction furnace. Heating to 900 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. And (3) dissolving excessive salt by using clear water, washing for a plurality of times, and drying to obtain the final product with the nominal composition of BaZnOS and 2 percent Mn.
Example 11
SrZn 2 S 2 O, 4% Mn fluorescent powder.
First, 5g ZnS,2.145SrO (stoichiometric ratio 2:1), and 0.406g MnCl were accurately weighed out 2 ·4H 2 O, grinding for 10min, loading into a corundum crucible and compacting. Then weighing 20g of NaCl, grinding, loading into the same corundum crucible, and then placing into a box-type reaction furnace. Heating to 900 ℃ at a heating rate of 10 ℃/min, reacting for 4 hours, and naturally cooling to room temperature.
The bulk salt crystals containing the final product are removed and the upper salt cake is removed, leaving only the salt cake with the product in layers. Dissolving excessive salt with clear water, washing with water for several times, and oven drying to obtain SrZn 2 S 2 O4% Mn final product.
Referring to FIG. 3 (e), srZn obtained in this example 2 S 2 O4% Mn phosphor exhibits a broad peak emission of orange light.
Comparative example 1
ZnS is synthesized by a high-temperature solid-phase method of 2% Mn fluorescent powder.
Firstly, accurately weighing 10g ZnS and 0.238g MnCO 3 Adding 20mL of alcohol, grinding until the alcohol is completely volatilized, repeating the steps for 3 times to ensure that the alcohol is fully and uniformly mixed, putting the mixture into a baking oven for baking at 80 ℃ for 1h, putting the raw materials into a corundum crucible, compacting the corundum crucible, and then putting the corundum crucible into a tubular atmosphere protection reaction furnace. After vacuum pumping, ar is introduced to the chamber pressure, and the air flow is maintained at 40cc/min at 10 ℃/mThe temperature rising rate of in is raised to 1100 ℃, and the reaction is carried out for 4 hours and then the reaction product is naturally cooled to room temperature.
Taking out the synthesized ZnS 2% Mn material in a sintered block shape, mechanically grinding, and sieving with a 150-mesh sieve to obtain the final product with the nominal composition ZnS 2% Mn.
As can be seen from comparison of fig. 2, the stress luminescent phosphor prepared by the method of example 1 has smooth particle surface, uniform shape and uniform particle size; whereas the stress luminescent phosphor particles prepared in comparative example 1 by the conventional high temperature solid phase method have rough surfaces and uncontrollable shape and particle diameters. Therefore, the stress luminescent fluorescent powder product obtained by the reaction method protected by the molten medium has regular powder shape, good uniformity and high performance stability. Meanwhile, the synthesis reaction scale is easy to expand by using the method, and the method is suitable for mass production.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The preparation method of the stress luminescent fluorescent powder is characterized by comprising the following steps:
adding solid reaction raw materials and solid protective agents into a reaction container, wherein the protective agents do not participate in the reaction and the addition amount is enough to completely submerge a reaction system in a molten state;
heating to the reaction temperature of the reaction raw materials for reaction, wherein the boiling point of the reaction raw materials and the boiling point of a reaction product are not lower than the reaction temperature, the melting point of the protective agent is lower than the reaction temperature and the boiling point of the protective agent is not lower than the reaction temperature, and the density of the protective agent in a molten state is lower than that of the reaction raw materials and the reaction product in a solid state or a molten state;
collecting the reaction product after the reaction;
the mode of adding the solid main raw materials and the solid protective agent into the reaction vessel depends on the types and the amounts of the reaction raw materials, and comprises the following steps:
when only a single main raw material is in a solid state at the reaction temperature, firstly mixing the reaction raw material with part of the protective agent and adding the mixture into the reaction container;
continuing to add the rest of the protective agent into the reaction container to cover the upper layer;
when more than one main raw material is in solid state at the reaction temperature, the reaction raw materials are firstly added into the reaction container,
adding the protective agent into the reaction vessel to cover the upper layer;
the reaction raw materials are various;
the reaction is carried out under an air atmosphere;
the protective agent is an inorganic salt;
the reaction raw material contains ZnS.
2. The method of claim 1, wherein the reaction materials further comprise one or more of MgO, caO, srO and BaO.
3. The method of claim 1, wherein the reaction raw materials further contain an element for doping, and the element for doping is one or more of a transition metal, a rare earth metal, and a main group metal element.
4. The method of claim 3, wherein the doping element is one or more of a halide, a nitrate, and a sulfate.
5. The method for preparing stress luminescent phosphor according to claim 4, wherein the material for doping in the reaction raw material is 0.01% -10% of the main raw material by mole.
6. The method of claim 4, wherein the protecting agent is one or more of an alkali metal or alkaline earth metal halide, carbonate, sulfate, and phosphate.
7. The method for producing a stress-luminescent phosphor according to any one of claims 1 to 2 and 4 to 5, wherein the temperature rise rate of the reaction performed by raising the temperature to the reaction temperature of the reaction raw material is 1 to 20 ℃/min.
8. The method for producing a stress luminescent phosphor according to any one of claims 1 to 2 and 4 to 5, wherein the reaction temperature is 600 to 1100 ℃.
9. The method for producing a stress-luminescent phosphor according to any one of claims 1 to 2 and 4 to 5, wherein the reaction time for the reaction by heating to the reaction temperature of the reaction raw material is 0.5 to 10 hours.
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