CN109912224B - Fluorapatite nano glass ceramic material for optical temperature measurement and preparation method thereof - Google Patents
Fluorapatite nano glass ceramic material for optical temperature measurement and preparation method thereof Download PDFInfo
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- CN109912224B CN109912224B CN201910076707.3A CN201910076707A CN109912224B CN 109912224 B CN109912224 B CN 109912224B CN 201910076707 A CN201910076707 A CN 201910076707A CN 109912224 B CN109912224 B CN 109912224B
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- 229910052587 fluorapatite Inorganic materials 0.000 title claims abstract description 16
- 239000006112 glass ceramic composition Substances 0.000 title claims abstract description 13
- 238000009529 body temperature measurement Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000003287 optical effect Effects 0.000 title claims abstract description 7
- 229940077441 fluorapatite Drugs 0.000 title abstract description 11
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 title abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 31
- 239000011521 glass Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000000075 oxide glass Substances 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000137 annealing Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 239000002159 nanocrystal Substances 0.000 claims abstract description 4
- 239000011812 mixed powder Substances 0.000 claims abstract 2
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910004261 CaF 2 Inorganic materials 0.000 claims 2
- 239000000156 glass melt Substances 0.000 claims 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract description 9
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006060 molten glass Substances 0.000 abstract description 8
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000002241 glass-ceramic Substances 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Abstract
The invention discloses a fluorapatite nano glass ceramic material for optical temperature measurement and a preparation method thereof. The nano glass ceramic material comprises an oxide glass matrix, wherein the oxide glass matrix contains doped Yb3+And Er3+Ca5(PO4)3F nanocrystals; the composition of the oxide glass matrix at least contains 15-25 mol% of CaF225 to 35 mol% of ZnO, 6 to 12 mol% of P2O5And 34 to 44 mol% of B2O3And Yb in an amount of 0.5 to 1.5 mol% based on the total amount of the above oxides2O3And 0.04 to 0.08 mol% of Er2O3. The preparation method of the nano glass ceramic material comprises the following steps: according to the composition proportion of the oxide glass matrix, the prepared mixed powder is ground, uniformly mixed and then placed in a crucible, heated to 1100-1250 ℃, and kept warm for 1-2 hours; then quickly pouring the obtained molten glass into a preheated copper mold at the temperature of 420-450 ℃ for molding and annealing for 10 hours to obtain matrix glass; and keeping the annealed substrate glass at 660-680 ℃ for 2-6 hours to crystallize.
Description
Technical Field
The invention belongs to the field of solid conversion luminescent materials, and particularly relates to a fluorapatite nano glass ceramic material for optical temperature measurement and a preparation method thereof.
Background
Biological research often involves micro-and nano-scale temperature measurement and manipulation, and in many special environments, temperature sensing also requires non-contact and fast-responding temperature detectors. Most of the traditional temperature detectors adopt a contact type, the condition that a measured object is larger than 10 mu m can be met, the detection speed is influenced by heat conduction, and the application environment is limited. The key point of the non-contact temperature sensor based on the optical temperature sensing characteristic is the fluorescent material used as a temperature probe. The fluorescent material must have more than two fluorescence emission peaks, and the intensities of different emission peaks are different with respect to temperatureThe reaction of (1); in addition, certain wavelength intervals are required among different emission peaks so as to discriminate signals. For example, Chinese patent CN106634988A discloses a nanocrystalline material for a fluorescence temperature probe, which respectively shows Er under the excitation of 980nm laser3+Ion and Tm3+Single band luminescence of ions at 650nm and 800nm, Er increasing gradually from 60 deg.C to 200 deg.C3+The fluorescence intensity of the ion at 650nm is constant, whereas Tm is3+The fluorescence intensity of the ion at 800nm is gradually increased, and the sensitivity is 1.73 percent K-1And the temperature measuring area is 60-200 ℃. The temperature measurement sensitivity of the technology reaches practical requirements, and the temperature measurement area range is not wide enough, so that the practical application is limited to a certain extent.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the fluorapatite nano glass ceramic material which can be used for a fluorescent temperature probe and has a wide temperature measuring area and enough temperature reaction sensitivity, wherein the temperature measuring area of the material reaches 30-525 ℃, and the sensitivity also reaches 1-1.35 percent K-1(ii) a Meanwhile, the invention also provides a preparation method of the material.
The oxide glass matrix of the glass ceramic material contains uniformly distributed Yb-doped glass3+And Er3+Ca5(PO4)3F (fluorapatite) nanocrystals. The composition of the oxide glass matrix at least contains 15-25 mol% of CaF225 to 35 mol% of ZnO, 6 to 12 mol% of P2O5And 34 to 44 mol% of B2O3And Yb in an amount of 0.5 to 1.5 mol% based on the total amount of the above oxides2O3And 0.04 to 0.08 mol% of Er2O3. The doping proportion is the preferred proportion given by the invention, the effect of the invention is obtained and is not limited to the proportion range, and the person skilled in the art can make appropriate adjustment according to the actual situation.
The preparation method of the glass ceramic material comprises the following steps: grinding and uniformly mixing all the powder raw materials, placing the powder raw materials in a crucible, heating to 1100-1250 ℃, and preserving heat for 1-2 hours; then quickly pouring the obtained molten glass into a preheated copper mold at the temperature of 420-450 ℃ for molding and annealing to obtain matrix glass; and keeping the annealed substrate glass at 660-680 ℃ for 2-6 hours to crystallize.
Drawings
FIG. 1 is a graph of the transmission spectrum of a sample of an embodiment of the present invention. FIG. 2 is an X-ray diffraction pattern of a sample of an embodiment of the present invention. FIG. 3 is a transmission electron micrograph of a sample according to an embodiment of the present invention. FIG. 4 is a graph of temperature dependent emission spectra of samples of examples of the present invention. FIG. 5 is a graph of intensity ratio versus temperature for samples of examples of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1: mixing CaF2、ZnO、NH4H2PO4、H3BO3、Yb2O3、Er2O3Powder of 25CaF by mol percent2：25ZnO：10P2O5：40B2O3Addition of 1Yb2O3、0.04Er2O3The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace insulated at 420 ℃ for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass (represented by PG); the obtained matrix glass was put into a heat-treatment resistance furnace and kept at 660 ℃ for 4 hours to obtain a nano glass ceramic (represented by GC 660).
The transmission spectrum shows that the glass-ceramic has high transparency (FIG. 1); x-ray diffraction pattern showed Ca precipitation in oxide glass matrix5(PO4)3Crystalline phase F (fig. 2); transmission electron microscope observation proves that the glass ceramic contains a large amount of Ca with the average size of about 5nm5(PO4)3The F crystals are uniformly distributed in the matrix (FIG. 3); the fluorescence spectrometer measures the temperature dependence under the excitation condition of 980nmPhotoluminescence emission spectrum (FIG. 4), detectable from2H11/2Radiative transition emission of energy levels and4S3/2radiative transition emission of energy levels. As the temperature is raised, the temperature of the solution is raised,2H11/2the radiative transition emission intensity of the energy level increases rapidly, and4S3/2the radiation transition emission intensity of the energy level only changes slightly, the fluorescence intensity ratio of the two is taken as a temperature measurement parameter (figure 5), and the sensitivity of the obtained nano glass ceramic material is 1.35 percent K within the temperature range of 298K-798K (25-525 ℃)-1。
Example 2: mixing CaF2、ZnO、NH4H2PO4、H3BO3、Yb2O3、Er2O3Powder of 25CaF by mol percent2：25ZnO：10P2O5：40B2O3Addition of 1Yb2O3、0.08Er2O3The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 2 hours at 660 ℃, obtaining fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.28 percent K-1。
Example 3: mixing CaF2、ZnO、NH4H2PO4、H3BO3、Yb2O3、Er2O3Powder of 25CaF by mol percent2：25ZnO：10P2O5：40B2O3Addition of 1Yb2O3、0.06Er2O3The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, ground for more than 15 minutes to be uniformly mixed, then the mixture is placed in a crucible, heated to 1150 ℃ in a high-temperature resistance furnace and then kept warm for 1 hour to be filledMelting; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; putting the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 4 hours at 670 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.32 percent K-1。
Example 4: mixing CaF2、ZnO、NH4H2PO4、H3BO3、Yb2O3、Er2O3Powder of 25CaF by mol percent2：25ZnO：10P2O5：40B2O3Addition of 1.5Yb2O3、0.02Er2O3The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 4 hours at 660 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.17 percent K-1。
Example 5: mixing CaF2、ZnO、NH4H2PO4、H3BO3、Yb2O3、Er2O3Powder of 25CaF by mol percent2：25ZnO：10P2O5：40B2O3Addition of 0.5Yb2O3、0.04Er2O3The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, the molten glass is quickly poured into a copper mold preheated at the temperature of 420 ℃ for forming, and the formed glass is put into a muffle furnace with the temperature of 420 ℃ for annealingCooling the glass along with the furnace after 10 hours to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 2 hours at 660 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.09 percent K-1。
Example 6: mixing CaF2、ZnO、NH4H2PO4、H3BO3、Yb2O3、Er2O3Powder of 25CaF by mol percent2：25ZnO：10P2O5：40B2O3Addition of 1Yb2O3、0.05Er2O3The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 2 hours at 660 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.31 percent K-1。
In each of the above examples, 25CaF2：25ZnO：10P2O5：40B2O3The ratio (in mol%) is not the only limiting value, and those skilled in the art know that the above components are the essential components constituting the matrix glass, and that the ratio of the components may be varied within the given range without affecting the final effect of the present invention. The preferred proportions of the basic components of the matrix glass given in the present invention are: 15-25 mol% of CaF225 to 35 mol% of ZnO, 6 to 12 mol% of P2O5And 34 to 44 mol% of B2O3。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251564A (en) * | 1997-04-03 | 2000-04-26 | 康宁股份有限公司 | Transparent apatite glass-ceramics |
| CN105198225A (en) * | 2015-10-13 | 2015-12-30 | 杭州电子科技大学 | Double active ion doped bicrystal glass ceramic fluorescence temperature probe materials and preparation method thereof |
| CN107129154A (en) * | 2017-07-02 | 2017-09-05 | 桂林电子科技大学 | Transparent glass ceramics material and preparation method for fluorescence temperature probe |
| CN108896201A (en) * | 2018-05-15 | 2018-11-27 | 中国科学院福建物质结构研究所 | A kind of high-resolution organism thermometry of high sensitivity |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1251564A (en) * | 1997-04-03 | 2000-04-26 | 康宁股份有限公司 | Transparent apatite glass-ceramics |
| CN105198225A (en) * | 2015-10-13 | 2015-12-30 | 杭州电子科技大学 | Double active ion doped bicrystal glass ceramic fluorescence temperature probe materials and preparation method thereof |
| CN107129154A (en) * | 2017-07-02 | 2017-09-05 | 桂林电子科技大学 | Transparent glass ceramics material and preparation method for fluorescence temperature probe |
| CN108896201A (en) * | 2018-05-15 | 2018-11-27 | 中国科学院福建物质结构研究所 | A kind of high-resolution organism thermometry of high sensitivity |
Non-Patent Citations (1)
| Title |
|---|
| Highly Efficient Near-Infrared Luminescence in Er3 + /Yb3 + Co-Doped Nano-FAP Glass Ceramics;ZHANG Jing-hui et al.;《Journal of Kunming University of Science and Technology ( Natural Science Edition)》;20120229;第37卷(第1期);25-29 * |
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