CN115678554B - Eu (+2, +3) coactivated fluorescent temperature measurement material and preparation and application thereof - Google Patents
Eu (+2, +3) coactivated fluorescent temperature measurement material and preparation and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 64
- 238000009529 body temperature measurement Methods 0.000 title abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910052693 Europium Inorganic materials 0.000 claims description 41
- 238000001354 calcination Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 238000004861 thermometry Methods 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
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- 238000002156 mixing Methods 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 229910001940 europium oxide Inorganic materials 0.000 claims description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 230000035945 sensitivity Effects 0.000 abstract description 34
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- 239000011159 matrix material Substances 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 description 9
- -1 rare earth ion Chemical class 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 5
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 4
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 150000001768 cations Chemical class 0.000 description 2
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
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- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of non-contact optical temperature measurement materials, and discloses a Eu (+2, +3) coactivated fluorescent temperature measurement material, and preparation and application thereof. The fluorescent temperature measuring material comprises Eu 2+ 、Eu 3+ Co-doped borophosphate. The fluorescent temperature measuring material of the invention is prepared by doping Eu into a borophosphate matrix 2+ /Eu 3+ Build Eu 2+ /Eu 3+ The corresponding standard curve between the characteristic emission peak intensity ratio (FIR) and the temperature accurately reflects the change of the environmental temperature, and has high sensitivity and high signal discrimination. Unique advantages in terms of non-contact, rapid response, high sensitivity, etc., facilitate working in harsh environments or detecting the temperature of rapidly moving objects. The method can effectively avoid a plurality of defects of the traditional contact type temperature measurement method.
Description
Technical Field
The invention belongs to the field of non-contact optical temperature measurement materials, and particularly relates to a Eu (+2, +3) coactivated fluorescent temperature measurement material, and preparation and application thereof.
Background
Europium element exists in normal trivalent form in nature to obtain Eu 2+ The preparation method of (2) is mainly reducing by using a reducing agent. Eu currently used 2+ Eu in doped phosphor 2+ The ion is mainly prepared by a high-temperature solid phase method under the conditions of reducing atmosphere, reducing powder and the like. Under these reducing agent conditions, eu 3+ Can be reduced well, but the complexity and severity of the preparation process cause them to have great limitations.
In recent years, a temperature measurement method based on fluorescence optical characteristics of a substance is becoming a research hotspot. In a certain temperature range of the water-soluble polymer,certain optical characteristics of the rare earth fluorescent powder, such as peak position, spectrum linewidth, fluorescence lifetime attenuation and the like, change regularly along with temperature change, and have monotonicity and repeatability, and the temperature can be calibrated by utilizing the change of the optical characteristics. In this respect, conventional research has focused on Ho 3+ And Er 3+ 、Nd 3+ The ratio of fluorescence intensities of the thermally coupled energy levels of (c) is used for temperature measurement. However, to satisfy the thermal coupling condition, the energy level of the thermal coupling must be between 200cm -1 ～2000cm -1 And the temperature measurement sensitivity is proportional to the energy level difference of the thermal coupling. Therefore, the temperature measurement sensitivity obtained by the technology cannot meet the requirement of high-precision measurement, and the simultaneous optimization and promotion of the temperature measurement sensitivity and the signal discrimination cannot be realized.
Therefore, there is a need to prepare an optical temperature measurement material with high sensitivity and high signal discrimination.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides a Eu (+2, +3) coactivated fluorescent temperature measuring material, and preparation and application thereof. The fluorescent temperature measuring material is doped with rare earth luminescent ions Eu with multivalent state in a borophosphate matrix 2+ 、Eu 3+ . By establishing Eu 2+ /Eu 3+ The corresponding standard curve between the characteristic emission peak intensity ratio (FIR) and the temperature accurately reflects the change of the environmental temperature, and has high sensitivity and high signal discrimination. Unique advantages in terms of non-contact, rapid response, high sensitivity, etc., facilitate working in harsh environments or detecting the temperature of rapidly moving objects. The method can effectively avoid various defects of the traditional contact type temperature measurement method, such as low resolution, long response time and the like.
The preparation method of the fluorescent temperature measurement material is a self-reduction method, and Eu can be obtained in air atmosphere 2+ Also based on the high temperature solid phase method, the reaction can be carried out in a device without airtight function since no special atmosphere is required. The method has simple treatment process, direct product obtaining, low cost, and good yieldLarge amount and no pollution.
Doped trivalent rare earth ion Eu 3+ Generally substituted divalent alkaline earth metal ions Ca 2+ But in order to maintain charge conservation, two trivalent rare earth ions Eu 3+ To replace three alkaline earth metal ions Ca 2+ Each such substitution brings about a divalent cation defect which, due to the absence of divalent cations, carries two units of negative charge which can serve as electron donors, which, under thermal excitation at a given temperature, migrate to the trivalent rare earth ions Eu 3+ Is trapped nearby so that trivalent rare earth ions Eu 3+ Valence-changing to divalent Eu 2+ 。
A first aspect of the present invention provides a Eu (+2, +3) co-activated fluorescent thermometry material.
Specifically, a Eu (+2, +3) coactivated fluorescent temperature measurement material comprises Eu 2+ 、Eu 3+ Co-doped borophosphate.
Preferably, the Eu 2+ 、Eu 3+ The molar fraction of the borophosphate is 0.1-1%; further preferably, the Eu 2+ 、Eu 3+ The molar fraction of the borophosphate is 0.1-0.5%.
Preferably, the chemical formula of the fluorescent temperature measuring material is CaBPO 5 :Eu 2+ /Eu 3+ . The CaBPO 5 Is hexagonal system.
Preferably, the Eu 2+ /Eu 3+ Occupying the CaBPO 5 The mole fraction of (2) is 0.1-1%; further preferably, the Eu 2+ /Eu 3+ Occupying the CaBPO 5 The mole fraction of (2) is 0.1-0.5%.
Preferably, under 280nm ultraviolet excitation, emission peaks at 402nm, 588nm, 612nm, 653nm and 694nm, respectively, are generated.
Preferably, the fluorescent thermometry material has two main emission peaks at 402nm and 612nm in the range of 303K-403K. Emission peak at 402nm is derived from Eu 2+ The ion 5d-4f energy level transition, the emission peak at 612nm is derived from Eu 3+ Ion(s) 5 D 0 - 7 F 2 Energy level transitions.
Preferably, the chemical formula of the fluorescent temperature measuring material is CaBPO 5 :0.1％Eu 2+ /Eu 3+ The standard curve between the characteristic emission peak intensity ratio FIR at 402nm and 612nm and the temperature T is expressed as: fir=9819.4 x exp (-T/34.39) +0.157.
Preferably, the chemical formula of the fluorescent temperature measuring material is CaBPO 5 :0.5％Eu 2+ /Eu 3+ The standard curve between the characteristic emission peak intensity ratio FIR at 402nm and 612nm and the temperature T is expressed as: fir=253523.9 x exp (-T/28.07) +0.178.
A second aspect of the invention provides a method for preparing a Eu (+2, +3) co-activated fluorescent temperature measurement material.
Specifically, the preparation method of the Eu (+2, +3) coactivated fluorescent temperature measurement material comprises the following steps:
grinding, mixing, presintering and then grinding and calcining metal salt, phosphate, boric acid and europium oxide to obtain the fluorescent temperature measuring material.
Preferably, the metal salt comprises an alkali metal salt or an alkaline earth metal salt, such as calcium carbonate.
Preferably, the phosphate comprises monoammonium phosphate, monopotassium phosphate or sodium phosphate monobasic.
Preferably, the molar ratio of the metal salt, phosphate, boric acid and europium oxide is 1: (0.8-1.2): (0.8-1.5): (0.0005-0.0025); preferably 1:1:1.25:0.0005 or 1:1:1.25:0.0025.
preferably, the pre-firing and calcining are performed under an air atmosphere.
Preferably, the presintering temperature is 350-480 ℃, and the presintering time is 1.8-2.5 hours; further preferably, the temperature of the pre-sintering is 350-450 ℃, and the time of the pre-sintering is 1.9-2 hours.
Preferably, the calcination temperature is 950-1100 ℃, and the calcination time is 2-6 hours; further preferably, the calcination temperature is 950-1050 ℃, and the calcination time is 3-6 hours. The fluorescent temperature measuring material is prepared by adopting a presintering and calcining method.
A third aspect of the present invention provides the use of Eu (+2, +3) co-activated fluorescent thermometry materials.
Specifically, the Eu (+2, +3) coactivated fluorescent temperature measurement material is applied to the field of temperature measurement.
Compared with the prior art, the invention has the following beneficial effects:
(1) The fluorescent temperature measuring material is prepared by doping Eu into a borophosphate matrix 2+ /Eu 3+ Build Eu 2+ /Eu 3+ The corresponding standard curve between the characteristic emission peak intensity ratio (FIR) and the temperature accurately reflects the change of the environmental temperature, and has high sensitivity and high signal discrimination. Unique advantages in terms of non-contact, rapid response, high sensitivity, etc., facilitate working in harsh environments or detecting the temperature of rapidly moving objects. The method can effectively avoid a plurality of defects of the traditional contact type temperature measurement method.
(2) The fluorescent temperature measuring material adopts a high-temperature solid phase method, is synthesized in air atmosphere, and is Eu 3+ Self-reduction of ions to Eu 2+ The ion does not need reducing atmosphere synthesis, the preparation process is safe and simple, the synthesis temperature is low, and the reaction condition is easy to control.
(3) The sample phase prepared by the method has high purity, is completely consistent with a standard card, has no miscellaneous items, and has good crystallinity.
(4) The fluorescent temperature measuring material prepared by the invention is nontoxic, pollution-free, stable in physical and chemical properties, and can not react with oxygen, carbon dioxide and water in the air when being exposed to the air for a long time.
(5) The fluorescent temperature measurement material prepared by the invention can be excited by ultraviolet or near ultraviolet, and the emission peak is positioned in a blue-violet light wave band with the dominant wavelength of 402nm and a red light wave band with the dominant wavelength of 612nm, so that the fluorescent temperature measurement material has good resolution.
(6) The fluorescent temperature measuring material prepared by the invention has good temperature sensitivity, high temperature measuring sensitivity, and the maximum value of absolute sensitivity Sa and relative sensitivity Sr are 0.1842K respectively -1 And 3.444％K -1 。
Drawings
FIG. 1 shows CaBPO produced in example 1 and example 2 of the present invention 5 :0.1％Eu 2+ /Eu 3+ 、CaBPO 5 :0.5％Eu 2+ /Eu 3+ An XRD pattern of (b);
FIG. 2 shows the CaBPO produced in example 1 and example 2 of the present invention 5 :xEu 2+ /Eu 3+ (x=0.1%, 0.5%) of the normal temperature emission spectrum;
FIG. 3 is a CaBPO prepared in example 1 of the present invention 5 :0.1％Eu 2+ /Eu 3+ Is a variable temperature spectrum of (2);
FIG. 4 shows a CaBPO prepared in example 1 of the present invention 5 :0.1％Eu 2+ /Eu 3+ The intensities of emission peaks at 402nm and 612 nm;
FIG. 5 is a CaBPO prepared in example 2 5 :0.5％Eu 2+ /Eu 3+ Is a variable temperature spectrum of (2);
FIG. 6 shows a CaBPO produced in example 2 of the present invention 5 :0.5％Eu 2+ /Eu 3+ The intensities of emission peaks at 402nm and 612 nm;
FIG. 7 shows CaBPO produced in example 1 and example 2 of the present invention 5 :0.1％Eu 2+ /Eu 3+ 、CaBPO 5 :0.5％Eu 2+ /Eu 3+ Fitting a fluorescent intensity ratio FIR to a temperature T;
FIG. 8 shows a CaBPO produced in example 1 of the present invention 5 :0.1％Eu 2+ /Eu 3+ Absolute sensitivity S of (2) a And relative sensitivity S r A curve;
FIG. 9 is a CaBPO produced in example 2 of the present invention 5 :0.5％Eu 2+ /Eu 3+ Absolute sensitivity S of (2) a And relative sensitivity S r A curve.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1: caBPO (CaBPO) 5 :0.1％Eu 2+ /Eu 3+ Preparation of fluorescent temperature measuring material
Eu (+2, +3) coactivated fluorescent temperature measuring material with chemical formula of CaBPO 5 :0.1％Eu 2+ /Eu 3+ .0.1% represents Eu 2+ 、Eu 3+ Occupy CaBPO 5 The mole fraction of (2) was 0.1%.
A method for preparing a Eu (+2, +3) coactivated fluorescent temperature measurement material, comprising the following steps:
4 mmole CaCO 3 、4mmolNH 4 H 2 PO 4 、4mmolH 3 BO 3 、0.002mmolEu 2 O 3 Grinding in agate mortar for 20 min, mixing, placing in corundum crucible, placing in muffle furnace (heating rate of 2 min/deg.C), presintering at 400deg.C for 2 hr, cooling to room temperature of 20deg.C, grinding, calcining at 1000deg.C for 4 hr, cooling to room temperature, taking out, grinding and dispersing to obtain fluorescent temperature measuring material (chemical formula of CaBPO) 5 :0.1％Eu 2+ /Eu 3+ )。
Example 2: caBPO (CaBPO) 5 :0.5％Eu 2+ /Eu 3+ Preparation of fluorescent temperature measuring material
Eu (+2, +3) coactivated fluorescent temperature measuring material with chemical formula of CaBPO 5 :0.1％Eu 2+ /Eu 3+ .0.1% represents Eu 2+ 、Eu 3+ Occupy CaBPO 5 The mole fraction of (2) was 0.1%.
A method for preparing a Eu (+2, +3) coactivated fluorescent temperature measurement material, comprising the following steps:
4 mmole CaCO 3 、4mmolNH 4 H 2 PO 4 、4mmolH 3 BO 3 、0.01mmolEu 2 O 3 Grinding in agate mortar for 20 min, mixing, placing into corundum crucible, placing into muffle furnace (heating rate of 2 min/deg.C), presintering at 450deg.C for 1.9 hr, cooling to room temperature of 20deg.C, and grindingGrinding, calcining at 1050 deg.C for 3 hr, cooling to room temperature, taking out, grinding and dispersing to obtain fluorescent temperature measuring material (chemical formula CaBPO) 5 :0.5％Eu 2+ /Eu 3+ )。
Product effect test
FIG. 1 shows CaBPO produced in example 1 and example 2 of the present invention 5 :0.1％Eu 2+ /Eu 3+ 、CaBPO 5 :0.5％Eu 2+ /Eu 3+ An XRD pattern of (b); as can be seen from FIG. 1 (the ordinate "Intensity" in FIG. 1 indicates Intensity, and the abscissa "2 Theta" indicates 2 Theta), the diffraction peaks of the fluorescent thermometry material prepared in examples 1-2 correspond to standard cards, and no impurity phase is generated.
FIG. 2 shows the CaBPO produced in example 1 and example 2 of the present invention 5 :xEu 2+ /Eu 3+ (x=0.1%, 0.5%) of the normal temperature emission spectrum; FIG. 2 (ordinate "Intensity" in FIG. 2 indicates Intensity, and abscissa "Wavelength" indicates Wavelength) shows CaBPO produced in example 1 and example 2 5 :xEu 2+ /Eu 3+ (x=0.1% and 0.5%) fluorescent temperature measuring material generates emission peaks respectively at 402nm, 588nm, 612nm, 653nm and 694nm under the excitation of 280nm ultraviolet light, wherein the emission peak at 402nm is derived from Eu 2+ Ions 5d-4f energy level transitions. Emission peaks at 588nm, 612nm, 653nm and 694nm are derived from Eu 3+ Ion(s) 5 D 0 - 7 F J (J=1, 2, 3, 4) energy level transitions, and further prove that Eu exists in the prepared fluorescent temperature measuring material simultaneously 2+ And Eu 3+ Ions.
FIG. 3 is a CaBPO prepared in example 1 of the present invention 5 :0.1％Eu 2+ /Eu 3+ Is a variable temperature spectrum of (2); from FIG. 3 (in FIG. 3, "Intensity" represents Intensity, "Wavelength" represents Wavelength, "Temperature" represents Temperature, λ ex =280 nm means that the fluorescent thermometry material is excited by ultraviolet light at 280 nm), the CaBPO prepared in example 1 5 :0.1％Eu 2+ /Eu 3+ The fluorescence temperature measuring material has two stronger main emission peaks at 402nm and 612nm in the range of 303K-403K, and a signal peak (I 402 And I 612 ，I 402 Represents the emission peak intensity at 402nm, I 612 The emission peak intensity at 612 nm) wavelength interval is 210nm, has excellent signal discrimination, and effectively avoids the mutual interference of monitoring signals.
FIG. 4 shows a CaBPO prepared in example 1 of the present invention 5 :0.1％Eu 2+ /Eu 3+ The intensities of emission peaks at 402nm and 612 nm; in FIG. 4 (a) is CaBPO 5 :0.1％Eu 2+ /Eu 3+ The fluorescence temperature measuring material is positioned at 402nm and has the emission peak intensity (the temperature range is 303K-403K), (b) is CaBPO 5 :0.1％Eu 2+ /Eu 3+ The fluorescence temperature measuring material is positioned at 612nm and has emission peak intensity (the temperature range is 303K-403K). As shown in FIG. 4 (a), the temperature increases from 303K to 403K, at 402nm (Eu 2+ Emission peak intensity I at 5d-4 f) 402 (taking the integral intensity of 360nm-450 nm) is obviously reduced; and as shown in FIG. 4 (b), 612nm (Eu 3+ : 5 D 0 - 7 F 2 ) Intensity of the emission peak I 612 (taking the integrated intensity of 603nm-630 nm), eu can be utilized 2+ And Eu 3+ Temperature monitoring was performed with different fluorescent thermal response characteristics.
FIG. 5 is a CaBPO prepared in example 2 5 :0.5％Eu 2+ /Eu 3+ Is a variable temperature spectrum of (2); from FIG. 5 (in FIG. 5, "Intensity" represents Intensity, "Wavelength" represents Wavelength, "Temperature" represents Temperature, λ ex =280 nm means that the fluorescent thermometry material is excited by ultraviolet light at 280 nm), the CaBPO prepared in example 2 5 :0.5％Eu 2+ /Eu 3+ The fluorescence temperature measuring material has two stronger main emission peaks at 402nm and 612nm in the range of 303K-403K, and a signal peak (I 402 And I 612 ，I 402 Representing the signal peak intensity at 402nm, I 612 The signal peak intensity at 612 nm) wavelength interval is 210nm, has excellent signal discrimination, and effectively avoids the mutual interference of monitoring signals.
FIG. 6 shows a CaBPO produced in example 2 of the present invention 5 :0.5％Eu 2+ /Eu 3+ Is located at 402nm and 612nmIntensity of peak; FIG. 6 (a) is CaBPO 5 :0.5％Eu 2+ /Eu 3+ The fluorescence temperature measuring material is positioned at 402nm and has the emission peak intensity (the temperature range is 303K-403K), (b) is CaBPO 5 :0.5％Eu 2+ /Eu 3+ The fluorescence temperature measuring material is positioned at 612nm and has emission peak intensity (the temperature range is 303K-403K). As shown in FIG. 6 (a), the temperature increases from 303K to 403K, at 402nm (Eu 2+ Emission peak intensity I at 5d-4 f) 402 (taking the integral intensity of 360nm-450 nm) is obviously reduced; as shown in FIG. 6 (b), 612nm (Eu) 3+ : 5 D 0 - 7 F 2 ) Intensity of the emission peak I 612 (taking the integrated intensity of 603nm-630 nm), eu can be utilized 2+ And Eu 3+ Temperature monitoring was performed with different fluorescent thermal response characteristics.
FIG. 7 shows CaBPO produced in example 1 and example 2 of the present invention 5 :0.1％Eu 2+ /Eu 3+ 、CaBPO 5 :0.5％Eu 2+ /Eu 3+ Fitting a fluorescent intensity ratio FIR to a temperature T; FIG. 7 (ordinate FIR in FIG. 7 shows I) 402 /I 612 The abscissa "Temperature" represents Temperature, "Fitted Curve" represents Fitted Curve), where (a) is CaBPO 5 :0.1％Eu 2+ /Eu 3+ Fitting map of fluorescence intensity ratio FIR and temperature T of fluorescence temperature measuring material, (b) is CaBPO 5 :0.5％Eu 2+ /Eu 3+ Fitting map of fluorescence intensity ratio FIR and temperature T of fluorescence temperature measuring material; as can be seen from FIG. 7, the fluorescence intensity is better than the FIR and the temperature T, R 2 The value was 0.999.
FIG. 8 shows a CaBPO produced in example 1 of the present invention 5 :0.1％Eu 2+ /Eu 3+ Absolute sensitivity S of (2) a And relative sensitivity S r A curve; FIG. 8 (Temperature in FIG. 8) is CaBPO 5 :0.1％Eu 2+ /Eu 3+ Absolute sensitivity S of fluorescent temperature measurement material a And relative sensitivity S r The absolute sensitivity of the fluorescent temperature measuring material obtained by calculation is S a :0.043K -1 And a relative sensitivity of S r :2.262％K -1 (calculation of absolute sensitivity: FIR-Male)The absolute value of the equation derived from the temperature T. Calculation of relative sensitivity: the absolute sensitivity divided by the value of FIR multiplied by the absolute value of 100).
FIG. 9 is a CaBPO produced in example 2 of the present invention 5 :0.5％Eu 2+ /Eu 3+ Absolute sensitivity S of (2) a And relative sensitivity S r A curve. FIG. 9 (Temperature in FIG. 9) is CaBPO 5 :0.5％Eu 2+ /Eu 3+ Absolute sensitivity S of fluorescent temperature measurement material a And relative sensitivity S r The absolute sensitivity of the curve obtained by calculation is S a :0.184K -1 And a relative sensitivity of S r :3.444％K -1 。
Fig. 8-9 show that the fluorescent temperature measuring material of the invention has ultrahigh temperature measuring sensitivity and can be applied to the field of non-contact optical temperature measurement.
The fluorescent temperature measuring material of the invention irradiates with 280nm ultraviolet light, measures CaBPO with FLS980 fluorescent spectrometer 5 :x Eu 2+ /Eu 3+ Variable temperature emission spectrum (x=0.1%, 0.5%) to calculate I 402 /I 612 And (3) establishing a functional relation between the emission peak intensity and the temperature to calibrate the temperature of the monitored object.
Claims (7)
1. The application of the fluorescent temperature measuring material in the temperature measuring field is characterized in that the fluorescent temperature measuring material comprises Eu 2+ 、Eu 3+ Co-doped borophosphate of the formula CaBPO 5 The method comprises the steps of carrying out a first treatment on the surface of the The Eu 2+ 、Eu 3+ The molar fraction of the borophosphate is 0.1-1%.
2. The use according to claim 1, wherein the fluorescent thermometry material has the chemical formula CaBPO 5 :Eu 2 + /Eu 3+ 。
3. The use according to claim 1, wherein the fluorescent thermometry material generates emission peaks at 402nm, 588nm, 612nm, 653nm and 694nm, respectively, under ultraviolet excitation at 280 nm.
4. The use according to claim 1, wherein the fluorescent thermometry material has the chemical formula CaBPO 5 :0.1%Eu 2+ /Eu 3+ The standard curve between the characteristic emission peak intensity ratio FIR at 402nm and 612nm and the temperature T is expressed as: fir=9819.4 x exp (-T/34.39) +0.157.
5. The use according to claim 1, wherein the fluorescent thermometry material has the chemical formula CaBPO 5 :0.5%Eu 2+ /Eu 3+ The standard curve between the characteristic emission peak intensity ratio FIR at 402nm and 612nm and the temperature T is expressed as: fir=253523.9 x exp (-T/28.07) +0.178.
6. The use according to any one of claims 1 to 5, wherein the method for preparing the fluorescent thermometry material comprises the steps of:
grinding, mixing, presintering and then grinding and calcining metal salt, phosphate, boric acid and europium oxide to obtain the fluorescent temperature measuring material.
7. The use according to claim 6, wherein the pre-firing temperature is 350-480 ℃ and the pre-firing time is 1.8-2.5 hours; the calcination temperature is 950-1100 ℃, and the calcination time is 2-6 hours.
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| CN112745836A (en) * | 2021-03-04 | 2021-05-04 | 沈阳大学 | Eu (Eu)2+、Eu3+Ion co-activated optical temperature sensing material and preparation method thereof |
| CN114736673A (en) * | 2022-04-22 | 2022-07-12 | 五邑大学 | Europium ion multivalent double-center optical temperature probe material |
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| CN112745836A (en) * | 2021-03-04 | 2021-05-04 | 沈阳大学 | Eu (Eu)2+、Eu3+Ion co-activated optical temperature sensing material and preparation method thereof |
| CN114736673A (en) * | 2022-04-22 | 2022-07-12 | 五邑大学 | Europium ion multivalent double-center optical temperature probe material |
Non-Patent Citations (2)
| Title |
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| 梁宏斌，等.空气条件下合成的CaBPO5:Eu、SrB4O7:Eu和Ba3（PO4）2:Eu的XANES和发光性质.核技术.2003,第26卷(第12期),905-908. * |
| 空气条件下合成的CaBPO5:Eu、SrB4O7:Eu和Ba3（PO4）2:Eu的XANES和发光性质;梁宏斌，等;核技术;第26卷(第12期);905-908 * |
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