A fluorescent temperature measuring material and its preparation method and application

Abstract

A fluorescent temperature measuring material and its preparation method and application, which relates to the technical field of luminescent materials, solves the problem of poor optical temperature measurement accuracy in a wide temperature range. The general chemical formula of the fluorescent temperature measuring material is A 5‑x (PO4)2BO4:xDy 3+ , wherein A is selected from Ca, Sr or Ba, B is selected from Si or Ge, and x is Dy 3+ The doping amount is 0.01 mol ≤ x ≤ 0.11 mol, more preferably 0.05 mol ≤ x ≤ 0.11 mol. The preparation method comprises: thoroughly mixing a dysprosium source, a substance containing element A, and a substance containing element B, and grinding to obtain a mixture; pre-calcining the mixture, cooling it, and then grinding it to obtain a pre-calcined mixture; and sintering the pre-calcined mixture, cooling it, and then grinding it to obtain a fluorescent temperature measurement material. The present invention can be applied to temperature sensors to achieve high-precision optical temperature measurement over a wide temperature range.

Description

Technical Field

[0001] The present invention relates to the technical field of luminescent materials, and in particular to a fluorescent temperature measuring material and a preparation method and application thereof. Background Art

[0002] Temperature is one of the most fundamental measurement parameters in numerous fields of natural science. Temperature sensors are widely used in everyday applications, including biosensing, environmental monitoring, medicine, and diagnostics. Unlike traditional thermometers, non-contact optical thermometers offer unique advantages such as fast response, non-invasive operation, and high spatial and temperature resolution. They can operate in harsh environments such as medical, high-temperature, electromagnetic, thermal, and corrosive environments, and detect fast-moving objects. This has led to widespread interest in non-contact temperature measurement technology based on fluorescent materials.

[0003] The core of fluorescence thermometry technology relies on establishing a relationship between the optical properties of lanthanide ions and temperature. By attaching the material as a coating to the surface of the model being measured, changes in the material's luminescence properties are monitored to dynamically measure surface temperature changes in real time. The temperature-sensitive optical properties of lanthanide ions typically include emission peak width, fluorescence intensity ratio, fluorescence lifetime, absolute intensity, and long afterglow time. The fluorescence intensity ratio can minimize the influence of external factors.

[0004] Currently, temperature measurement using the thermal coupling energy levels of single ions can effectively avoid the influence of the external environment. However, the small energy gap of the thermal coupling energy levels of most ions is not conducive to the discrimination of optical signals, which also limits further improvement of temperature measurement sensitivity and is not suitable for high-precision optical temperature measurement over a wide temperature range. Summary of the Invention

[0005] In order to solve the problem of poor optical temperature measurement accuracy of existing materials in a wide temperature range, the present invention proposes a fluorescent temperature measurement material and a preparation method and application thereof.

[0006] The technical solutions of the present invention are as follows:

[0007] A fluorescent temperature measuring material has the following general chemical formula:

[0008] A 5-x (PO4)2BO4:xDy 3+ ,

[0009] Wherein, element A is selected from Ca, Sr or Ba, element B is selected from Si or Ge, and x is Dy 3+The doping amount is 0.01mol≤x≤0.11mol, such as 0.01mol, 0.03mol, 0.05mol, 0.07mol, 0.09mol, 0.11mol, and more preferably 0.05mol≤x≤0.11mol.

[0010] A method for preparing the fluorescent temperature measuring material as described above comprises the following steps:

[0011] S1. Fully mixing the dysprosium source, the substance containing element A, and the substance containing element B, and grinding to obtain a mixture;

[0012] S2, pre-calcining the mixture, cooling it, and then grinding it to obtain a pre-calcined mixture;

[0013] S3. Sintering the pre-fired mixture, cooling it, and then grinding it to obtain a fluorescent temperature measuring material.

[0014] Preferably, the dysprosium source is one or a mixture of at least two of dysprosium oxide, dysprosium hydroxide, dysprosium halide, dysprosium oxalate, dysprosium acetate, and dysprosium nitrate, such as one or more of Dy2O3, Dy(NO3)3, and Dy(CH3COO)3.

[0015] Preferably, the substance containing element A is one or a mixture of at least two of an oxide containing element A, a halide containing element A, a carbonate containing element A, an oxalate containing element A, a citrate containing element A, an acetate containing element A, or a nitrate containing element A, such as one or more of CaCO3, SrCO3, BaCO3, Ca(NO3)2 and Ca(CH3COO)2.

[0016] Preferably, the substance containing element B is one or a mixture of at least two of an oxide containing element B, a carbonate containing element B, a nitrate containing element B, an oxalate containing element B, a citrate containing element B, or an acetate containing element B, such as one or more of SiO2, GeO2, and Si(CH3COO)4.

[0017] Preferably, the pre-calcination temperature in step S2 is 200-800°C, such as 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C, 800°C, and more preferably 300-700°C; the pre-calcination time is 0.5-24h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and more preferably 1-20h.

[0018] Preferably, the sintering temperature in step S3 is 850°C to 1550°C, such as 1000°C, 1050°C, 1200°C, 1250°C, 1300°C, 1350°C, 1400°C, 1450°C, 1500°C, 1550°C, and more preferably 1000-1550°C; the sintering time is 0.5h to 24h, such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h, 24h, and more preferably 1-20h.

[0019] Preferably, the grinding time is 5 min to 120 min, such as 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 65 min, 70 min, 75 min, 80 min, 85 min, 90 min, 95 min, 100 min, 105 min, 110 min, 115 min, 120 min, more preferably 10 to 100 min.

[0020] The present invention also provides an application of the fluorescent temperature measuring material or the fluorescent temperature measuring material prepared by the preparation method in a temperature sensor.

[0021] Compared with the prior art, the present invention has the following specific beneficial effects:

[0022] 1. The fluorescent temperature measuring material provided by the present invention is based on a compound with an apatite structure, Dy 3+ Ions are luminescence centers and can be effectively excited by near-ultraviolet light, with high light conversion efficiency and good luminescence detectability;

[0023] 2. The present invention utilizes Dy 3+ The thermal coupling energy level of ions (453nm and 480nm) is used to realize non-contact fluorescence temperature measurement. 3+ The ion thermal coupling energy level is in the blue region of the spectrum, which can effectively avoid the influence of blackbody radiation, thereby widening the temperature measurement range. Therefore, the fluorescent material provided by the present invention is more suitable for high-precision optical temperature measurement in a wide temperature range. In the wide temperature range of 296K to 1073K, its temperature measurement accuracy can reach 1.746% / K.

[0024] 3. The preparation process provided by the present invention is simple to operate, has low raw material and equipment costs, is environmentally friendly, and has stable product chemical properties, making it suitable for promotion and use. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is the X-ray diffraction spectrum of the fluorescent temperature measurement material prepared in Example 1;

[0026] Figure 2 This is the emission spectrum of the fluorescent temperature measurement material prepared in Example 1 at room temperature;

[0027] Figure 3 The emission spectra of the fluorescent temperature measurement material prepared in Example 1 at different temperatures;

[0028] Figure 4 This is a fitting diagram of the fluorescence intensity ratio of the fluorescent thermometric material prepared in Example 1;

[0029] Figure 5 This is the relative sensitivity curve and temperature response curve of the fluorescent temperature measurement material prepared in Example 1. DETAILED DESCRIPTION

[0030] In order to make the technical solution of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the specification of the present invention. It should be noted that the following embodiments are only used to better understand the technical solution of the present invention and should not be understood as limiting the present invention.

[0031] Example 1.

[0032] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0033] The X-ray diffractometer was used to test the fluorescent thermometric phosphor. The results were as follows: Figure 1 As shown, it can be seen that 0.05molDy 3+ The doping does not affect the crystal structure of the host matrix;

[0034] The fluorescence thermometry phosphor was detected by a steady-state transient fluorescence spectrometer, and its emission spectrum at room temperature was obtained as shown in the figure below. Figure 2 As shown in the figure, it can be seen that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 jump;

[0035] Measure the emission spectra of the fluorescent thermometric material at different temperatures. The results are as follows: Figure 3 As shown in the figure, it can be seen that as the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply; the fluorescence intensity of the fluorescent temperature measuring material is higher than that of the fluorescent temperature measuring material. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) and temperature have a certain exponential function relationship, and the fitting results are as follows Figure 4 As shown;

[0036] The relative sensitivity curve of the fluorescent temperature measuring material in the range of 296K to 1073K is as follows: Figure 5 As shown, it can be demonstrated that the best temperature sensitivity of this material is 1.746% / K.

[0037] Example 2.

[0038] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.99:2:1:0.005, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.99 (PO4)2SiO4:0.01Dy 3+ .

[0039] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.01molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.24% / K.

[0040] Example 3.

[0041] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 0.5h. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4h. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0042] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 Transition; as the temperature increases from 296K

[0043] At 1073K, the emission peak intensity at 453nm increased significantly, while the emission peak intensity at 480nm decreased sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.17% / K.

[0044] Example 4.

[0045] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 400°C for 0.5h. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4h. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0046] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 Transition; as the temperature increases from 296K

[0047] At 1073K, the emission peak intensity at 453nm increased significantly, while the emission peak intensity at 480nm decreased sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.28% / K.

[0048] Example 5.

[0049] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 200°C for 0.5h. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4h. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0050] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.09% / K.

[0051] Example 6.

[0052] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 800°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0053] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.31% / K.

[0054] Example 7.

[0055] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 0.5 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0056] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.24% / K.

[0057] Example 8.

[0058] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 24 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0059] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.18% / K.

[0060] Example 9.

[0061] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 850°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0062] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.13% / K.

[0063] Example 10.

[0064] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1350°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0065] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.24% / K.

[0066] Example 11.

[0067] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1450°C for 0.5 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0068] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.44% / K.

[0069] Example 12.

[0070] CaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1450°C for 0.5 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0071] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.36% / K.

[0072] Example 13.

[0073] SrCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Sr 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0074] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.16% / K.

[0075] Example 14.

[0076] SrCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, placed in an agate mortar, mixed evenly, and ground for about 30 minutes. The mixture was placed in an alumina crucible and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to be calcined at 1350°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Sr 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0077] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.46% / K.

[0078] Example 15.

[0079] CaCO3 (99.99%), NH4H2PO4 (99.99%), GeO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2GeO4:0.05Dy 3+ .

[0080] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.31% / K.

[0081] Example 16.

[0082] BaCO3 (99.99%), NH4H2PO4 (99.99%), SiO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ba 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0083] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.25% / K.

[0084] Example 17.

[0085] BaCO3 (99.99%), NH4H2PO4 (99.99%), GeO2 (99.999%), and Dy2O3 (99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600°C for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550°C for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ba 4.95 (PO4)2GeO4:0.05Dy 3+ .

[0086] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.31% / K.

[0087] Example 18.

[0088] Ca(NO3)2(99.99%), NH4H2PO4(99.99%), SiO2(99.999%) and Dy(NO3)3(99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600℃ for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550℃ for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0089] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) conforms to a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 0.93% / K.

[0090] Example 19.

[0091] Ca(CH3COO)2(99.99%), NH4H2PO4(99.99%), Si(CH3COO)4(99.999%), and Dy(CH3COO)3(99.99%) were weighed in a molar ratio of 4.95:2:1:0.025, mixed evenly in an agate mortar and ground for about 30 minutes, placed in an alumina crucible, and pre-fired at 600℃ for 6 hours. The pre-fired sample was taken out, ground and mixed again, and then placed in an alumina crucible and continued to calcine at 1550℃ for 4 hours. After natural cooling, the sample was taken out and carefully ground to obtain a white fluorescent temperature measuring phosphor with the molecular formula of Ca 4.95 (PO4)2SiO4:0.05Dy 3+ .

[0092] The fluorescence temperature measuring phosphor was tested by X-ray diffractometer. The results showed that 0.05 molDy 3+ The doping of the phosphor does not affect the crystal structure of the main matrix; the fluorescence temperature measuring phosphor was detected by steady-state transient fluorescence spectrometer. The results showed that under the excitation of 349nm near-ultraviolet light, its emission spectrum has two blue emission peaks at 453nm and 480nm, which belong to 4 I 15 / 2 → 6 H 15 / 2 and 4 F 9 / 2 → 6 H 15 / 2 As the temperature increases from 296K to 1073K, the emission peak intensity at 453nm increases significantly, while the emission peak intensity at 480nm decreases sharply. 453 / I 480 ( 4 I 15 / 2 → 6 H 15 / 2 / 4 F 9 / 2 → 6 H 15 / 2 ) has a certain exponential function relationship with temperature; the optimal temperature sensitivity of the fluorescent temperature measuring material in the range of 296K to 1073K is 1.01% / K.

Claims

1. An application of a fluorescent temperature measuring material, characterized in that: Used in temperature sensors; The fluorescent temperature measuring material has the following general chemical formula: A 5-x (PO4)2BO4:xDy 3+ , Wherein, element A is selected from Ca, Sr or Ba, element B is selected from Si or Ge, and x is Dy 3+ Doping amount, 0.01mol≤x≤0.11mol; The preparation method of the fluorescent temperature measuring material comprises the following steps: S1. Fully mixing the dysprosium source, the substance containing element A, and the substance containing element B, and grinding to obtain a mixture; S2, pre-calcining the mixture, cooling it, and then grinding it to obtain a pre-calcined mixture; S3, sintering the pre-fired mixture, cooling it, and then grinding it to obtain a fluorescent temperature measuring material; Furthermore, the pre-firing temperature in step S2 is 200° C. to 800° C., and the pre-firing time is 0.5 h to 24 h; Furthermore, the sintering temperature in step S3 is 850° C. to 1550° C., and the sintering time is 0.5 h to 24 h.

2. The use of the fluorescent temperature measuring material according to claim 1, characterized in that: The dysprosium source is one of dysprosium oxide, dysprosium hydroxide, dysprosium halide, dysprosium oxalate, dysprosium acetate, and dysprosium nitrate, or a mixture of at least two of them.

3. The use of the fluorescent temperature measuring material according to claim 1, characterized in that: The substance containing element A is one or a mixture of at least two of an oxide containing element A, a halide containing element A, a carbonate containing element A, an oxalate containing element A, a citrate containing element A, an acetate containing element A, and a nitrate containing element A.

4. The use of the fluorescent temperature measuring material according to claim 1, characterized in that: The substance containing element B is one or a mixture of at least two of oxides containing element B, carbonates containing element B, nitrates containing element B, oxalates containing element B, citrates containing element B, and acetates containing element B.

5. The use of the fluorescent temperature measuring material according to claim 1, characterized in that: The grinding time is 5 min to 120 min.

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