Temperature-sensitive fluorescent material as well as preparation method and application thereof

What is AI technical title?
AI technical title is built by Patsnap AI team. It summarizes the technical point description of the patent document.
By introducing non-rare earth Mn elements into the apatite structure, Sr8.7Tb(PO4)5(Si1-xGexO4)F2:0.3Mn2+ type temperature-sensitive fluorescent material was prepared, and its fluorescence intensity ratio was used to achieve high-precision temperature measurement, which solved the problem of The lack of sensitivity and response speed of traditional temperature sensors in complex environments provides a new thermosensitive fluorescent material suitable for many fields.

CN119307259AInactive Publication Date: 2025-01-14CHINA UNIV OF GEOSCIENCES (BEIJING)

View PDF 0 Cites 0 Cited by

Patent Information

Application Number: CN202411327266.7
Authority / Receiving Office: CN · China
Patent Type: Applications(China)
Current Assignee / Owner
Filing Date: 2024-09-23
Publication Date: 2025-01-14
Estimated Expiration: Not applicable · inactive patent

AI Technical Summary

Technical Problem

Traditional temperature sensors are difficult to meet the requirements of high sensitivity and rapid response in complex environments. The existing temperature measurement technology based on fluorescence intensity ratio requires the development of new and efficient temperature measurement devices.

Method used

Non-rare earth Mn element doping was introduced into the apatite structure fluorescent material system, and Sr8.7Tb(PO4)5(Si1-xGexO4)F2:0.3Mn2+ type temperature-sensitive fluorescent material was prepared, and sintered and cooled by high-temperature solid phase method in one step. Post-grinding, maintain the apatite structure, and use the fluorescence intensity ratio of the characteristic emission peaks of Tb3+ and Mn2+ to measure the temperature with temperature.

Benefits of technology

It realizes high-precision temperature measurement in complex environments, provides a new temperature-sensitive fluorescent material suitable for multiple fields, has good temperature measurement performance, and is simple in preparation, suitable for large-scale production.

✦ Generated by Eureka AI based on patent content.

Smart Images

Figure CN119307259A_ABST

Patent Text Reader

Abstract

The invention belongs to the technical field of luminescent materials, and particularly relates to a temperature-sensitive fluorescent material and a preparation method and application thereof. The chemical composition formula of the fluorescent material is Sr8.7Tb (PO4) 5 (Si1-xGexO4) F2: 0.3 Mn < 2 + >, x is greater than or equal to 0 and less than or equal to 0.5, carbonate, oxide or corresponding salts in the structural formula are selected as raw materials, and the luminescent material is prepared by a solid-phase synthesis method in a reducing atmosphere. The fluorescence intensity ratio of the luminescent material corresponding to Tb < 3 + > and Mn < 2 + > changes correspondingly along with temperature, and the luminescent material can be applied to the field of temperature measurement based on the fluorescence intensity ratio. In addition, the temperature-sensitive fluorescent material provided by the invention is simple in preparation process, efficient and easy to operate.

Need to check novelty before this filing date? Find Prior Art

Description

Technical Field

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

[0002] Accurate temperature detection is of great significance in many fields such as industrial production, electronics industry, life sciences, aerospace and national defense construction. With the development of science and technology and society, temperature detection technology has also ushered in new challenges: traditional temperature sensors can no longer meet the temperature measurement requirements under different conditions. The development of science and technology in various fields requires temperature sensors to be able to work in complex and diverse environments, and puts forward higher requirements for the performance of measurement sensitivity, response speed, etc. The temperature measurement technology based on fluorescence intensity ratio (FIR) calibrates the temperature by measuring the relative ratio of emission peaks in the spectrum. Due to its wide operating temperature range, high temperature measurement accuracy, and excellent spatial resolution, it is suitable for accurate temperature measurement or temperature surface distribution measurement in harsh environments or in the presence of strong electromagnetic interference. It can provide temperature calibration for other radiation temperature measurement technologies and has broad application prospects in metrology, gas mechanics, atmosphere and maritime, electronics industry, chemical industry, medicine, bioengineering and military fields. It is urgent to develop new and efficient temperature measurement devices based on FIR. Therefore, it is very necessary to study and develop high-performance new temperature-sensitive fluorescent materials. Summary of the invention

[0003] In order to solve the above problems, the applicant has conducted a doping preparation experiment based on non-rare earth Mn elements in an apatite structure fluorescent material system, and obtained a temperature-sensitive fluorescent material with good properties that can be applied to the field of temperature measurement based on fluorescence intensity ratio: the raw materials are mixed in proportion, sintered in a reducing atmosphere by a high-temperature solid-phase method in one step, and ground after cooling to obtain a Mn with an apatite structure. 2+ Excited temperature-sensitive fluorescent material.

[0004] The technical solution of the present invention is described in detail below:

[0005] One of the purposes of the present invention is to provide a novel temperature-sensitive fluorescent material Sr having temperature measurement performance. 8.7 Tb(PO4)5(Si 1- x Ge x O4)F2:0.3Mn 2+ , where 0≤x≤0.5.

[0006] A second object of the present invention is to provide a method for preparing the above-mentioned temperature-sensitive fluorescent material.

[0007] A third object of the present invention is to provide application of the above-mentioned temperature-sensitive fluorescent material in temperature sensor devices.

[0008] According to one of the purposes of the present invention, a temperature-sensitive fluorescent material is provided. The temperature-sensitive fluorescent material of the present invention has a chemical formula of Sr 8.7 Tb(PO4)5(Si 1-x Ge x O4)F2:0.3Mn 2+ , wherein x is the molar ratio of substituted Ge, wherein 0≤x≤0.5.

[0009] In a preferred embodiment of the present invention, the chemical composition of the fluorescent material is: Sr 8.7 Tb(PO4)5(SiO4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.95 Ge 0.05 O4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.8 Ge 0.2 O4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.7 Ge 0.3 O4)F2:0.3Mn 2+ .

[0010] In the fluorescent material of the present invention, Ge replaces Si and enters the crystal structure without destroying the crystal structure, and the fluorescent material has an apatite-type mineral structure.

[0011] The fluorescent material of the present invention has an emission spectrum of Tb 3+ and Mn 2+ Characteristic emission peak composition, corresponding to Tb 3+ and Mn 2+ The peak fluorescence intensity ratio changes accordingly with temperature.

[0012] According to the second object of the present invention, the preparation method of the temperature-sensitive fluorescent material is as follows: 8.7 Tb(PO4)5(Si 1- x Ge x O4)F2:0.3Mn 2+ The required raw materials are weighed in a metered ratio, fully ground and mixed, sintered, cooled and ground into powder. The sintering conditions are: calcined at 1300-1500°C for 2-6 hours in a reducing atmosphere (95% N2+5% H2).

[0013] Furthermore, the phosphor Sr 8.7 Tb(PO4)5(Si 1-x Ge x O4)F2:0.3Mn 2+ The invention is prepared from Sr source, Tb source, P source, Si source, Ge source, F source and Mn source, wherein the molar ratio of the elements Sr:Tb:P:Si:Ge:F:Mn in the Sr source, Tb source, P source, Si source, Ge source, F source and Mn source is 8.7:1:5:1-0.5:0-0.5:2:0.3.

[0014] The Sr source raw material is selected from one or more of SrO, SrCO3, etc., and further, the Sr source raw material is SrCO3.

[0015] The Tb source raw material is selected from one or more of TbNO3, Tb4O7, etc., and further, the Tb source raw material is Tb4O7.

[0016] The P source raw material is selected from one or more of NH4H2PO4, (NH4)2HPO4, etc. Further, the P source raw material is (NH4)2HPO4.

[0017] The Si source raw material is SiO2.

[0018] The Ge source material is GeO2.

[0019] The F source raw material is NH4HF2.

[0020] The Mn source raw material is selected from one or more of MnCO3, KMnO4, and MnO2. Further, the Mn source raw material is MnCO3.

[0021] According to the third objective of the present invention, the temperature-sensitive fluorescent material is applied to the field of temperature measurement based on fluorescence intensity ratio.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The fluorescent material Sr provided by the present invention 8.7 Tb(PO4)5(Si 1-x Ge x O4)F2:0.3Mn 2+ Using non-rare earth Mn 2+ Ion doping, Tb 3+ and Mn 2+The peak fluorescence intensity ratio changes with temperature, has good temperature measurement properties, and can be applied to FIR-based temperature measurement. The substitution of Ge for Si does not destroy the crystal structure of the apatite-type fluorescent material, and a series of new temperature-sensitive fluorescent materials are obtained.

[0024] The raw materials for preparing the fluorescent material of the present invention are cheap and easily available. The required raw materials are fully ground and then sintered at high temperature in a reducing atmosphere. The preparation method is simple to operate, with a one-step reaction, and is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 XRD patterns of samples and standard cards prepared for the examples;

[0026] Figure 2 Excitation and emission spectra of samples prepared for the examples;

[0027] Figure 3 The emission spectra of the samples at different temperatures were obtained for the examples;

[0028] Figure 4 This is the FIR fitting diagram of the sample prepared in the embodiment. DETAILED DESCRIPTION

[0029] The present invention is further described in detail with reference to the following specific examples, but the protection scope of the present invention is not limited to the following specific examples.

[0030] Example 1: Material composition is Sr 8.7 Tb(PO4)5(SiO4)F2:0.3Mn 2+

[0031] (1) Press Sr 8.7 Tb(PO4)5(SiO4)F2:0.3Mn 2+ According to the stoichiometric ratio of each element, accurately weigh 1.028g SrCO3, 0.149g Tb4O7, 0.528g (NH4)2HPO4, 0.048g SiO2, 0.046g NH4HF2, and 0.028g MnCO3 powder raw materials, place them in an agate mortar and grind them for about 30 minutes to fully mix the raw materials;

[0032] (2) transferring the mixed raw material obtained in step 1 into an alumina crucible, placing it in a high-temperature tube furnace in a reducing atmosphere (95% N2 + 5% H2), calcining it at 1350°C for 3 hours, and taking it out after natural cooling;

[0033] (3) Grind the sintered body obtained in step 2 to obtain Sr 8.7 Tb(PO4)5(SiO4)F2:0.3Mn 2+ Temperature sensitive fluorescent material.

[0034] Example 2: Material composition is Sr 8.7 Tb(PO4)5(Si 0.95 Ge 0.05 O4)F2:0.3Mn 2+

[0035] (1) Press Sr 8.7 Tb(PO4)5(Si 0.95 Ge 0.05 O4)F2:0.3Mn 2+ According to the stoichiometric ratio of each element, accurately weigh 1.028g SrCO3, 0.149g Tb4O7, 0.528g (NH4)2HPO4, 0.046g SiO2, 0.004g GeO2, 0.046g NH4HF2, and 0.028g MnCO3 powder raw materials, place them in an agate mortar and grind them for about 30 minutes to fully mix the raw materials;

[0036] (2) transferring the mixed raw material obtained in step 1 into an alumina crucible, placing it in a high-temperature tube furnace in a reducing atmosphere (95% N2 + 5% H2), calcining it at 1400°C for 2 hours, and taking it out after natural cooling;

[0037] (3) Grind the sintered body obtained in step 2 to obtain Sr 8.7 Tb(PO4)5(Si 0.95 Ge 0.05 O4)F2:0.3Mn 2+ Temperature sensitive fluorescent material.

[0038] Example 3: Material composition is Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn 2+

[0039] (1) Press Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn 2+ Accurately weigh 1.028g SrCO3, 0.149g Tb4O7, 0.528g (NH4)2HPO4, 0.043g SiO2, 0.008g GeO2, 0.046g NH4HF2, and 0.028g MnCO3 powder raw materials according to the stoichiometric ratio of each element, and grind them in an agate mortar for about 30 minutes to fully mix the raw materials;

[0040] (2) transferring the mixed raw material obtained in step 1 into an alumina crucible, placing it in a high-temperature tube furnace in a reducing atmosphere (95% N2 + 5% H2), calcining it at 1460°C for 3 hours, and taking it out after natural cooling;

[0041] (3) Grind the sintered body obtained in step 2 to obtain Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn 2+ Temperature sensitive fluorescent material.

[0042] Example 4: Material composition is Sr 8.7 Tb(PO4)5(Si 0.8 Ge 0.2 O4)F2:0.3Mn 2+

[0043] (1) Press Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn 2+ Accurately weigh 1.028g SrCO3, 0.149g Tb4O7, 0.528g (NH4)2HPO4, 0.038g SiO2, 0.017g GeO2, 0.046g NH4HF2, and 0.028g MnCO3 powder raw materials according to the stoichiometric ratio of each element, and grind them in an agate mortar for about 30 minutes to fully mix the raw materials;

[0044] (2) transferring the mixed raw material obtained in step 1 into an alumina crucible, placing it in a high-temperature tube furnace in a reducing atmosphere (95% N2 + 5% H2), calcining it at 1380°C for 4 hours, and taking it out after natural cooling;

[0045] (3) Grind the sintered body obtained in step 2 to obtain Sr 8.7 Tb(PO4)5(Si 0.8 Ge 0.2 O4)F2:0.3Mn 2+ Temperature sensitive fluorescent material.

[0046] Example 5: Material composition is Sr 8.7 Tb(PO4)5(Si 0.7 Ge 0.3 O4)F2:0.3Mn 2+

[0047] (1) Press Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn2+ Accurately weigh 1.028g SrCO3, 0.149g Tb4O7, 0.528g (NH4)2HPO4, 0.034g SiO2, 0.025g GeO2, 0.046g NH4HF2, and 0.028g MnCO3 powder raw materials according to the stoichiometric ratio of each element, and grind them in an agate mortar for about 30 minutes to fully mix the raw materials;

[0048] (2) transferring the mixed raw material obtained in step 1 into an alumina crucible, placing it in a high-temperature tube furnace in a reducing atmosphere (95% N2 + 5% H2), calcining it at 1450°C for 2 hours, and taking it out after natural cooling;

[0049] (3) Grind the sintered body obtained in step 2 to obtain Sr 8.7 Tb(PO4)5(Si 0.7 Ge 0.3 O4)F2:0.3Mn 2+ Temperature sensitive fluorescent material.

[0050] Example 6: XRD analysis of samples

[0051] The general structural formula of the fluorescent materials prepared in Examples 1 to 5 is Sr 8.7 Tb(PO4)5(Si 1-x Ge x O4)F2:0.3Mn 2+ According to the general formula, subsequent verification experiments show that when 0≤x≤0.5, the materials prepared by weighing the raw materials according to the ratio of each element in the general formula can maintain the apatite crystal structure. The specific analysis content is as follows:

[0052] Determination of Sr prepared in Example 1 8.7 Tb(PO4)5(SiO4)F2:0.3Mn 2+ Fluorescent material and Sr prepared in Example 5 8.7 Tb(PO4)5(Si 0.7 Ge 0.3 O4)F2:0.3Mn 2+ The XRD spectrum of the fluorescent material is compared with the standard card. The results are as follows Figure 1 As shown. Among them,

[0053] Curve 1 represents the spectrum of standard card JCPDS 89-6495;

[0054] Curve 2 represents the XRD spectrum of the sample obtained in Example 1;

[0055] Curve 3 represents the XRD spectrum of the sample prepared in Example 5.

[0056] As can be seen from the figure, the XRD spectra of the samples prepared in Example 1 and Example 5 have a high degree of match with the apatite structure compound standard card and have no impurity peaks, indicating that the samples prepared under the experimental conditions are pure phase, and the incorporation of Mn and the substitution of Ge for Si do not destroy the crystal structure.

[0057] Example 7: Excitation and emission spectra of samples

[0058] The excitation and emission spectra of the sample prepared in Test Example 2 were obtained with an excitation wavelength of 375 nm and a detection wavelength of 547 nm. The results are as follows: Figure 2 shown.

[0059] As can be seen from the figure, the excitation spectrum of the sample is composed of a broadband in the range of 300-400nm. Under 375nm excitation, the emission spectrum is composed of Tb with a main peak at 547nm. 3+ of 5 D→ 7 F characteristic emission and Mn with main peak at 593nm 2+ of 4 T1( 4 G)- 6 A1( 6 S) Characteristic transition emission composition.

[0060] Example 8: Emission spectral analysis of samples at different temperatures

[0061] The emission spectra of the samples prepared in Example 3 at different temperatures were tested, with an excitation wavelength of 375 nm. The results are as follows: Figure 3 Curves 1 to 6 respectively represent the emission spectra of the sample obtained in Example 3 at 30°C, 100°C, 150°C, 200°C, 250°C, and 300°C.

[0062] As can be seen from the figure, under 375nm excitation, the emission spectrum intensity of the sample decreases with increasing temperature, Tb 3+ Characteristic emission and Mn 2+ The intensity of the characteristic emission peak varies to different degrees. Further, the ratio of the fluorescence intensity at 547nm and 593nm is fitted, as shown in Figure 4 As shown, Tb 3+ Characteristic emission and Mn 2+ The characteristic emission fluorescence intensity ratio increases monotonically with temperature and can be used for FIR-based temperature determination.

[0063] Although the present invention has been described in detail above by general description and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all belong to the scope of protection claimed by the present invention.

Claims

1. A temperature-sensitive fluorescent material, characterized in that: The chemical formula of the temperature-sensitive fluorescent material is Sr 8.7 Tb(PO4)5(Si 1- x Ge x O4)F2:0.3Mn 2+ , where 0≤x≤0.

5.

2. The temperature-sensitive fluorescent material according to claim 1, characterized in that: The chemical formula of the temperature-sensitive fluorescent material is Sr 8.7 Tb(PO4)5(SiO4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.95 Ge 0.05 O4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.9 Ge 0.1 O4)F2:0.3Mn 2+ , Sr 8.7 Tb(PO4)5(Si 0.8 Ge 0.2 O4)F2:0.3Mn 2+ or Sr 8.7 Tb(PO4)5(Si 0.7 Ge 0.3 O4)F2:0.3Mn 2+ .

3. The method for preparing the temperature-sensitive fluorescent material according to claim 1, characterized in that: Press Sr 8.7 Tb(PO4)5(Si 1- x Ge x O4)F2:0.3Mn 2+ The required raw materials are weighed in a metered ratio, fully ground and mixed, sintered, cooled and ground into powder. The sintering conditions are: calcination at 1300-1500° C. for 2-6 hours in a reducing atmosphere (95% N2+5% H2).

4. The method according to claim 3, characterized in that Among the raw materials, the compound containing Sr is SrCO3, the compound containing Tb is Tb4O7, the compound containing P is (NH4)2HPO4, the compound containing Si is SiO2, the compound containing Ge is GeO2, the compound containing F is NH4HF2, and the compound containing Mn is MnCO3.

5. The temperature-sensitive fluorescent material according to claim 1 or 2 corresponds to Tb 3+ and Mn 2+ The emitted fluorescence intensity ratio changes accordingly with temperature and can be applied to the field of temperature measurement based on fluorescence intensity ratio.