Thermal quenching resistant fluorescent powder, preparation method and application thereof

Abstract

The application discloses a kind of anti-thermal quenching fluorescent powder and its preparation method and application, belong to thermal imaging field.The application is with ZrMgMo3O 12 As matrix, by doping rare earth element Dy to obtain general formula ZrMgMo3O 12 :Dy yellow light fluorescent powder, realize anti-luminescence thermal quenching by energy transfer between rare earth element Dy and matrix and defect effect, using 292nm, 360nm, 393nm, 471nm light source excitation, by detecting the intensity and wavelength of fluorescence, to obtain temperature distribution image.Fluorescent powder preparation method is as follows: Dy2O3 is added in the mixture of ZrO2, MgO, MoO3 respectively, grinding is obtained after adding ethanol mixture A;Then calcine mixture A obtains ZrMgMo3O 12 :Dy fluorescent powder.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of anti-thermal quenching fluorescent powder and its preparation method and application, belong to thermal imaging field. BACKGROUND

[0002] With the development of science and technology, the requirement of material performance under high temperature environment is higher and higher. In the field of aerospace, energy, electronics, etc., the material needs to have the ability to maintain stable performance under high temperature environment. Thermal imaging fluorescent powder is a special fluorescent material that can be used in thermal imaging technology. Its application background is to improve the performance and image quality of thermal imaging equipment, so that the thermal distribution and morphology of target objects can be clearly observed under low light conditions or high temperature environment. The application of thermal imaging fluorescent powder can play an important role in many fields, such as industrial detection, security monitoring, fire rescue, medical diagnosis, etc. It can help people more accurately detect and analyze the temperature distribution of objects, find potential problems or abnormal situations, and improve work efficiency and safety.

[0003] The technology of thermal imaging fluorescent powder mainly involves the following aspects: 1. Preparation of fluorescent powder: prepare the fluorescent powder into a uniform coating or dope it into other materials by suitable method to ensure its uniform distribution and effective excitation in thermal imaging equipment. 2. Excitation light source: thermal imaging equipment usually uses infrared laser or other near-infrared light source to excite fluorescent powder to emit visible light. 3. Image processing: the collected thermal imaging fluorescent powder image needs to be enhanced and analyzed by specific image processing algorithm to extract useful thermal information.

[0004] 4. Temperature measurement and analysis: by analyzing the visible light emitted by the fluorescent powder, the temperature distribution and change of the target object can be determined to realize the function of thermal imaging. The specific technology and application of thermal imaging fluorescent powder may vary depending on different needs and equipment. In actual application, factors such as stability, life, compatibility with other components of the fluorescent powder also need to be considered.

[0005] However, there are some limitations in fluorescent powder thermal imaging. When the temperature is too high, the fluorescent powder will undergo thermal quenching phenomenon, which will greatly affect the function of fluorescent powder thermal imaging, for example: CaWO4: Yb, Er fluorescent powder, under 980nm laser excitation, the luminescence gradually decreases with the increase of temperature, and reaches 300℃, which causes serious thermal quenching. The excitation light source is relatively single, so its application in thermal imaging is limited.

[0006] In summary, fluorescent powder thermal imaging technology provides a fast, non-contact and intuitive temperature measurement method in many applications, but the existing fluorescent powder is prone to quenching at high temperature, and can only emit light under single excitation light, so its application field is limited. SUMMARY

[0007] In order to solve the problems of the existing fluorescent powder, one of the purposes of the present application is to provide a kind of anti-thermal quenching fluorescent powder, the general formula of the anti-thermal quenching fluorescent powder is ZrMgMo3O 12 :Dy.

[0008] Another purpose of the present application is to provide a kind of anti-thermal quenching fluorescent powder in thermal imaging.

[0009] The third purpose of the present application is to provide a kind of anti-thermal quenching fluorescent powder with the general formula ZrMgMo3O 12 :Dy, and the preparation method thereof is as follows:

[0010] (1) Dy2O3 is added to the mixture of ZrO2, MgO and MoO3 respectively, and ethanol is ground to obtain mixture I.

[0011] (2) the mixture I is calcined to obtain ZrMgMo3O 12 :Dy fluorescent powder.

[0012] Preferably, the mass ratio of Dy2O3, ZrO2, MgO and MoO3 in step (1) is 0.0933:0.5545:0.2015:2.1591.

[0013] Preferably, the temperature of the calcination in step (2) is 800-900℃, the time is 5-6 hours, the heating rate is 2-5℃ / min, and the atmosphere is air.

[0014] The beneficial effects of the present application

[0015] (1) The present application first uses the negative thermal expansion material ZrMgMo3O 12 as a matrix, and obtains a kind of fluorescent powder with the general formula ZrMgMo3O 12 :Dy by doping Dy, and the prepared fluorescent powder has good anti-thermal quenching property, most of the existing fluorescent powder will be quenched from 100℃, and the fluorescent powder prepared by the present application maintains good luminescent property at 300℃, so the fluorescent powder has a wider application.

[0016] (2) Most of the existing fluorescent powder can only emit light under a single excitation light, and the excitation light source is single, while the present application uses the negative thermal expansion material ZrMgMo3O 12 as a matrix, and obtains yellow light by doping Dy, and due to the negative thermal expansion effect, the Dy and ZrMgMo3O 12The energy transmission between the matrix is more efficient and faster, so that the yellow light emission of Dy is enhanced; therefore, by using 292nm, 360nm, 393nm, 471nm ultraviolet lamps as the excitation light source, the excitation light source of the fluorescent powder prepared by the application is wider, so that the application has a wider application field. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The fluorescence spectrum of the fluorescent powder of Example 1 under the excitation of a 292nm ultraviolet lamp at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃ is measured by an F7000 fluorescence spectrometer.

[0018] Figure 2 The fluorescence spectrum of the fluorescent powder of Example 1 under the excitation of a 360nm ultraviolet lamp at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃ is measured by an F7000 fluorescence spectrometer.

[0019] Figure 3 The fluorescence spectrum of the fluorescent powder of Example 1 under the excitation of a 393nm ultraviolet lamp at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃ is measured by an F7000 fluorescence spectrometer.

[0020] Figure 4 The fluorescence spectrum of the fluorescent powder of Example 1 under the excitation of a 471nm ultraviolet lamp at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃ is measured by an F7000 fluorescence spectrometer. DETAILED DESCRIPTION

[0021] The technical solutions of the application are further described below in combination with the drawings and through specific embodiments, but the following examples are only simple examples of the application and do not represent or limit the protection scope of the application, and the protection scope of the application is subject to the claims.

[0022] Example 1

[0023] A preparation method of a fluorescent powder resistant to thermal quenching comprises the following steps:

[0024] (1) 0.0933g of Dy2O3 is added to a mixture of 0.5545g of ZrO4, 2.1591g of MoO3 and 0.2015g of MgO, and ethanol is added to grind to obtain a mixture Ⅰ.

[0025] (2) The mixture Ⅰ is placed in an alumina crucible and put into a box furnace, and sintered at 800℃ for 6 hours under air atmosphere at a temperature rising rate of 5℃ / min, and then cooled to obtain ZrMgMo3O12 :Dy phosphor.

[0026] The prepared ZrMgMo3O 12 :Application of Dy phosphor as thermal imaging:

[0027] (1) ZrMgMo3O 12 :Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer is shown in Figure 1 The spectrum shows that the yellow light peak (580nm) gradually increases with the increase of temperature under the excitation of 292nm light source, showing excellent anti-thermal quenching performance, indicating that its thermal imaging function is excellent.

[0028] (2) ZrMgMo3O 12 :Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer is shown in Figure 2 The spectrum shows that the yellow light peak (580nm) first increases and then decreases with the increase of temperature under the excitation of 360nm light source, and still maintains 1.5 times the initial fluorescence intensity at 300℃, indicating that its thermal imaging function is excellent.

[0029] (3) ZrMgMo3O 12 :Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer is shown in Figure 3 The spectrum shows that the yellow light peak (580nm) first increases and then decreases with the increase of temperature under the excitation of 393nm light source, and still maintains 1.2 times the initial fluorescence intensity at 300℃, indicating that its thermal imaging function is excellent.

[0030] (4) ZrMgMo3O 12 :Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer is shown in Figure 4 The spectrum shows that the yellow light peak (580nm) remains basically unchanged with the increase of temperature under the excitation of 471nm light source, and the luminescence intensity is stable at 20-300℃, indicating that its thermal imaging function is excellent.

[0031] Comparative Example 1

[0032] A preparation method of a heat quenching resistant fluorescent powder comprises:

[0033] (1) 0.0880g of Eu2O3 is added to a mixture of 0.5545g of ZrO4, 2.1591g of MoO3 and 0.2015g of MgO, and ethanol is added for grinding to obtain a mixture I.

[0034] (2) The mixture I is placed in an alumina crucible and put into a box furnace, and sintered at 800℃ for 6 hours at a temperature rising rate of 5℃ / min under an air atmosphere, and after cooling, ZrMgMo3O 12 :Eu fluorescent powder is obtained.

[0035] The prepared ZrMgMo3O 12 :Eu fluorescent powder is applied to thermal imaging:

[0036] (1) The ZrMgMo3O 12 :Eu fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum diagram obtained by F7000 fluorescence spectrometer testing shows that the fluorescence intensity gradually increases with the temperature rising under the 292nm excitation light source, and the heat quenching resistance performance is shown, indicating that it has the function of thermal imaging.

[0037] (2) The ZrMgMo3O 12 :Eu fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum diagram obtained by F7000 fluorescence spectrometer testing shows that the fluorescence intensity gradually decreases with the temperature rising under the 360nm excitation light source, and the luminescence is seriously quenched, and its application range is limited. 12 (3) The ZrMgMo3O

[0038] (4) The ZrMgMo3O 12 :Eu fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum diagram obtained by F7000 fluorescence spectrometer testing shows that the fluorescence intensity gradually decreases with the temperature rising under the 471nm excitation light source, and the luminescence is seriously quenched, and its application range is limited. 12The Eu fluorescent powder can resist thermal quenching under the excitation light source of 292nm, but serious thermal quenching occurs under 360nm, 393nm and 471nm, which is limited to the excitation light source, and the thermal imaging function is limited to the single excitation light source.

[0039] Comparative Example 2

[0040] A preparation method of a thermal quenching resistant fluorescent powder comprises:

[0041] (1) 0.0934g of Tb4O7 is added into a mixture of 0.5545g of ZrO4, 2.1591g of MoO3 and 0.2015g of MgO, and ethanol is added for grinding to obtain a mixture I.

[0042] (2) The mixture I is loaded into an alumina crucible and placed in a box furnace, and sintered at 800℃ for 6 hours under air atmosphere at a heating rate of 5℃ / min, and after cooling, ZrMgMo3O 12 :Tb fluorescent powder is obtained.

[0043] The prepared ZrMgMo3O 12 :Tb fluorescent powder is applied to thermal imaging:

[0044] (1) The ZrMgMo3O 12 :Tb fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer testing shows that the fluorescence intensity gradually decreases with the temperature rising under the excitation light source of 292nm, and the luminescence occurs serious quenching, which has limited application range.

[0045] (2) The ZrMgMo3O 12 :Tb fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer testing shows that the fluorescence intensity gradually decreases with the temperature rising under the excitation light source of 360nm, and the luminescence occurs serious quenching, which has limited application range.

[0046] (3) The ZrMgMo3O 12 :Tb fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum obtained by F7000 fluorescence spectrometer testing shows that the fluorescence intensity gradually decreases with the temperature rising under the excitation light source of 393nm, and the luminescence occurs serious quenching, which has limited application range.

[0047] (4) The ZrMgMo3O 12: Tb fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, and the fluorescence spectrum diagram obtained by using F7000 fluorescence spectrometer is tested. The fluorescence intensity gradually decreases with the increase of temperature under 471nm excitation light source, and the luminescence is seriously quenched, so the application range is limited. Summary: Compared with the examples, ZrMgMo3O 12 : Tb fluorescent powder is heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, 300℃, and the fluorescence spectrum diagram obtained by using F7000 fluorescence spectrometer is tested. The fluorescence intensity gradually decreases with the increase of temperature under 471nm excitation light source, and the luminescence is seriously quenched, so the application range is limited. Summary: Compared with the examples, ZrMgMo3O

[0048] Comparative Example 3

[0049] A kind of anti-thermal quenching fluorescent powder is prepared, as a comparison, the difference between this comparative example and example 1 is that the negative expansion material used is Y2Mo3O 12 , the specific preparation steps are as follows:

[0050] (1) 0.0856g of Dy2O3 is added to the mixture of 0.9867g of Y2O3 and 1.9864g of MoO3, and ethanol is ground to obtain a mixture I.

[0051] (2) The mixture I is placed in an alumina crucible and put into a box furnace, and sintered at 800℃ for 6 hours under air atmosphere at a heating rate of 5℃ / min, and Y2Mo3O 12 : Dy fluorescent powder is obtained after cooling.

[0052] The anti-thermal quenching performance of the fluorescent powder prepared in this comparative example is not as good as that of example 1, because Y2Mo3O 12 : Dy is relatively poor, has hygroscopicity, and there is lattice water at low temperature, which hinders the negative thermal expansion performance of Y2Mo3O 12 : Dy, resulting in poor anti-thermal quenching performance of Y2Mo3O 12 : Dy in low temperature area, while ZrMgMo3O 12 : Dy fluorescent powder, because ZrMgMo3O 12 : Dy has good crystal structure rigidity and weak hygroscopicity, and the anti-thermal quenching performance at low temperature will not be affected.

[0053] The above specific embodiments of the present application are described in detail, but the present application is not limited to the above examples, and various changes can be made within the knowledge of those skilled in the art without departing from the purpose of the present application.

Claims

1. A heat-resistant quenching phosphor, characterized in that: The general formula of the heat-resistant quenching phosphor is ZrMgMo3O 12 :Dy.

2. The method for preparing the heat-quenching phosphor according to claim 1, characterized in that: Specifically, the steps include the following: (1) Add Dy2O3 to a mixture of ZrO2, MgO and MoO3, add ethanol and grind to obtain mixture I; (2) Calcine the mixture I to obtain ZrMgMo3O 12 :Dy fluorescent powder.

3. The method for preparing the heat-resistant quenching phosphor according to claim 2, characterized in that: In step (1), the mass ratio of Dy2O3, ZrO2, MgO and MoO3 is 0.0933:0.5545:0.2015:2.1591.

4. The method for preparing the heat-quenching phosphor according to claim 2, characterized in that: The calcination temperature in step (2) is 800~900℃, the time is 5~6 hours, the heating rate is 2~5℃ / min, and the atmosphere is air.

5. The application of the heat-resistant quenching phosphor according to claim 1 in thermal imaging.

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