Heat-quenching-resistant fluorescent powder as well as preparation method and application thereof

Abstract

The invention discloses heat-quenching-resistant fluorescent powder as well as a preparation method and application thereof, and belongs to the field of thermal imaging. ZrMgMo3O12 is used as a matrix, rare earth element Dy is doped to obtain the fluorescent powder which emits yellow light and has a general formula of ZrMgMo3O12: Dy, luminescence thermal quenching resistance is realized by utilizing energy transfer and defect action between the rare earth element Dy and the matrix, light sources of 292 nm, 360 nm, 393 nm and 471 nm are used for excitation, the temperature of the fluorescent powder is increased from 20 DEG C to 300 DEG C, and an image of temperature distribution is obtained by detecting the intensity and wavelength of fluorescence. The preparation method of the fluorescent powder comprises the following steps: respectively adding Dy2O3 into a mixture of ZrO2, MgO and MoO3, adding ethanol, and grinding to obtain a mixed material A; and calcining the mixed material A to obtain the ZrMgMo3O12: Dy fluorescent powder.

Description

Technical Field

[0001] The invention relates to a thermal quenching resistant fluorescent powder and a preparation method and application thereof, belonging to the field of thermal imaging. Background Art

[0002] With the development of science and technology, the requirements for material performance in high temperature environments are getting higher and higher. In the fields of aerospace, energy, electronics, etc., materials need to have the ability to maintain stable performance in high temperature environments. Thermal imaging phosphor 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 the target object can be clearly observed under low light conditions or high temperature environments; the application of thermal imaging phosphor can play an important role in many fields, such as industrial detection, security monitoring, fire rescue, medical diagnosis, etc. It can help people detect and analyze the temperature distribution of objects more accurately, find potential problems or abnormalities, and improve work efficiency and safety.

[0003] The technology of thermal imaging phosphors mainly involves the following aspects: 1. Preparation of phosphors: The phosphors are prepared into a uniform coating or doped into other materials by appropriate methods to ensure their uniform distribution and effective excitation in thermal imaging equipment. 2. Excitation light source: Thermal imaging equipment usually uses infrared lasers or other near-infrared light sources to excite phosphors to emit visible light. 3. Image processing: The collected thermal imaging phosphor images need to be enhanced and analyzed by specific image processing algorithms to extract useful thermal information.

[0004] 4. Temperature measurement and analysis: By analyzing the visible light emitted by the phosphor, the temperature distribution and changes of the target object can be determined, thereby realizing the thermal imaging function; the specific thermal imaging phosphor technology and application will vary depending on different needs and equipment. In actual applications, factors such as the stability, lifespan, and compatibility with other components of the phosphor also need to be considered.

[0005] However, phosphor thermal imaging also has some limitations. When the temperature is too high, the phosphor will undergo thermal quenching, causing the luminescence to weaken or disappear, which will greatly affect the phosphor thermal imaging function. For example, CaWO4:Yb, Er phosphor, under 980nm laser excitation, the luminescence gradually decreases with increasing temperature, and severe thermal quenching occurs at 300℃, and the excitation light source is relatively single, so its application in thermal imaging is limited.

[0006] In general, phosphor thermal imaging technology provides a fast, non-contact and intuitive temperature measurement method in many applications, but the existing phosphors are easily quenched at high temperatures and can only emit light under a single excitation light, which limits their application areas. Summary of the invention

[0007] In order to solve the problems existing in the existing phosphors, one of the purposes of the present invention is to provide a thermal quenching resistant phosphor. The general formula of the thermal quenching resistant phosphor is ZrMgMo3O 12 :Dy.

[0008] Another object of the present invention is to provide an application of thermal quenching resistant phosphor in thermal imaging.

[0009] The third object of the present invention is to provide a ZrMgMo3O 12 The preparation method of the heat quenching resistant phosphor of Dy is as follows:

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

[0011] (2) Calcine the mixed material I to obtain ZrMgMo3O 12 :Dy phosphor.

[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 calcination temperature in step (2) is 800-900° C., the time is 5-6 hours, the heating rate is 2-5° C. / min, and the atmosphere is air.

[0014] Beneficial effects of the present invention

[0015] (1) This invention uses negative thermal expansion material ZrMgMo3O for the first time 12 As a matrix, a ZrMgMo3O 12 :Dy fluorescent powder, the prepared fluorescent powder has good resistance to thermal quenching. Most of the existing fluorescent powders will be quenched at 100°C, while the fluorescent powder prepared by the present invention maintains good luminescence performance at 300°C. Therefore, the fluorescent powder of the present invention has a wider range of uses.

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

[0017] Figure 1 This is a fluorescence spectra of the phosphor in Example 1 measured by an F7000 fluorescence spectrometer at temperatures of 20°C, 60°C, 100°C, 140°C, 180°C, 220°C, 260°C, and 300°C under the excitation of a 292nm ultraviolet lamp.

[0018] Figure 2 This is a fluorescence spectra of the phosphor in Example 1 measured by an F7000 fluorescence spectrometer at temperatures of 20°C, 60°C, 100°C, 140°C, 180°C, 220°C, 260°C, and 300°C under the excitation of a 360nm ultraviolet lamp.

[0019] Figure 3 This is a fluorescence spectra of the phosphor in Example 1 measured by an F7000 fluorescence spectrometer at temperatures of 20°C, 60°C, 100°C, 140°C, 180°C, 220°C, 260°C, and 300°C under the excitation of a 393nm ultraviolet lamp.

[0020] Figure 4 This is a fluorescence spectra of the phosphor in Example 1 measured by an F7000 fluorescence spectrometer at temperatures of 20°C, 60°C, 100°C, 140°C, 180°C, 220°C, 260°C, and 300°C under the excitation of a 471nm ultraviolet lamp. DETAILED DESCRIPTION

[0021] The technical solution of the present invention is further described below in conjunction with the accompanying drawings and through specific implementation methods. However, the following embodiments are merely simple examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0022] Example 1

[0023] A method for preparing a thermal quenching resistant fluorescent powder comprises:

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

[0025] (2) The mixed material I was placed in an alumina crucible and placed in a box furnace. The temperature was raised to 800°C at a rate of 5°C / min and sintered for 6 hours in an air atmosphere. After cooling, ZrMgMo3O12 :Dy phosphor.

[0026] Prepared ZrMgMo3O 12 :Dy phosphor for thermal imaging applications:

[0027] (1) ZrMgMo3O 12 The Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the results were obtained by using F7000 fluorescence spectrometer. Figure 1 As shown in the fluorescence spectrum, it can be seen from the spectrum that the fluorescence intensity of the yellow light peak (580nm) gradually increases with the increase of temperature under the 292nm excitation light source, showing excellent resistance to thermal quenching, indicating that its thermal imaging function is excellent.

[0028] (2) ZrMgMo3O 12 The Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the results were obtained by using F7000 fluorescence spectrometer. Figure 2 As shown in the fluorescence spectrum, it can be seen from the spectrum that the fluorescence intensity of the yellow light peak (580nm) first increases and then decreases with the increase of temperature under the 360nm excitation light source, and can still maintain 1.5 times the initial fluorescence intensity at 300°C, indicating that it has excellent thermal imaging function.

[0029] (3) ZrMgMo3O 12 The Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the results were obtained by using F7000 fluorescence spectrometer. Figure 3 As shown in the fluorescence spectrum, it can be seen from the spectrum that the fluorescence intensity of the yellow light peak (580nm) first increases and then decreases with the increase of temperature under the 393nm excitation light source, and can still maintain 1.2 times the initial fluorescence intensity at 300°C, indicating that it has excellent thermal imaging function.

[0030] (4) ZrMgMo3O 12 The Dy phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the results were obtained by using F7000 fluorescence spectrometer. Figure 4 As shown in the fluorescence spectrum, it can be seen from the spectrum that the fluorescence intensity of the yellow light peak (580nm) remains basically unchanged with the increase of temperature under the 471nm excitation light source, and the luminous intensity stability is good at 20-300℃, indicating that it has excellent thermal imaging function.

[0031] Comparative Example 1

[0032] A method for preparing a thermal quenching resistant fluorescent powder comprises:

[0033] (1) Add 0.0880 g of Eu2O3 to a mixture of 0.5545 g of ZrO4, 2.1591 g of MoO3, and 0.2015 g of MgO, add ethanol and grind to obtain a mixture I.

[0034] (2) The mixed material I was placed in an alumina crucible and placed in a box furnace. The temperature was raised to 800°C at a rate of 5°C / min and sintered for 6 hours in an air atmosphere. After cooling, ZrMgMo3O 12 :Eu phosphor.

[0035] Prepared ZrMgMo3O 12 :Eu phosphor as thermal imaging application:

[0036] (1) ZrMgMo3O 12 The Eu phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum obtained by testing with F7000 fluorescence spectrometer showed that the fluorescence intensity gradually increased with the increase of temperature under 292nm excitation light source, showing resistance to thermal quenching, indicating that it has thermal imaging function.

[0037] (2) ZrMgMo3O 12 :Eu phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, and 300℃, and the fluorescence spectrum obtained by using F7000 fluorescence spectrometer was tested. Under 360nm excitation light source, the fluorescence intensity gradually decreased with the increase of temperature, and the luminescence was severely quenched, so its application range was limited. (3) ZrMgMo3O 12 :Eu phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum was obtained by testing with F7000 fluorescence spectrometer. Under 393nm excitation light source, the fluorescence intensity gradually decreased with increasing temperature, and the luminescence was severely quenched, so its application range is limited.

[0038] (4) ZrMgMo3O 12 :Eu phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃, and 300℃, and the fluorescence spectrum obtained by using F7000 fluorescence spectrometer showed that the fluorescence intensity gradually decreased with the increase of temperature under 471nm excitation light source, and the luminescence was severely quenched, so its application range was limited. 12:Eu phosphor is resistant to thermal quenching under 292nm excitation light source, but it suffers from severe thermal quenching at 360nm, 393nm and 471nm. It has limitations on excitation light source, resulting in the limitation of thermal imaging function to a single excitation light source.

[0039] Comparative Example 2

[0040] A method for preparing a thermal quenching resistant fluorescent powder comprises:

[0041] (1) 0.0934 g of Tb4O7 was added to a mixture of 0.5545 g of rhodium oxide, 2.1591 g of MoO3 and 0.2015 g of MgO, and ethanol was added to grind the mixture to obtain a mixture material I.

[0042] (2) The mixed material I was placed in an alumina crucible and placed in a box furnace. The temperature was raised to 800°C at a rate of 5°C / min and sintered for 6 hours in an air atmosphere. After cooling, ZrMgMo3O 12 :Tb phosphor.

[0043] Prepared ZrMgMo3O 12 :Tb phosphor as thermal imaging application:

[0044] (1) ZrMgMo3O 12 :Tb phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum was obtained by testing with F7000 fluorescence spectrometer. Under 292nm excitation light source, the fluorescence intensity gradually decreased with increasing temperature, and the luminescence was severely quenched, so its application range is limited.

[0045] (2) ZrMgMo3O 12 :Tb phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum was obtained by testing with F7000 fluorescence spectrometer. Under 360nm excitation light source, the fluorescence intensity gradually decreased with increasing temperature, and the luminescence was severely quenched, so its application range is limited.

[0046] (3) ZrMgMo3O 12 :Tb phosphor was heated at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃, and the fluorescence spectrum was obtained by testing with F7000 fluorescence spectrometer. Under 393nm excitation light source, the fluorescence intensity gradually decreased with increasing temperature, and the luminescence was severely quenched, so its application range is limited.

[0047] (4) ZrMgMo3O 12The fluorescence spectrum of the Tb phosphor was obtained by heating it at 20℃, 60℃, 100℃, 140℃, 180℃, 220℃, 260℃ and 300℃ using a F7000 fluorescence spectrometer. The fluorescence intensity gradually decreased with the increase of temperature under the 471nm excitation light source, and the luminescence was severely quenched, so its application range was limited. 12 :Tb phosphor undergoes severe thermal quenching under 292nm excitation light, 360nm, 393nm, and 471nm, and does not have thermal imaging function.

[0048] Comparative Example 3

[0049] Preparation of a thermal quenching resistant fluorescent powder. For 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) 0.0856 g of Dy2O3 was added to a mixture of 0.9867 g of Y2O3 and 1.9864 g of MoO3, and ethanol was added to grind to obtain a mixture I.

[0051] (2) The mixed material I was placed in an alumina crucible and placed in a box furnace. The temperature was raised to 800°C at a rate of 5°C / min and sintered for 6 hours in an air atmosphere. After cooling, Y2Mo3O 12 :Dy phosphor.

[0052] The thermal quenching resistance of the fluorescent powder prepared in this comparative example is not as good as that in Example 1. 12 :Dy is relatively poor and hygroscopic. At low temperatures, the presence of lattice water will hinder the formation of Y2Mo3O 12 Negative thermal expansion properties lead to Y2Mo3O 12 :Dy has poor thermal quenching resistance, while ZrMgMo3O 12 :Dy phosphor, due to ZrMgMo3O 12 The crystal structure has good rigidity and weak hygroscopicity, and its thermal quenching resistance will not be affected at low temperatures.

[0053] The specific embodiments of the present invention are described in detail above, but the present invention is not limited to the above embodiments. Various changes can be made within the knowledge scope of ordinary technicians in this field without departing from the purpose of the present invention.

Claims

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

2. The method for preparing the heat quenching resistant phosphor according to claim 1, characterized in that: The specific steps include: (1) Dy2O3 is added to a mixture of ZrO2, MgO and MoO3 respectively, and ethanol is added and ground to obtain a mixed material I; (1) Calcine the mixed material I to obtain ZrMgMo3O 12 :Dy phosphor.

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

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

5. Application of the thermal quenching resistant fluorescent powder according to claim 1 in thermal imaging.

Images