WO2023221150A1 - 一种荧光测温材料及其制备方法和应用 - Google Patents

一种荧光测温材料及其制备方法和应用 Download PDF

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WO2023221150A1
WO2023221150A1 PCT/CN2022/094635 CN2022094635W WO2023221150A1 WO 2023221150 A1 WO2023221150 A1 WO 2023221150A1 CN 2022094635 W CN2022094635 W CN 2022094635W WO 2023221150 A1 WO2023221150 A1 WO 2023221150A1
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temperature
fluorescent
temperature measurement
fluorescence
fluorescent thermometer
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French (fr)
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高妍
崔燕
宋济安
孟智超
胡桃
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五邑大学
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K11/00—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00
    • G01K11/20—Measuring temperature based upon physical or chemical changes not covered by groups G01K3/00, G01K5/00, G01K7/00 or G01K9/00 using thermoluminescent materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G35/00—Compounds of tantalum
    • C01G35/006—Compounds containing, besides tantalum, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
    • C09K11/7703—Chalogenides with alkaline earth metals
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K15/00—Testing or calibrating of thermometers
    • G01K15/002—Calibrated temperature sources, temperature standards therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
    • G01K15/00—Testing or calibrating of thermometers
    • G01K15/005—Calibration
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

Definitions

  • the invention belongs to the technical field of fluorescent temperature sensing, and specifically relates to a fluorescent temperature measurement material and its preparation method and application.
  • Temperature measurement is closely related to our daily life. It plays a vital role in medicine, chemistry, military technology and life production. Today, with the rapid development of science, technology and medical protection, people have put forward higher requirements for the accuracy and applicable range of temperature measurement instruments. However, traditional contact thermometers such as glass thermometers, thermocouples, and thermistors are difficult to meet. New requirements.
  • Fluorescent temperature sensing technology is considered to be a promising optical temperature measurement technology due to its fast response speed, high spatial resolution and non-contact characteristics.
  • the fluorescence intensity ratio (FIR) temperature measurement technology uses the law of the change of the two emission peak intensities of luminescent materials with temperature to realize temperature detection. It is not affected by the surrounding environment, has low requirements on the temperature detection environment, and has fast response speed and With the advantages of high spatial resolution, self-calibration and high sensitivity, it has broader application prospects.
  • FIR fluorescence thermometers use the fluorescence intensity ratio of two thermal coupling energy levels of lanthanide ions such as Er 3+ , Tm 3+ and Ho 3+ to measure temperature.
  • the energy gap of the thermal coupling energy level of this type of ion is small, which is not conducive to the discrimination of optical signals and also limits the further improvement of temperature measurement sensitivity. Therefore, the preparation of fluorescent temperature measurement materials with better light signal discrimination and higher sensitivity is a technical problem that needs to be solved at present.
  • the purpose of the present invention is to overcome the problems existing in the above-mentioned prior art and provide a fluorescent temperature measurement material and its preparation method and application.
  • the energy level difference is around 3500cm -1 , and their emission peak positions are respectively located in the blue light band ( 3 P 0 ⁇ 3 H 4 ) and red light band ( 1 D 2 ⁇ 3 H 4 ), with good optical signal discrimination.
  • Pr 3+ ions are incorporated into orthorhombic phase perovskite, and the prepared fluorescent temperature measurement material has ultra-high temperature measurement sensitivity.
  • Another object of the present invention is to provide a method for preparing the fluorescent thermometer material, which includes the following steps: weighing raw materials according to the chemical composition, mixing, adding solvent, grinding, pre-calcining, grinding again, and calcining.
  • the raw materials include Na 2 CO 3 , SrCO 3 , Ta 2 O 5 , and Pr 6 O 11 .
  • the solvent is absolute ethanol
  • the grinding time is 20 to 40 minutes; preferably, the grinding time is 30 minutes.
  • the pre-calcining temperature is 300°C to 500°C and the time is 1h to 3h; preferably, the pre-calcining temperature is 400°C and the time is 2h.
  • the re-grinding time is 10 min to 20 min; preferably, the re-grinding time is 15 min.
  • the calcination temperature is 900°C to 1050°C and the time is 6h to 10h; preferably, the calcination time is 8h.
  • Another object of the present invention is to provide the application of the fluorescent temperature measurement material and its preparation method in temperature sensing.
  • the fluorescent thermometer material of the present invention 290 nm ultraviolet light is used to excite the fluorescent thermometer material, and the ratio of the emission peak intensity at 492 nm and the emission peak intensity at 610 nm of the material is measured, which is the calibration temperature.
  • the fluorescent thermometer material of the present invention produces emission peaks at 492nm and 610nm when excited by 290nm ultraviolet light, corresponding to the 3 P 0 ⁇ 3 H 4 and 1 D 2 ⁇ 3 H 4 radiation transitions of Pr 3+ .
  • the fluorescence intensity ratio of the material 1 D 2 ⁇ 3 H 4 / 3 P 0 ⁇ 3 H 4 ) has an exponential function relationship with the temperature, which can be used to calibrate the temperature, and one of the two emission peaks is located in the blue light band (492nm), and one in the red band (610nm), with excellent signal discrimination.
  • the particle size of the fluorescent temperature measurement material of the present invention is less than 1 ⁇ m, has good spatial resolution, and the CIE coordinates change significantly with temperature. It has ultra-high sensitivity and signal resolution, and has huge applications in the field of optical temperature measurement. potential.
  • Figure 1 is an XRD pattern of the fluorescent thermometer material of Example 1-3;
  • Figure 3 is an SEM image of the fluorescent thermometer material of Example 1;
  • Figure 4 is the variable temperature spectrum (303K-483K) of the fluorescent thermometer material in Example 1, and the excitation wavelength is 290nm;
  • Figure 5(a) shows the intensity (303K-483K) of the emission peak of the fluorescent thermometer material of Example 1 at 492nm (blue), and (b) shows the intensity of the emission peak of the fluorescent thermometer material of Example 1 at 610nm (red). Strength (303K-483K);
  • Figure 6 is a fitting diagram of the fluorescence intensity ratio ( 1 D 2 ⁇ 3 H 4 / 3 P 0 ⁇ 3 H 4 ) of the fluorescent thermometer material in Example 1;
  • Figure 7 shows the CIE color coordinates of the fluorescent thermometer material of Example 1 in the range of 303K-483K;
  • Figure 8 is the absolute sensitivity S a and relative sensitivity S r curves of the fluorescent thermometer material in Example 1;
  • Figure 9 is the variable temperature spectrum (303K-483K) of the fluorescent thermometer material in Example 2, and the excitation wavelength is 290nm;
  • Figure 10 is the variable temperature spectrum (303K-483K) of the fluorescent thermometer material in Example 3, and the excitation wavelength is 290nm;
  • Figure 12 shows the variable temperature spectrum (303K-483K) of the fluorescent thermometer material of Comparative Example 1, with an excitation wavelength of 290nm;
  • Figure 13(a) is the XRD pattern of the fluorescent thermometer material of Comparative Example 2
  • Figure 14 shows the variable temperature spectrum (303K-483K) of the fluorescent thermometer material of Comparative Example 2, and the excitation wavelength is 290nm.
  • test methods used in the examples are conventional methods; unless otherwise specified, the materials and reagents used can be obtained from commercial sources.
  • the material of the invention is used for non-contact temperature measurement.
  • Example 3 A scanning electron microscope was used to detect the SEM image of the fluorescent temperature measuring material of Example 1. The results are shown in Figure 3.
  • the Na 0.85 Sr 0.15 TaO 3 :0.5% Pr 3+ fluorescent temperature measuring material prepared in Example 1 has a particle size of less than 1 ⁇ m. , with better spatial resolution.
  • FIG. 4 shows the variable temperature spectrum (303K-483K) of the material of Example 1. It can be seen from Figure 4 that the Na 0.85 Sr 0.15 TaO 3 of Example 1 :0.5% Pr 3+ material has two strong main emission peaks at 492nm and 610nm in the range of 303K-483K, indicating that the material of Example 1 has good temperature measurement performance in the range of 303K-483K ;
  • Figure 5(a) is the intensity (303K-483K) of the emission peak of the fluorescent thermometer material of Example 1 at 492nm (blue),
  • (b) is the emission peak of the fluorescent thermometer material of Example 1 at 610nm (red) intensity (303K-483K); as shown in Figure 5a, as the temperature increases from 303K to 483K, the emission peak intensity I 492 located at 492nm ( 3 P 0 ⁇ 3 H 4 ) (take the integrated intensity from
  • Figure 6 shows the fluorescence intensity ratio of the fluorescent thermometer material in Example 1 ( 1 D 2 ⁇ 3 H 4 / 3 P 0 ⁇ 3 H 4 ) fitting diagram.
  • Figure 7 shows the CIE color coordinates of the fluorescent thermometer material of Example 1 in the range of 303-483K. As the temperature increases, the CIE color coordinates change significantly, indicating that the temperature can be judged by the change in the sample's luminescence color.
  • Figure 8 shows the absolute sensitivity S a and relative sensitivity S r curves of the fluorescent temperature measurement material in Example 1, indicating that the material has ultra-high temperature measurement sensitivity.
  • Figure 9 is the temperature-changing spectrum of the fluorescent thermometric material of Example 2
  • Figure 10 is the temperature-changing spectrum of the fluorescent thermometric material of Example 3.
  • the excitation wavelength is 290 nm. It can be seen from Figure 9 and Figure 10 that the Na 0.9 Sr 0.1 TaO 3 :0.5% Pr 3+ material of Example 2 and the Na 0.8 Sr 0.2 TaO 3 :0.5% Pr 3+ material of Example 3 are at 303K-483K. Within the range, they all have two strong main emission peaks at 492nm and 610nm, and their fluorescence intensity ratio I 610 /I 492 ( 1 D 2 ⁇ 3 H 4 / 3 P 0 ⁇ 3 H 4 ) is consistent with the temperature. Exponential function relationship, can be used as temperature measurement material.
  • Figure 12 is the emission spectrum of the fluorescent thermometer material of Comparative Example 1 Variable temperature spectrum (303K-483K), excitation wavelength is 290nm; as can be seen from Figure 12, as the temperature increases, the emission peak intensity of the fluorescent thermometer material of Comparative Example 1 at 492nm and the emission peak intensity at 610nm both change significantly. decreases. At this time, the 610nm emission peak cannot be used as a reference signal, indicating that the Na 0.95 Sr 0.05 TaO 3 :0.5% Pr 3+ material of Comparative Example 1 is not suitable for use as a proportional temperature sensing material.
  • Figure 14 is the emission spectrum of the fluorescent thermometer material of Comparative Example 2 Variable temperature spectrum (303K-483K), excitation wavelength is 290nm; as can be seen from Figure 14, the Na 0.7 Sr 0.3 TaO 3 :0.5% Pr 3+ material of Comparative Example 2 increases as the temperature increases, and the intensity of the emission peak at 492nm decreases. It is relatively slow and is not conducive to monitoring signals as a temperature probe.

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Abstract

一种荧光测温材料及其制备方法和应用，属于荧光温度传感技术领域。荧光测温材料，其化学组成为Na 1-xSr xTaO 3:yPr 3+，其中x＝0.1～0.2，y＝0.4％～0.6％。荧光测温材料通过高温固相法制备，在290nm紫外光激发下产生位于492nm( 3P 0→ 3H 4)的蓝色发光和位于610nm( 1D 2→ 3H 4)的红色发光。两个发射峰的荧光强度比( 1D 2→ 3H 4/ 3P 0→ 3H 4)与温度呈现指数函数关系，能够标定温度，具有较好的温敏性能。此外，荧光测温材料的颗粒尺寸小于1μm，具有较好的空间分辨率，且CIE色坐标随温度变化显著。荧光测温材料具有超高灵敏度和信号分辨力，在光学测温领域具有很高的应用潜力。

Description

一种荧光测温材料及其制备方法和应用 技术领域
本发明属于荧光温度传感技术领域，具体涉及一种荧光测温材料及其制备方法和应用。
背景技术
温度测量与我们的日常生活密切相关，它在医学、化学、军事技术和生活生产中都起着至关重要的作用。在科学技术与医疗防护快速发展的今天，人们对测温仪器的准确度和其能够适用的范围提出了更高的要求，但是玻璃温度计、热电偶、热敏电阻等传统的接触式温度计难以满足新要求。
荧光温度传感技术由于其响应速度快、空间分辨率高以及非接触式等特点，被认为是一种具有发展前景的光学测温技术。其中利用发光材料两个发射峰强度随温度变化的规律实现温度探测的荧光强度比(FIR)测温技术，不受周围环境的影响，对温度探测环境的要求较低，又具备响应速度快、高空间分辨率、自校准以及高灵敏度等优点，应用前景更广阔。
多数已报道的FIR荧光温度计都是利用Er 3+、Tm 3+和Ho 3+等镧系离子两个热耦合能级的荧光强度比来进行测温的。这类离子的热耦合能级的能隙较小，不利于光信号的甄别，也限制了测温灵敏度的进一步提高。因此，制备有较好的光信号甄别度，灵敏度更高的荧光测温材料是目前需解决的技术问题。
发明内容
本发明的目的在于克服上述现有技术中存在的问题，提供一种荧光测温材料及其制备方法和应用。
本发明是通过下述技术方案进行实现的：
本发明提供一种荧光测温材料，其化学组成为Na 1-xSr xTaO 3:yPr 3+，其中x＝0.1～0.2，y＝0.4％～0.6％。
本发明将Pr 3+离子掺入正交相钙钛矿Na 1-xSr xTaO 3(x＝0.1～0.2)固溶体中，Pr 3+离子的 3P 0和 1D 2能级之间的能级差在3500cm -1左右，它们的发射峰位置分别位于蓝光波段( 3P 0→ 3H 4)和红光波段( 1D 2→ 3H 4)，具有较好的光信号甄别度。本发明将Pr 3+离子掺入正交相钙钛矿中，制得的荧光测温材料具有超高的测温灵敏度。
作为本发明所述荧光测温材料的优选实施方式，所述x＝0.15，y＝0.5％。
本发明的又一目的在于提供所述荧光测温材料的制备方法，包括以下步骤：按所述化学组成称取原料，混均，加入溶剂，研磨，预烧，再次研磨，煅烧，即得。
作为本发明所述荧光测温材料的制备方法的优选实施方式，所述原料包括Na 2CO 3、SrCO 3、Ta 2O 5、Pr 6O 11。
作为本发明所述荧光测温材料的制备方法的优选实施方式，所述溶剂为无水乙醇，所述研磨的时间为20min～40min；优选地，所述研磨的时间为30min。
作为本发明所述荧光测温材料的制备方法的优选实施方式，所述预烧的温度为300℃～500℃，时间为1h～3h；优选地，所述预烧的温度为400℃，时间为2h。
作为本发明所述荧光测温材料的制备方法的优选实施方式，所述再次研磨的时间为10min～20min；优选地，所述再次研磨的时间为15min。
作为本发明所述荧光测温材料的制备方法的优选实施方式，所述煅烧的温度为900℃～1050℃，时间为6h～10h；优选地，所述煅烧的时间为8h。
本发明的再一目的在于提供所述荧光测温材料及其制备方法在温度传感中的应用。
作为本发明所述荧光测温材料的应用的优选实施方式，使用290nm紫外光激发所述荧光测温材料，测量该材料492nm处发射峰强度和610nm处发射峰强度的比值，即为标定温度。
本发明的有益效果为：
(1)本发明的荧光测温材料在290nm紫外光激发下产生位于492nm、610nm的发射峰，对应Pr 3+的 3P 0→ 3H 4和 1D 2→ 3H 4辐射跃迁。在303K-483K范围内，材料的荧光强度比( 1D 2→ 3H 4/ 3P 0→ 3H 4)与温度具有指数函数关系，可用于标定温度，且这两个发射峰一个位于蓝光波段(492nm)，一个位于红光波段(610nm)，具备优异的信号甄别度。
(2)本发明的荧光测温材料的颗粒尺寸小于1μm，具有较好的空间分辨率，且CIE坐标随温度变化显著，具有超高灵敏度和信号分辨力，在光学测温领域具有巨大的应用潜力。
附图说明
图1为实施例1-3荧光测温材料的XRD图；
图2为实施例1-3荧光测温材料的常温发射光谱(λ ex＝290nm)；
图3为实施例1荧光测温材料的SEM图；
图4为实施例1荧光测温材料的变温光谱(303K-483K)，激发波长为290nm；
图5(a)为实施例1荧光测温材料位于492nm(蓝色)处发射峰的强度(303K-483K)，(b)为实施例1荧光测温材料位于610nm(红色)处发射峰的强度(303K-483K)；
图6为实施例1荧光测温材料的荧光强度比( 1D 2→ 3H 4/ 3P 0→ 3H 4)的拟合图；
图7为实施例1荧光测温材料在303K-483K范围内的CIE色坐标；
图8为实施例1荧光测温材料的绝对灵敏度S a和相对灵敏度S r曲线；
图9为实施例2荧光测温材料的变温光谱(303K-483K)，激发波长为290nm；
图10为实施例3荧光测温材料的变温光谱(303K-483K)，激发波长为290nm；
图11(a)为对比例1荧光测温材料的XRD图，(b)为对比例1荧光测温材料的常温发射光谱(λ ex＝290nm)；
图12为对比例1荧光测温材料的变温光谱(303K-483K)，激发波长为290nm；
图13(a)为对比例2荧光测温材料的XRD图，(b)为对比例2荧光测温材料的常温发射光谱(λ ex＝290nm)；
图14为对比例2荧光测温材料的变温光谱(303K-483K)，激发波长为290nm。
具体实施方式
为更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例对本发明作进一步说明。本领域技术人员应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。
实施例中所用的试验方法如无特殊说明，均为常规方法；所用的材料、试剂等，如无特殊说明，均可从商业途径得到。本发明材料用于非接触式温度测量。
实施例1
将0.3mmol SrCO 3，0.85mmol Na 2CO 3，1mmol Ta 2O 5以及0.00167mmol Pr 6O 11混合均匀，加入5ml无水乙醇在玛瑙研钵中研磨30min，装入刚玉坩埚中并放入马弗炉内在400℃下预烧2h。待样品冷却后，再将其置于研钵中匀速研磨15min。将重新研磨好的粉末装入坩埚中送入马弗炉内在1000℃下煅烧8h，最后将冷却 的样品重新研磨至颗粒均匀后，得到Na 0.85Sr 0.15TaO 3:0.5％Pr 3+材料。
实施例2
将0.2mmol SrCO 3，0.9mmol Na 2CO 3，1mmol Ta 2O 5以及0.00167mmol Pr 6O 11混合均匀，加入5ml无水乙醇在玛瑙研钵中研磨30min，装入刚玉坩埚中并放入马弗炉内在400℃下预烧2h。待样品冷却后，再将其置于研钵中匀速研磨15min。将重新研磨好的粉末装入坩埚中送入马弗炉内在1000℃下煅烧8h，最后将冷却的样品重新研磨至颗粒均匀后，得到Na 0.9Sr 0.1TaO 3:0.5％Pr 3+材料。
实施例3
将0.4mmol SrCO 3，0.8mmol Na 2CO 3，1mmol Ta 2O 5以及0.00167mmol Pr 6O 11混合均匀，加入5ml无水乙醇在玛瑙研钵中研磨30min，装入刚玉坩埚中并放入马弗炉内在400℃下预烧2h。待样品冷却后，再将其置于研钵中匀速研磨15min。将重新研磨好的粉末装入坩埚中送入马弗炉内在1000℃下煅烧8h，最后将冷却的样品重新研磨至颗粒均匀后，得到Na 0.8Sr 0.2TaO 3:0.5％Pr 3+材料。
对比例1
将0.1mmol SrCO 3，0.95mmol Na 2CO 3，1mmol Ta 2O 5以及0.00167mmol Pr 6O 11混合均匀，加入5ml无水乙醇在玛瑙研钵中研磨30min，装入刚玉坩埚中并放入马弗炉内在400℃下预烧2h。待样品冷却后，再将其置于研钵中匀速研磨15min。将重新研磨好的粉末装入坩埚中送入马弗炉内在1000℃下煅烧8h，最后将冷却的样品重新研磨至颗粒均匀后，得到Na 0.95Sr 0.05TaO 3:0.5％Pr 3+材料。
对比例2
将0.6mmol SrCO 3，0.7mmol Na 2CO 3，1mmol Ta 2O 5以及0.00167mmol Pr 6O 11混合均匀，加入5ml无水乙醇在玛瑙研钵中研磨30min，装入刚玉坩埚中并放入马弗炉内在400℃下预烧2h。待样品冷却后，再将其置于研钵中匀速研磨15min。将重新研磨好的粉末装入坩埚中送入马弗炉内在1000℃下煅烧8h，最后将冷却的样品重新研磨至颗粒均匀后，得到Na 0.7Sr 0.3TaO 3:0.5％Pr 3+材料。
应用例
采用X射线衍射仪检测实施例1-3荧光测温材料的XRD图，结果如图1所示，可以看出，0.5％Pr 3+的掺杂不会影响正交相钙钛矿的晶体结构。
采用荧光光谱仪检测实施例1-3的荧光测温材料的常温发射光谱(λ ex＝290nm)，结果如图2所示，在290nm的紫外光激发下，实施例1的 Na 0.85Sr 0.15TaO 3:0.5％Pr 3+材料、实施例2的Na 0.9Sr 0.1TaO 3:0.5％Pr 3+材料、实施例3的Na 0.8Sr 0.2TaO 3:0.5％Pr 3+材料均表现出两个较强的主发射峰，分别位于492nm和610nm，对应 3P 0→ 3H 4和 1D 2→ 3H 4跃迁。
采用扫描电子显微镜检测实施例1荧光测温材料的SEM图，结果如图3所示，实施例1制备的Na 0.85Sr 0.15TaO 3:0.5％Pr 3+荧光测温材料,其颗粒尺寸小于1μm，具有较好的空间分辨率。
采用FLS980荧光光谱仪对实施例1荧光测温材料进行变温光谱测试，图4为实施例1材料的变温光谱(303K-483K)，从图4可以看出，实施例1的Na 0.85Sr 0.15TaO 3:0.5％Pr 3+材料在303K-483K的范围内，均具有位于492nm和610nm处的两个较强的发射主峰，表明实施例1的材料在303K-483K范围内具有较好的测温性能；图5(a)为实施例1荧光测温材料位于492nm(蓝色)处发射峰的强度(303K-483K)，(b)为实施例1荧光测温材料位于610nm(红色)处发射峰的强度(303K-483K)；如图5a所示，随着温度从303K升高到483K，位于492nm( 3P 0→ 3H 4)处的发射峰强度I 492(取480nm～510nm积分强度)明显下降，而610nm( 1D 2→ 3H 4)处发射峰强度I 610(取585nm～638nm积分强度)则先增高后下降(如图5b所示)，其荧光强度比I 610/I 492( 1D 2→ 3H 4/ 3P 0→ 3H 4)与温度符合一定的指数函数关系，图6为实施例1荧光测温材料的荧光强度比( 1D 2→ 3H 4/ 3P 0→ 3H 4)的拟合图。通过计算492nm处发射峰强度与610nm发射峰强度比值I 610/I 492，然后在指数函数关系图中进行比对，即可得到待测物体的温度。
图7为实施例1荧光测温材料在303-483K范围内的CIE色坐标，随着温度的升高，CIE色坐标变化显著，表明可以通过样品发光颜色变化判断温度的高低。图8为实施例1荧光测温材料的绝对灵敏度S a和相对灵敏度S r曲线，表明该材料具有超高的测温灵敏度。
图9为实施例2荧光测温材料的变温光谱，图10为实施例3荧光测温材料的变温光谱，激发波长为290nm。从图9和图10可以看出，实施例2的Na 0.9Sr 0.1TaO 3:0.5％Pr 3+材料和实施例3的Na 0.8Sr 0.2TaO 3:0.5％Pr 3+材料在303K-483K的范围内，均具有位于492nm和610nm处的两个较强的发射主峰，其荧光强度比I 610/I 492( 1D 2→ 3H 4/ 3P 0→ 3H 4)与温度符合一定的指数函数关系，可用作测温材料。
图11(a)为对比例1荧光测温材料的XRD图，(b)为对比例1荧光测温材料 的常温发射光谱(λ ex＝290nm)；图12为对比例1荧光测温材料的变温光谱(303K-483K)，激发波长为290nm；从图12中可以看出，随着温度升高，对比例1的荧光测温材料在492nm处发射峰强度与610nm发射峰强度均发生了明显下降，此时610nm发射峰不能作为参比信号，表明对比例1的Na 0.95Sr 0.05TaO 3:0.5％Pr 3+材料不利于用作比例型温度传感材料。
图13(a)为对比例2荧光测温材料的XRD图，(b)为对比例2荧光测温材料的常温发射光谱(λ ex＝290nm)；图14为对比例2荧光测温材料的变温光谱(303K-483K)，激发波长为290nm；从图14中可以看出，对比例2的Na 0.7Sr 0.3TaO 3:0.5％Pr 3+材料随着温度升高，492nm处发射峰强度下降较为缓慢，不利于作为温度探针的监测信号。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种荧光测温材料，其特征在于，其化学组成为Na 1-xSr xTaO 3:yPr 3+，其中x＝0.1～0.2，y＝0.4％～0.6％。
  2. 根据权利要求1所述的荧光测温材料，其特征在于，所述x＝0.15，y＝0.5％。
  3. 权利要求1或2所述荧光测温材料的制备方法，其特征在于，包括以下步骤：按所述化学组成称取原料，混均，加入溶剂，研磨，预烧，再次研磨，煅烧，即得。
  4. 根据权利要求3所述的荧光测温材料的制备方法，其特征在于，所述原料包括Na 2CO 3、SrCO 3、Ta 2O 5、Pr 6O 11。
  5. 根据权利要求3所述的荧光测温材料的制备方法，其特征在于，所述研磨的时间为20min～40min。
  6. 根据权利要求3所述的荧光测温材料的制备方法，其特征在于，所述预烧的温度为300℃～500℃，时间为1h～3h。
  7. 根据权利要求3所述的荧光测温材料的制备方法，其特征在于，所述再次研磨的时间为10min～20min。
  8. 根据权利要求3所述的荧光测温材料的制备方法，其特征在于，所述煅烧的温度为900℃～1050℃，时间为6h～10h。
  9. 权利要求1或2所述荧光测温材料、权利要求3～8任一项权利要求所述的制备方法在温度传感中的应用。
  10. 根据权利要求9所述的荧光测温材料的应用，其特征在于，使用290nm紫外光激发所述荧光测温材料，测量该材料492nm处发射峰强度和610nm处发射峰强度的比值，即为标定温度。
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