CN110669508A - Temperature sensing material based on europium and manganese elements and preparation and application methods thereof - Google Patents
Temperature sensing material based on europium and manganese elements and preparation and application methods thereof Download PDFInfo
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- 239000011540 sensing material Substances 0.000 title claims abstract description 71
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 54
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 51
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000009529 body temperature measurement Methods 0.000 claims abstract description 18
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- 239000012190 activator Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 150000002823 nitrates Chemical class 0.000 claims description 8
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- 229910052733 gallium Inorganic materials 0.000 claims description 7
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- 150000001875 compounds Chemical class 0.000 description 8
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- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
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- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Inorganic materials [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
- CQQZFSZWNXAJQN-UHFFFAOYSA-K europium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Eu+3] CQQZFSZWNXAJQN-UHFFFAOYSA-K 0.000 description 1
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Inorganic materials [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
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- 150000002500 ions Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000012544 monitoring process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
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- 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
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
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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
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a temperature sensing material based on europium and manganese elements and a preparation method and an application method thereof, and the temperature sensing material has (Ca)14‑m‑xSrm)(Al10‑n‑yGan)(Zn6‑tMgt)O35:Eux 3+,Mny 4+Is used as a base material. The preparation method synthesizes the temperature sensing material under normal pressure and air atmosphere, does not need reducing atmosphere synthesis, and is simple and safe. Trivalent europium Eu (III) and tetravalent manganese Mn (IV) in the application method are used as double luminescence centers to simultaneously emit respective characteristic spectrums, the integral luminescence intensity ratio of the trivalent europium Eu (III) and the tetravalent manganese Mn (IV) is regularly changed along with the change of temperature, a standard working curve can be used for fitting, and two characteristic emission peaks with long wavelength distances of the trivalent europium Eu (III) and the tetravalent manganese Mn (IV) are detected, so that high signal discrimination is obtained, and the mutual interference of detection signals is avoided. The inventionThe temperature can be accurately calibrated, the temperature measurement range is wide, and the signal detection discrimination is high.
Description
Technical Field
The invention relates to the technical field of temperature sensing, in particular to a temperature sensing material based on europium and manganese elements and a preparation method and an application method thereof.
Background
The accurate measurement of temperature is of great significance in scientific research, technical application, daily life and various industries. With the rapid development and progress of the 5G technology and the technology of the Internet of things, higher requirements are put on the characteristics of the temperature sensor. In this context, non-contact temperature detection represented by optical temperature sensing technology is becoming a hot point of research.
Certain optical properties of the luminescent material may change with a change in temperature over a range of temperatures, and thus the change in optical properties of the luminescent material may be used to calibrate and detect the temperature. The most representative method is to adopt fluorescence intensity ratio for temperature measurement, and the conventional method for temperature measurement by using fluorescence intensity ratio at present is to select single rare earth ions as fluorescence activators to be doped into a main body matrix, and then select two energy levels with relatively close luminescent ion positions as thermal coupling pairs to realize temperature measurement. In order to satisfy this requirement for thermal coupling, the energy level of the thermal coupling must be limited to a small range. However, thermometric sensitivity is proportional to the difference in thermal coupling energy levels. Therefore, the temperature measurement sensitivity obtained by the technology cannot meet the requirement of high-precision measurement, and the simultaneous optimization and improvement of the temperature measurement sensitivity and the signal discrimination cannot be realized.
Therefore, it is very important to develop a new high-sensitivity temperature sensing method based on luminescent materials.
Disclosure of Invention
The invention aims to solve the technical problem of providing a temperature sensing material based on europium and manganese elements and a preparation and application method thereof, the temperature sensing material overcomes the defect of temperature measurement of the traditional fluorescence intensity ratio, the temperature measuring material has high sensitivity through the dual-luminescence characteristic of the europium and manganese elements, the preparation method is simple and safe, the temperature can be accurately calibrated by utilizing the fluorescence intensity ratio of the dual-luminescence center, and the temperature sensing material has the characteristics of wide temperature measurement range and high signal monitoring discrimination.
In order to solve the above technical problems, the temperature sensing material based on europium and manganese elements of the present invention has an atomic ratio composition represented by the following general formula (1):
(Ca14-m-xSrm)(Al10-n-yGan)(Zn6-tMgt)O35:Eux 3+,Mny 4+（1）
wherein (Ca)14-m-xSrm)(Al10-n-yGan)(Zn6-tMgt)O35Is an inorganic oxide host matrix, Eux 3+,Mny 4+For the activator doped into the inorganic oxide host matrix, the composition of the inorganic oxide host matrix needs to satisfy the valence and charge balance, m, n and t respectively represent the composition content parameters of the inorganic oxide host matrix, x and y respectively represent the doping content of the activator, and m, n and t satisfy the following conditions: m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and t is more than or equal to 0 and less than or equal to 1; x and y satisfy the following condition: x is more than or equal to 0.001 and less than or equal to 0.3, and y is more than or equal to 0.001 and less than or equal to 0.3.
Further, the temperature sensing material has an atomic ratio composition represented by the following general formula (2):
(Ca13.80Sr0.1)(Al9.75Ga0.1)(Zn5.9Mg0.1)O35:Eu0.10 3+,Mn0.15 4+（2）
wherein m =0.10, n =0.10, t =0.10, x =0.10, y = 0.15.
Further, the temperature sensing material has an atomic ratio composition represented by the following general formula (3):
(Ca13.45Sr0.5)(Al9.45Ga0.5)(Zn5.8Mg0.2)O35:Eu0.05 3+,Mn0.05 4+（3）
wherein m =0.50, n =0.50, t =0.20, x =0.05, y = 0.05.
Further, the form of the temperature sensing material is powder, a film or ceramic.
According to the preparation method, raw materials of carbonate, nitrate, oxide or hydroxide corresponding to Ca, Sr, Al, Ga, Zn, Mg, Eu and Mn are accurately weighed according to the atomic ratio, fully ground and mixed, then calcined at high temperature, cooled to room temperature and ground to obtain the temperature sensing material.
According to the preparation method, nitrates corresponding to Ca, Sr, Al, Ga, Zn, Mg, Eu and Mn are accurately weighed according to the atomic ratio, dissolved in deionized water to obtain a mixed solution, then citric acid is added into the mixed solution, dried to form gel, and sintered at low temperature to obtain the temperature sensing material.
An application method of the temperature sensing material based on the europium and manganese elements comprises the following steps:
doping trivalent europium Eu (III) and tetravalent manganese Mn (IV) activators into an inorganic oxide main body matrix to prepare a fluorescent temperature sensing material with trivalent europium Eu (III) and tetravalent manganese Mn (IV) emitting light together;
detecting the emission spectra of the fluorescent temperature sensing material at different temperatures, and establishing a standard working curve of the integral luminous intensity ratio of the trivalent europium Eu (III) emission peak and the tetravalent manganese Mn (IV) emission peak along with the temperature change;
placing the fluorescent temperature sensing material in a temperature environment to be measured, and measuring the emission spectrum of the fluorescent temperature sensing material so as to obtain the integral luminous intensity ratio of the trivalent europium Eu (III) emission peak and the tetravalent manganese Mn (IV) emission peak;
and step four, searching the integral luminous intensity ratio in the temperature environment to be measured according to the standard working curve so as to obtain the temperature measurement value of the environment to be measured, and completing the high-sensitivity optical temperature measurement based on the trivalent europium Eu (III) and tetravalent manganese Mn (IV) codoped dual-luminous characteristic.
Further, in the second step, the emission spectrum of the fluorescence temperature sensing material is detected within the temperature range of 303-563K.
Further, the standard working curve equation is as follows:
FIR=IMn4+/IEu3+=1553.69×exp(-2976/T)+0.8222 （4）
wherein FIR is the ratio of integrated luminous intensity, IEu3+And IMn4+The integral luminous intensity of the emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV) respectively, and T is absolute temperature.
Further, the integrated luminous intensity ratio and the absolute temperature satisfy the following exponential equation:
FIR = IMn4+/IEu3+= A×exp(B/T) + C （5）
wherein FIR is the ratio of integrated luminous intensity, T is absolute temperature, IEu3+And IMn4+The integrated luminescence intensities of the emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV), A, B, C are constants respectively.
Because the temperature sensing material based on europium and manganese elements and the preparation and application methods thereof adopt the technical scheme, the temperature sensing material has the structure of (Ca)14-m-xSrm)(Al10-n-yGan)(Zn6-tMgt)O35:Eux 3+,Mny 4+Wherein m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and t is more than or equal to 0 and less than or equal to 1; x is more than or equal to 0.001 and less than or equal to 0.3, and y is more than or equal to 0.001 and less than or equal to 0.3. The preparation method synthesizes the temperature sensing material under normal pressure and air atmosphere, does not need reducing atmosphere synthesis, and is simple and safe. Under the effective excitation of ultraviolet light, trivalent europium Eu (III) and quadrivalent manganese Mn (IV) are used as double luminescence centers to simultaneously emit respective characteristic spectrums, the integral luminescence intensity ratio of the trivalent europium Eu (III) and the quadrivalent manganese Mn (IV) shows regular change along with the change of temperature, a standard working curve can be used for fitting, and two characteristic emission peaks with far distance of wavelength, namely trivalent europium Eu (III) and quadrivalent manganese Mn (IV), are detected, so that high signal discrimination is obtained, and the mutual interference of detection signals is avoided. The invention can utilize double hairThe luminous intensity ratio of the optical center accurately calibrates the temperature, the temperature measurement range is wide, and the signal detection discrimination is high.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1 is a graph of an emission spectrum of a temperature sensing material under excitation of an ultraviolet light source according to an embodiment of the present invention;
FIG. 2 is a graph of the relationship between the luminescence intensity ratio and the temperature of the temperature sensing material and the corresponding fitting curve according to the embodiment of the present invention;
FIG. 3 is a graph of temperature measurement relative sensitivity and absolute sensitivity of a temperature sensing material according to an embodiment of the present invention.
Detailed Description
The following describes embodiments of the present invention in more detail with reference to examples. The following examples are for the purpose of illustrating the invention only and do not limit the scope of the invention.
The raw materials, instruments and reagents used in the invention are all commercial products, and can be purchased from the market.
Example one
Firstly, doping rare earth europium and a transition metal manganese activator into an inorganic oxide main body matrix according to reasonable concentration to prepare a fluorescent temperature sensing material with trivalent europium Eu (III) and quadrivalent manganese Mn (IV) emitting light together;
detecting the emission spectra of the fluorescent temperature sensing material at different temperatures, and establishing a standard working curve of the integral luminous intensity ratio of the characteristic emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV) along with the change of the environmental temperature;
thirdly, placing the fluorescent temperature sensing material in an environment with temperature to be measured, and measuring the emission spectrum of the fluorescent temperature sensing material so as to obtain the integral luminous intensity ratio of the characteristic emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV);
and fourthly, substituting the integrated luminous intensity ratio into the standard working curve in the second step to obtain a temperature measurement value of the environment to be measured, and completing the high-sensitivity optical temperature measurement based on the double luminous characteristics of trivalent europium Eu (III) and quadrivalent manganese Mn (IV).
The fluorescence temperature sensing material in the first step comprises the following specific atomic ratio components: (Ca)13.80Sr0.1)(Al9.75Ga0.1)(Zn5.9Mg0.1)O35:Eu0.10 3+,Mn0.15 4+。
The preparation method comprises the steps of accurately weighing carbonates corresponding to Ca, Sr and Mn and oxides corresponding to Al, Ga, Zn, Mg and Eu according to specific atomic ratio, fully grinding and mixing the raw materials, sintering at 1200 ℃ for 6 hours, cooling to room temperature, and grinding to obtain the temperature sensing material.
Fig. 1 is a spectrum of an emission spectrum of the fluorescent temperature sensing material prepared in example 1 under the excitation of an ultraviolet light source, and it can be clearly seen from the graph that under the effective excitation of ultraviolet light, trivalent europium Eu (iii) and tetravalent manganese Mn (iv) as dual luminescence centers can simultaneously emit characteristic emission peaks at 615 nm and 717 nm, respectively.
FIG. 2 is a graph of the relationship between the ratio of the luminescence intensity of the fluorescent temperature sensing material of example 1 and the temperature and the corresponding fitting curve. The ratio FIR of the luminous intensity of the double luminous centers to the absolute temperature T meets the following exponential equation,
FIR = IMn4+/IEu3+= A*exp(B/T) + C，
wherein, IEu3+And IMn4+The integrated luminescence intensity respectively represents the characteristic emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV), A, B, C is a constant, and T is absolute temperature.
By detecting the emission spectra of the fluorescence temperature sensing material at different temperatures, experimental data points of the fluorescence intensity ratio FIR and the absolute temperature T of the double luminescence centers are obtained, and the standard working curve equation of the embodiment is obtained by fitting an exponential equation
FIR = IMn4+/IEu3+= 1553.69×exp(-2976/T) + 0.8222。
FIG. 3 is a graph of the temperature measurement relative sensitivity and the absolute sensitivity of the fluorescent temperature sensing material of example 1 as a function of temperature.
Example two
The second embodiment is different from the first embodiment in that the specific atomic ratio composition of the fluorescent temperature sensing material prepared in the first step is as follows: (Ca)13.45Sr0.5)(Al9.45Ga0.5)(Zn5.8Mg0.2)O35:Eu0.05 3+,Mn0.05 4+Other steps and parameters are the same as those in the first embodiment.
EXAMPLE III
The third embodiment is different from the previous embodiments in that the specific atomic ratio composition of the fluorescent temperature sensing material prepared in the first step is as follows: (Ca)13.05Sr0.9)(Al9.00Ga0.9)(Zn5.2Mg0.8)O35:Eu0.05 3+,Mn0.10 4+Other steps and parameters are the same as those in the previous embodiment.
Example four
Different from the previous embodiment, the specific atomic ratio composition of the fluorescent temperature sensing material prepared in the first step is as follows: (Ca)12.90Sr1.0)(Al8.80Ga1.0)(Zn5.0Mg1.0)O35:Eu0.10 3+,Mn0.20 4+Other steps and parameters are the same as those in the previous embodiment.
EXAMPLE five
The fifth embodiment is different from the previous embodiments in that the specific atomic ratio composition of the fluorescent temperature sensing material prepared in the first step is as follows: (Ca)13.55Sr0.3)(Al9.35Ga0.4)(Zn5.5Mg0.5)O35:Eu0.15 3+,Mn0.25 4+Other steps and parameters are the same as those in the previous embodiment.
EXAMPLE six
The sixth embodiment is different from the previous embodiments in that the specific atomic ratio composition of the fluorescent temperature sensing material prepared in the first step is as follows: (Ca)13.05Sr0.9)(Al9.08Ga0.9)(Zn5.3Mg0.7)O35:Eu0.05 3+,Mn0.02 4+Other steps and parameters are the same as those in the previous embodiment.
It should be understood that the specific atomic ratio composition of the temperature sensing material of the present invention is not limited to the above-described composition, and any suitable composition is within the scope of the present patent application.
EXAMPLE seven
Seventh embodiment is different from the previous embodiments in that, the first step fluorescent temperature sensing material is prepared by dissolving nitrates corresponding to Ca, Sr, Al, Ga, Zn, Mg, Eu, and Mn in deionized water according to atomic ratio under stirring to obtain a mixed solution, adding citric acid into the mixed solution, drying at 90 ℃ to form a gel, and sintering at 500 ℃ and 1100 ℃ for 3h in steps to obtain the temperature sensing material, and other steps and parameters are the same as those of the previous embodiments.
Example eight
The eighth embodiment is different from the previous embodiments in that the first step is to dope europium and manganese by a sol-gel method or a high temperature solid phase method to prepare the temperature sensing material, and other steps and parameters are the same as those of the previous embodiments.
The sol-gel method and the high temperature solid phase method described in this example are conventional methods in the art.
Example nine
The ninth embodiment is different from the first embodiment in that the fluorescent temperature sensing material prepared in the first step is in the form of powder, film or ceramic, and other steps and parameters are the same as those of the first embodiment.
It should be understood that the form of the temperature sensing material of the present invention is not limited to the above-mentioned form, and any suitable form is within the scope of the present patent application.
Example ten
The tenth embodiment is different from the previous embodiments in that the emission spectrum of the fluorescence temperature sensing material is detected in the second step at the temperature range of 303 to 563K, and other steps and parameters are the same as those of the previous embodiments.
EXAMPLE eleven
In the eleventh embodiment, the calcium-containing compound is a mixture of one or more of calcium oxide, hydroxide, nitrate or carbonate, the ratio of the materials in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
Example twelve
In the twelfth embodiment, the strontium-containing compound is a mixture of one or more of strontium oxide, strontium hydroxide, strontium nitrate and strontium carbonate, the mixture ratio of the materials in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
EXAMPLE thirteen
In the thirteenth embodiment, the zinc-containing compound is a mixture of one or more of oxides, hydroxides, nitrates or carbonates of zinc, the ratio of each material in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
Example fourteen
In the fourteenth embodiment, the magnesium-containing compound is a mixture of one or more of oxides, hydroxides, nitrates or carbonates of magnesium, the ratio of each material in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the foregoing embodiment.
Example fifteen
In the fifteenth embodiment, the aluminum-containing compound is a mixture of one or more of oxides, hydroxides, nitrates or carbonates of aluminum, the ratio of each material in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
Example sixteen
In the sixteenth embodiment, the gallium-containing compound is a mixture of one or more of gallium oxide, hydroxide, nitrate or carbonate, the ratio of the materials in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
Example seventeen
In seventeenth embodiment, the europium-containing compound is a mixture of one or more of europium carbonate, europium nitrate, europium oxide, and europium hydroxide, the mixture ratio of the materials in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
EXAMPLE eighteen
In eighteen, the manganese-containing compound is a mixture of one or more of manganese oxide, hydroxide, nitrate or carbonate, the mixture ratio of each material in the mixture can be arbitrarily selected, and other steps and parameters are the same as those in the previous embodiment.
It can be seen from the above embodiments that, in the temperature sensing material of the high-sensitivity rare earth europium and transition metal manganese co-doped dual luminescence system of the present invention, under effective excitation of ultraviolet light, trivalent europium Eu (iii) and tetravalent manganese Mn (iv) as dual luminescence centers can simultaneously emit respective characteristic spectra, the fluorescence intensity ratios thereof show regular changes with temperature changes, and a standard working curve can be used for fitting, by detecting the two characteristic emission peaks with relatively long wavelength intervals, a relatively high signal discrimination is obtained, mutual interference of detection signals is avoided, the signal detection discrimination is large, the luminescence intensity ratio of the dual luminescence centers can be used for accurately calibrating temperature, and the temperature measurement range is wide.
It will be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been shown and described in detail herein, many other variations and modifications can be made, which are within the scope of this patent application, and which are consistent with the principles of this invention, as may be determined directly from the disclosure of the invention.
Claims (10)
1. A temperature sensing material based on europium and manganese elements is characterized in that: the temperature sensing material has an atomic ratio composition represented by the following general formula (1):
(Ca14-m-xSrm)(Al10-n-yGan)(Zn6-tMgt)O35:Eux 3+,Mny 4+（1）
wherein (Ca)14-m-xSrm)(Al10-n-yGan)(Zn6-tMgt)O35Is an inorganic oxide main body matrix, and is characterized in that,Eux 3+,Mny 4+for the activator doped into the inorganic oxide host matrix, the composition of the inorganic oxide host matrix needs to satisfy the valence and charge balance, m, n and t respectively represent the composition content parameters of the inorganic oxide host matrix, x and y respectively represent the doping content of the activator, and m, n and t satisfy the following conditions: m is more than or equal to 0 and less than or equal to 1, n is more than or equal to 0 and less than or equal to 1, and t is more than or equal to 0 and less than or equal to 1; x and y satisfy the following condition: x is more than or equal to 0.001 and less than or equal to 0.3, and y is more than or equal to 0.001 and less than or equal to 0.3.
2. The europium and manganese element-based temperature sensing material of claim 1, wherein: the temperature sensing material has an atomic ratio composition represented by the following general formula (2):
(Ca13.80Sr0.1)(Al9.75Ga0.1)(Zn5.9Mg0.1)O35:Eu0.10 3+,Mn0.15 4+（2）
wherein m =0.10, n =0.10, t =0.10, x =0.10, y = 0.15.
3. The europium and manganese element-based temperature sensing material of claim 1, wherein: the temperature sensing material has an atomic ratio composition represented by the following general formula (3):
(Ca13.45Sr0.5)(Al9.45Ga0.5)(Zn5.8Mg0.2)O35:Eu0.05 3+,Mn0.05 4+（3）
wherein m =0.50, n =0.50, t =0.20, x =0.05, y = 0.05.
4. The europium and manganese-based temperature sensing material of claim 1, 2 or 3, wherein: the temperature sensing material is in the form of powder, a film or ceramic.
5. A method for preparing a temperature sensing material based on europium and manganese elements as claimed in any one of claims 1 to 4, wherein: and accurately weighing raw materials of carbonates, nitrates, oxides or hydroxides corresponding to Ca, Sr, Al, Ga, Zn, Mg, Eu and Mn according to the atomic ratio, fully grinding and mixing the raw materials, calcining at high temperature, cooling to room temperature, and grinding to obtain the temperature sensing material.
6. A method for preparing a temperature sensing material based on europium and manganese elements as claimed in any one of claims 1 to 4, wherein: and (2) accurately weighing nitrates corresponding to Ca, Sr, Al, Ga, Zn, Mg, Eu and Mn according to the atomic ratio, dissolving the nitrates into deionized water to obtain a mixed solution, adding citric acid into the mixed solution, drying to form gel, and sintering at low temperature to obtain the temperature sensing material.
7. A method for applying the temperature sensing material based on europium and manganese elements as claimed in any one of claims 1 to 4, which comprises the following steps:
doping trivalent europium Eu (III) and tetravalent manganese Mn (IV) activators into an inorganic oxide main body matrix to prepare a fluorescent temperature sensing material with trivalent europium Eu (III) and tetravalent manganese Mn (IV) emitting light together;
detecting the emission spectra of the fluorescent temperature sensing material at different temperatures, and establishing a standard working curve of the integral luminous intensity ratio of the trivalent europium Eu (III) emission peak and the tetravalent manganese Mn (IV) emission peak along with the temperature change;
placing the fluorescent temperature sensing material in a temperature environment to be measured, and measuring the emission spectrum of the fluorescent temperature sensing material so as to obtain the integral luminous intensity ratio of the trivalent europium Eu (III) emission peak and the tetravalent manganese Mn (IV) emission peak;
and step four, searching the integral luminous intensity ratio in the temperature environment to be measured according to the standard working curve so as to obtain the temperature measurement value of the environment to be measured, and completing the high-sensitivity optical temperature measurement based on the trivalent europium Eu (III) and tetravalent manganese Mn (IV) codoped dual-luminous characteristic.
8. The method of claim 7, wherein the europium and manganese based temperature sensing material is prepared by the following steps: and in the second step, detecting the emission spectrum of the fluorescence temperature sensing material within the temperature range of 303-563K.
9. The method of claim 7, wherein the europium and manganese based temperature sensing material is prepared by the following steps: the standard working curve equation is as follows:
FIR=IMn4+/IEu3+=1553.69×exp(-2976/T)+0.8222 （4）
wherein FIR is the ratio of integrated luminous intensity, IEu3+And IMn4+The integral luminous intensity of the emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV) respectively, and T is absolute temperature.
10. The method of claim 7, wherein the europium and manganese based temperature sensing material is prepared by the following steps: the ratio of the integrated luminous intensity to the absolute temperature satisfies the following exponential equation:
FIR = IMn4+/IEu3+= A×exp(B/T) + C （5）
wherein FIR is the ratio of integrated luminous intensity, T is absolute temperature, IEu3+And IMn4+The integrated luminescence intensities of the emission peaks of trivalent europium Eu (III) and tetravalent manganese Mn (IV), A, B, C are constants respectively.
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| CN104087292A (en) * | 2014-07-09 | 2014-10-08 | 中国科学院长春应用化学研究所 | A kind of Mn4+ doped red luminescent material, preparation method and new lighting source |
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| CN104087292A (en) * | 2014-07-09 | 2014-10-08 | 中国科学院长春应用化学研究所 | A kind of Mn4+ doped red luminescent material, preparation method and new lighting source |
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