CN109912224B

CN109912224B - Fluorapatite nano glass ceramic material for optical temperature measurement and preparation method thereof

Info

Publication number: CN109912224B
Application number: CN201910076707.3A
Authority: CN
Inventors: 陈国华; 刘丽敏; 刘翔宇
Original assignee: Guilin University of Electronic Technology
Current assignee: Guilin University of Electronic Technology
Priority date: 2019-01-26
Filing date: 2019-01-26
Publication date: 2021-09-21
Anticipated expiration: 2039-01-26
Also published as: CN109912224A

Abstract

The invention discloses a fluorapatite nano glass ceramic material for optical temperature measurement and a preparation method thereof. The nano glass ceramic material comprises an oxide glass matrix, wherein the oxide glass matrix contains doped Yb³⁺And Er³⁺Ca5(PO4)₃F nanocrystals; the composition of the oxide glass matrix at least contains 15-25 mol% of CaF₂25 to 35 mol% of ZnO, 6 to 12 mol% of P₂O₅And 34 to 44 mol% of B₂O₃And Yb in an amount of 0.5 to 1.5 mol% based on the total amount of the above oxides₂O₃And 0.04 to 0.08 mol% of Er₂O₃. The preparation method of the nano glass ceramic material comprises the following steps: according to the composition proportion of the oxide glass matrix, the prepared mixed powder is ground, uniformly mixed and then placed in a crucible, heated to 1100-1250 ℃, and kept warm for 1-2 hours; then quickly pouring the obtained molten glass into a preheated copper mold at the temperature of 420-450 ℃ for molding and annealing for 10 hours to obtain matrix glass; and keeping the annealed substrate glass at 660-680 ℃ for 2-6 hours to crystallize.

Description

Fluorapatite nano glass ceramic material for optical temperature measurement and preparation method thereof

Technical Field

The invention belongs to the field of solid conversion luminescent materials, and particularly relates to a fluorapatite nano glass ceramic material for optical temperature measurement and a preparation method thereof.

Background

Biological research often involves micro-and nano-scale temperature measurement and manipulation, and in many special environments, temperature sensing also requires non-contact and fast-responding temperature detectors. Most of the traditional temperature detectors adopt a contact type, the condition that a measured object is larger than 10 mu m can be met, the detection speed is influenced by heat conduction, and the application environment is limited. The key point of the non-contact temperature sensor based on the optical temperature sensing characteristic is the fluorescent material used as a temperature probe. The fluorescent material must have more than two fluorescence emission peaks, and the intensities of different emission peaks are different with respect to temperatureThe reaction of (1); in addition, certain wavelength intervals are required among different emission peaks so as to discriminate signals. For example, Chinese patent CN106634988A discloses a nanocrystalline material for a fluorescence temperature probe, which respectively shows Er under the excitation of 980nm laser³⁺Ion and Tm³⁺Single band luminescence of ions at 650nm and 800nm, Er increasing gradually from 60 deg.C to 200 deg.C³⁺The fluorescence intensity of the ion at 650nm is constant, whereas Tm is³⁺The fluorescence intensity of the ion at 800nm is gradually increased, and the sensitivity is 1.73 percent K^-1And the temperature measuring area is 60-200 ℃. The temperature measurement sensitivity of the technology reaches practical requirements, and the temperature measurement area range is not wide enough, so that the practical application is limited to a certain extent.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides the fluorapatite nano glass ceramic material which can be used for a fluorescent temperature probe and has a wide temperature measuring area and enough temperature reaction sensitivity, wherein the temperature measuring area of the material reaches 30-525 ℃, and the sensitivity also reaches 1-1.35 percent K^-1(ii) a Meanwhile, the invention also provides a preparation method of the material.

The oxide glass matrix of the glass ceramic material contains uniformly distributed Yb-doped glass³⁺And Er³⁺Ca5(PO4)₃F (fluorapatite) nanocrystals. The composition of the oxide glass matrix at least contains 15-25 mol% of CaF₂25 to 35 mol% of ZnO, 6 to 12 mol% of P₂O₅And 34 to 44 mol% of B₂O₃And Yb in an amount of 0.5 to 1.5 mol% based on the total amount of the above oxides₂O₃And 0.04 to 0.08 mol% of Er₂O₃. The doping proportion is the preferred proportion given by the invention, the effect of the invention is obtained and is not limited to the proportion range, and the person skilled in the art can make appropriate adjustment according to the actual situation.

The preparation method of the glass ceramic material comprises the following steps: grinding and uniformly mixing all the powder raw materials, placing the powder raw materials in a crucible, heating to 1100-1250 ℃, and preserving heat for 1-2 hours; then quickly pouring the obtained molten glass into a preheated copper mold at the temperature of 420-450 ℃ for molding and annealing to obtain matrix glass; and keeping the annealed substrate glass at 660-680 ℃ for 2-6 hours to crystallize.

Drawings

FIG. 1 is a graph of the transmission spectrum of a sample of an embodiment of the present invention. FIG. 2 is an X-ray diffraction pattern of a sample of an embodiment of the present invention. FIG. 3 is a transmission electron micrograph of a sample according to an embodiment of the present invention. FIG. 4 is a graph of temperature dependent emission spectra of samples of examples of the present invention. FIG. 5 is a graph of intensity ratio versus temperature for samples of examples of the present invention.

Detailed Description

The present invention will be further described with reference to the following specific examples.

Example 1: mixing CaF₂、ZnO、NH₄H₂PO₄、H₃BO₃、Yb₂O₃、Er₂O₃Powder of 25CaF by mol percent₂：25ZnO：10P₂O₅：40B₂O₃Addition of 1Yb₂O₃、0.04Er₂O₃The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace insulated at 420 ℃ for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass (represented by PG); the obtained matrix glass was put into a heat-treatment resistance furnace and kept at 660 ℃ for 4 hours to obtain a nano glass ceramic (represented by GC 660).

The transmission spectrum shows that the glass-ceramic has high transparency (FIG. 1); x-ray diffraction pattern showed Ca precipitation in oxide glass matrix₅(PO₄)₃Crystalline phase F (fig. 2); transmission electron microscope observation proves that the glass ceramic contains a large amount of Ca with the average size of about 5nm₅(PO₄)₃The F crystals are uniformly distributed in the matrix (FIG. 3); the fluorescence spectrometer measures the temperature dependence under the excitation condition of 980nmPhotoluminescence emission spectrum (FIG. 4), detectable from²H_11/2Radiative transition emission of energy levels and⁴S_3/2radiative transition emission of energy levels. As the temperature is raised, the temperature of the solution is raised,²H_11/2the radiative transition emission intensity of the energy level increases rapidly, and⁴S_3/2the radiation transition emission intensity of the energy level only changes slightly, the fluorescence intensity ratio of the two is taken as a temperature measurement parameter (figure 5), and the sensitivity of the obtained nano glass ceramic material is 1.35 percent K within the temperature range of 298K-798K (25-525 ℃)^-1。

Example 2: mixing CaF₂、ZnO、NH₄H₂PO₄、H₃BO₃、Yb₂O₃、Er₂O₃Powder of 25CaF by mol percent₂：25ZnO：10P₂O₅：40B₂O₃Addition of 1Yb₂O₃、0.08Er₂O₃The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 2 hours at 660 ℃, obtaining fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.28 percent K^-1。

Example 3: mixing CaF₂、ZnO、NH₄H₂PO₄、H₃BO₃、Yb₂O₃、Er₂O₃Powder of 25CaF by mol percent₂：25ZnO：10P₂O₅：40B₂O₃Addition of 1Yb₂O₃、0.06Er₂O₃The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, ground for more than 15 minutes to be uniformly mixed, then the mixture is placed in a crucible, heated to 1150 ℃ in a high-temperature resistance furnace and then kept warm for 1 hour to be filledMelting; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; putting the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 4 hours at 670 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.32 percent K^-1。

Example 4: mixing CaF₂、ZnO、NH₄H₂PO₄、H₃BO₃、Yb₂O₃、Er₂O₃Powder of 25CaF by mol percent₂：25ZnO：10P₂O₅：40B₂O₃Addition of 1.5Yb₂O₃、0.02Er₂O₃The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 4 hours at 660 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.17 percent K^-1。

Example 5: mixing CaF₂、ZnO、NH₄H₂PO₄、H₃BO₃、Yb₂O₃、Er₂O₃Powder of 25CaF by mol percent₂：25ZnO：10P₂O₅：40B₂O₃Addition of 0.5Yb₂O₃、0.04Er₂O₃The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, the molten glass is quickly poured into a copper mold preheated at the temperature of 420 ℃ for forming, and the formed glass is put into a muffle furnace with the temperature of 420 ℃ for annealingCooling the glass along with the furnace after 10 hours to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 2 hours at 660 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.09 percent K^-1。

Example 6: mixing CaF₂、ZnO、NH₄H₂PO₄、H₃BO₃、Yb₂O₃、Er₂O₃Powder of 25CaF by mol percent₂：25ZnO：10P₂O₅：40B₂O₃Addition of 1Yb₂O₃、0.05Er₂O₃The mixture ratio (mol percentage) is calculated and weighed, then the mixture is placed in an agate mortar, is ground for more than 15 minutes to be uniformly mixed, then is placed in a crucible, is heated to 1150 ℃ in a high-temperature resistance furnace and is kept warm for 1 hour to be fully melted; then, quickly pouring the molten glass into a copper mold preheated at 420 ℃ for forming, putting the formed glass into a muffle furnace with the 420 ℃ heat preservation for annealing for 10 hours, and then cooling along with the furnace to obtain matrix glass; placing the obtained matrix glass into a heat treatment resistance furnace, preserving the heat for 2 hours at 660 ℃ to obtain fluorapatite nano glass ceramic, and testing the sensitivity of the glass ceramic to be 1.31 percent K^-1。

In each of the above examples, 25CaF₂：25ZnO：10P₂O₅：40B₂O₃The ratio (in mol%) is not the only limiting value, and those skilled in the art know that the above components are the essential components constituting the matrix glass, and that the ratio of the components may be varied within the given range without affecting the final effect of the present invention. The preferred proportions of the basic components of the matrix glass given in the present invention are: 15-25 mol% of CaF₂25 to 35 mol% of ZnO, 6 to 12 mol% of P₂O₅And 34 to 44 mol% of B₂O₃。

Claims

1. A fluorapatite nano-glass ceramic material for optical thermometry contains at least CaF₂、ZnO、P₂O₅And B₂O₃The oxide glass substrate of (2), characterized in that: the oxide glass matrix also contains uniformly distributed Yb-doped glass³⁺And Er³⁺Ca of (2)₅(PO₄)₃F nanocrystals; yb of the above³⁺And Er³⁺The doping ratio of (A) is: yb in an amount of 0.5 to 1.5 mol% based on the total amount of the oxide glass substrate₂O₃And 0.04 to 0.08 mol% of Er₂O₃；

The composition of the oxide glass matrix at least contains 15-25 mol% of CaF₂25 to 35 mol% of ZnO, 6 to 12 mol% of P₂O₅And 34 to 44 mol% of B₂O₃。

2. The fluorapatite nano-glass ceramic material according to claim 1, characterized in that the Ca is₅(PO₄)₃The size of the F nanocrystal is 2-8 nm.

3. A preparation method of a fluorapatite nano glass ceramic material for optical temperature measurement is characterized by comprising the following steps: according to the composition proportion of the oxide glass matrix in claim 1, the prepared mixed powder is ground, uniformly mixed and then placed in a crucible, heated to 1100-1250 ℃, and kept warm for 1-2 hours; then quickly pouring the obtained molten glass into a preheated copper mold at the temperature of 420-450 ℃ for molding and annealing for 10 hours to obtain matrix glass; and keeping the annealed substrate glass at 660-680 ℃ for 2-6 hours to crystallize.