CN113149432A

CN113149432A - Anti-radiation boron tellurate luminescent glass and preparation method thereof

Info

Publication number: CN113149432A
Application number: CN202110262431.5A
Authority: CN
Inventors: 王珮; 陈红; 卡鲁帕亚·玛丽塞瓦姆; 刘俊成
Original assignee: Tianjin Polytechnic University
Current assignee: Tianjin Polytechnic University
Priority date: 2021-03-11
Filing date: 2021-03-11
Publication date: 2021-07-23

Abstract

The invention belongs to the technical field of luminescent material preparation, and discloses anti-radiation boron tellurate luminescent glass and a preparation method thereof₂、Nb₂O₅、H₃BO₃、CdF₂、SrCO₃Composition of, wherein TeO₂10‑40％，Nb₂O₅1‑20％，H₃BO₃5‑40％，CdF₂5‑15％，SrCO₃5 to 15 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.05-3%. Raw materials are processed according to the formulaAccurately weighing the fixed stoichiometric ratio, grinding and mixing, heating to 1000-1200 ℃ at the speed of 2-10 ℃/min, and preserving heat for 1-5 hours to fully melt the raw materials; then pouring the melt onto a copper template at 400-500 ℃ to solidify into glass, and keeping the temperature for 2-12 hours to fully remove the thermal stress; then cooled to room temperature at 1-5 deg.C/min. The invention relates to boron tellurate luminescent glass which takes boron tellurate as a matrix and rare earth element Dy as a luminescent agent, and the optical performance of the boron tellurate luminescent glass is adjusted by the mixture ratio of raw materials. The boron tellurate luminescent glass prepared by the technical scheme can be used for preparing white light emitting diodes and anti-radiation devices.

Description

Anti-radiation boron tellurate luminescent glass and preparation method thereof

Technical Field

The invention relates to a luminescent material and a preparation method thereof, in particular to anti-radiation boron tellurate luminescent glass and a preparation method thereof.

Background

The borate has high glass forming capacity, the borate glass has good mechanical property and high chemical stability, and is a wide transparent window from ultraviolet to infrared, and the solid solubility to rare earth ions is high; the tellurate glass has the advantages of low glass transition temperature, low phonon energy, high rare earth ion solubility, high thermal stability, high refractive index and the like. Therefore, the boron tellurate glass obtained by combining the two glasses has better glass quality, such as good chemical stability, high density, linear and nonlinear refractive index and the like. In rare earth ions, a Dy element can emit yellow light and blue light, and the combination of the two lights can generate white light. The blue light and the yellow light respectively fall in the wavelength regions of 470-500nm and 550-600nm, which respectively correspond to⁴F_9/2→⁶H_15/2And⁴F_9/2→⁶H_11/2and (4) transition.

The gamma ray is widely applied to medical clinical equipment sterilization and radiotherapy, agricultural breeding, soil moisture content diagnosis, industrial flaw detection, leak detection and the like. But such gamma radiation is also harmful to humans, resulting in nausea, vomiting and even cancer and death. There are many materials that shield gamma radiation, such as concrete, alloys, ceramics, clays, polymers, and the like. However, glass has high light transmittance, and thus has great advantages as a shielding material in many detection occasions.

At present, Dy doped with Dy disclosed in Chinese patent with publication number CN101759362A³⁺And Eu³⁺Phosphate glass, which can be applied to white light emitting diodes only by excitation with 360nm ultraviolet light, limits its practical application and development. The Yb sensitized germanium tellurate luminescent glass disclosed in the Chinese patent with the publication number of CN107601869A needs to be introduced with high-purity oxygen with the purity of more than 99.95 percent in a bubbling mode in the processes of heating and melting the glass, so that the manufacturing cost is increased, and the application and the development of the Yb sensitized germanium tellurate luminescent glass are not facilitated. Chinese patent publication No. CN102633436A on rare earth ion doped silicateThe required temperature of the optical glass during the preparation of the completely molten glass mixed material is 1550 ℃, and the technical economy is poor. The rare earth doped silicate luminescent glass disclosed in the Chinese patent with the publication number of CN103130414A can be synthesized only by melting in a reducing atmosphere (nitrogen and hydrogen) at a high temperature of 1750 ℃, and has lower technical economy.

xPbO prepared by Limkitjaroenporn et al: 20Na₂O：(80-x)B₂O₃The glass system, gamma ray shielding performance is enhanced along with the increase of PbO content, but the increase of lead content causes the reduction of light transmittance, and when the content reaches more than 35 mol%, the lead glass becomes light yellow; meanwhile, the stability of the glass is influenced to a certain extent by the excessively high content of PbO, such as the reduction of hardness, the deterioration of structural strength and no high temperature resistance, so that the application and the development of the glass are limited (Limkitjaroenporn P: J.Phys.chem. Solids, 2011, 72 (4): 245-. The barium-containing borate fly ash glass is prepared by Singh S et al, and parameters such as the mean free path, the effective atomic number and the like of a glass sample in the energy range of 356-1332KeV show that the shielding performance of the glass system is increased along with the increase of the BaO content, but Fe in the fly ash₂O₃Transition metal oxides cause the glass to be dark opaque and thus limit its applications. (Singh S: Nucl. Instrum. methods Phys. Res., A, 2008, 266: 140-146; DOI: 10.1016/i. nimb. 2007.10.018). The silicate glass prepared by Arbuzov et al has a large glass forming range, stable glass performance, high light transmittance and viscosity, and no crystallization after cooling and annealing. However, the high melting temperature and low transmittance of light in the blue and near ultraviolet range of the glass system limit its application as a radiation shielding transparent material. (Arbuzov V I: Glass Phys. chem., 2005, 31 (5): 583-010590; DOI: 10.1007/s 10720-005-0100-2). The phosphate glass prepared by Kharita et al has low melting preparation temperature, low glass transition temperature, high thermal expansion coefficient and high light transmittance, but the application is limited due to the defects of complicated preparation process, large volatilization amount, low chemical stability, high hygroscopicity and the like. (Kharita M H: radial. Phys. chem., 2012, 81 (10): 1568-1571; DOI: 10.1016/j. radial chem.2012.05.002). Therefore, turn offThe glass with the radiation resistance and the good luminescent performance is rarely reported in documents, and has wide application prospects in radiation-resistant devices.

The invention provides an anti-radiation boron tellurate luminescent glass and a preparation method thereof. Compared with the prior art or products, the invention has stable physical and chemical properties, has the functions of luminescence and ray shielding, and has white luminescence as luminescence and higher luminous efficiency; the preparation process is simple and has high technical economy.

Disclosure of Invention

The invention aims to provide the anti-radiation boron tellurate luminescent glass and the preparation method thereof, so as to overcome the defects in the prior art, the thermal stress and the luminous efficiency of the glass prepared by the method are improved, and the preparation method is simple and easy to realize industrialization.

In order to achieve the purpose, the invention adopts the following technical scheme:

an anti-radiation boron tellurate luminescent glass and a preparation method thereof are characterized in that: the raw material of the luminescent glass is Nb₂O₅、TeO₂、H₃BO₃、CdF₂、SrCO₃Composition of, wherein TeO₂10-40％，Nb₂O₅1-20％，H₃BO₃5-40％， CdF₂5-15％，SrCO ₃5 to 15 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.05-3%.

An anti-radiation boron tellurate luminescent glass and a preparation method thereof, comprising the following steps:

(1) raw material weighting: respectively weighing glass raw materials and rare earth oxide, wherein the glass raw materials are prepared from Nb₂O₅、TeO₂、H₃BO₃、 CdF₂、SrCO₃Composition of, wherein TeO₂10-40％，Nb₂O₅1-20％，H₃BO₃5-40％，CdF₂5-15％，SrCO ₃5 to 15 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.05-3%;

(2) preparing a glass premix: accurately weighing according to the stoichiometric ratio of the target product, and then grinding in an agate mortar to uniformly mix the target product;

(3) preparation of the frit in the completely molten state: pouring the glass premix into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1000-1200 ℃ at the speed of 2-10 ℃/min, and then preserving heat for 1-5 hours to completely melt the raw materials;

(4) preparing luminescent glass: and pouring the melt onto a copper template with the temperature of 400-500 ℃ to solidify into glass, keeping the temperature for 2-12 hours to eliminate thermal stress, and then cooling to room temperature at the temperature of 1-5 ℃/min to obtain the luminescent glass.

In order to improve the optical performance of Dy element doped glass, Nb₂O₅May affect the physicochemical properties of the glass, such as refractive index, dielectric constant and thermal expansion coefficient. H₃BO₃And TeO₂The boron tellurate is formed, and the transparency, density, refractive index, chemical durability and heat resistance of the sample are improved. CdF, a basic fluoride₂The energy of phonon of glass can be reduced, and luminescence is promoted. The Dy element doped boron tellurate glass prepared by the melt quenching method is fast in reaction and high in efficiency, belongs to a safe and effective glass preparation method, and can reduce the preparation cost while ensuring the glass quality.

Compared with the prior art, the invention has the following beneficial technical effects:

the invention takes boron tellurate as a glass matrix, takes rare earth elements as a luminescent agent, adopts a melt quenching method to prepare the anti-radiation boron tellurate luminescent glass, and improves the thermal stress and the luminous efficiency of the glass by adjusting the type and the concentration of glass raw materials. The melt quenching method adopted by the invention has the advantages of simple preparation process, low cost and easy realization of industrialization; the prepared boron tellurate glass has stable physical and chemical properties, has the functions of luminescence and ray shielding, has high luminous efficiency and is white cold light, and can be applied to the manufacture of illumination white light-emitting diodes and transparent anti-radiation devices.

Detailed Description

Radiation-resistant boron telluric acidThe raw material of the anti-radiation boron tellurate glass is Nb₂O₅、 TeO₂、H₃BO₃、CdF₂、SrCO₃Composition of, wherein TeO₂10-40％，Nb₂O₅1-20％，H₃BO₃5-40％，CdF₂5-15％， SrCO ₃5 to 15 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.05-3%.

the raw material of the luminescent glass is Nb₂O₅、TeO₂、H₃BO₃、CdF₂、SrCO₃Composition of, wherein TeO₂10-40％， Nb₂O₅1-20％，H₃BO₃5-40％，CdF₂5-15％，SrCO ₃5 to 15 percent; the preparation method of the luminescent glass comprises the steps of raw material weighting, ball milling and mixing, high-temperature melting of raw materials, model casting and heat preservation annealing.

The present invention is described in further detail below with reference to examples:

example one

(1) Weighing raw materials, namely weighing a glass raw material and a rare earth oxide respectively, wherein the glass raw material consists of Nb2O5, TeO2, H3BO3, CdF2 and SrCO3, wherein Gd is₂

O

₃5％，H₃BO₃54.95％，CdF ₂10％，SiO ₂15％，TiO ₂5％，SrCO ₃10 percent; the rare earth oxide is Dy₂O₃The mass percent is 0.05 percent;

(2) preparing a glass premix, accurately weighing according to the stoichiometric ratio of a target product, and then grinding in an agate mortar to uniformly mix the glass premix;

(3) preparing glass material in a completely molten state, pouring the glass premix into a pre-cleaned alumina crucible, placing the alumina crucible in a muffle furnace, heating to 1050 ℃ at a speed of 4 ℃/min, and then preserving heat for 1 hour to completely melt the raw materials;

(4) preparing luminescent glass, pouring the melt onto a copper template at 450 ℃ to solidify into glass, keeping the temperature for 8 hours to eliminate thermal stress, and then cooling to room temperature at 1-5 ℃/min to obtain the luminescent glass

Example two

The radiation-resistant boron tellurate luminescent glass and the preparation method thereof comprise the following steps:

O

₃5％，H₃BO₃54.7％，CdF ₂10％，SiO ₂15％，TiO ₂5％，SrCO ₃10 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.3 percent;

(4) preparing luminescent glass, pouring the melt onto a copper template at 450 ℃ to solidify into glass, keeping the temperature for 8 hours to eliminate thermal stress, and then cooling to room temperature at 1-5 ℃/min to obtain the luminescent glass.

EXAMPLE III

(1) weighing the raw materials, namely respectively weighing the glass raw material and the rare earth oxide, wherein the glass raw material is prepared from Nb₂O₅、TeO₂、H₃BO₃、 CdF₂、SrCO₃Composition of, wherein Gd₂O₃5％，H₃BO₃54.5％，CdF ₂10％，SiO ₂15％，TiO ₂5％，SrCO ₃10 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.5 percent;

Example four

(1) weighing the raw materials, namely respectively weighing the glass raw material and the rare earth oxide, wherein the glass raw material is prepared from Nb₂O₅、TeO₂、H₃BO₃、 CdF₂、SrCO₃Composition of, wherein Gd₂O₃5％，H₃BO₃54％，CdF ₂10％，SiO ₂15％，TiO ₂5％，SrCO ₃10 percent; the rare earth oxide is Dy₂O₃The mass percentage is 1 percent;

EXAMPLE five

(1) weighing the raw materials, namely respectively weighing the glass raw material and the rare earth oxide, wherein the glass raw material is prepared from Nb₂O₅、TeO₂、H₃BO₃、 CdF₂、SrCO₃Composition of, wherein Gd₂O₃5％，H₃BO₃53％，CdF ₂10％，SiO ₂15％，TiO ₂5％，SrCO ₃10 percent; the rare earth oxide is Dy₂O₃The mass percentage is 2 percent;

EXAMPLE six

The preparation method of the anti-radiation boron tellurate luminescent glass comprises the following steps:

(1) weighing the raw materials, namely respectively weighing the glass raw material and the rare earth oxide, wherein the glass raw material is prepared from Nb₂O₅、TeO₂、H₃BO₃、 CdF₂、SrCO₃Composition of, wherein Gd₂O₃5％，H₃BO₃52％，CdF ₂10％，SiO ₂15％，TiO ₂5％，SrCO ₃10 percent; the rare earth oxide is Dy₂O₃The mass percentage is 3 percent;

Dopings obtained in the above examples with 0.05%, 0.3%, 0.5%, 1%, 2% and 3% Dy₂O₃The boron tellurate glasses are respectively marked as 0.05DyNFBT, 0.3DyNFBT, 0.5DyNFBT, 1DyNFBT, 2DyNFBT and 3 DyNFBT.

Drawings

FIG. 1 shows Dy doped in an embodiment of the present invention₂O₃XRD spectrogram of the boron tellurate luminescent glass;

FIG. 2 shows an embodiment of the present invention doped with Dy of various concentrations₂O₃The emission spectrum of the boron tellurate luminescent glass;

FIG. 3 shows an embodiment of the present invention doped with Dy of various concentrations₂O₃The mass attenuation coefficient of the boron tellurate luminescent glass under the irradiation energy of 15 keV-15MeV, and an inset is the linear mass attenuation coefficient in the energy range;

FIG. 4 shows an embodiment of the present invention doped with Dy of various concentrations₂O₃The emission color of the boron tellurate luminescent glass has chromaticity coordinates in the CIE diagram (1931).

FIG. 5 shows an embodiment of the present invention doped with Dy of various concentrations₂O₃The boron tellurate luminescent glass;

FIG. 6 shows an embodiment of the present invention doped with Dy of various concentrations₂O₃The boron tellurate luminescent glass has the physical properties.

Fig. 1 shows the X-ray diffraction pattern of the sample, where no sharp bragg diffraction peak is seen, which demonstrates the amorphous state of the sample, i.e. indeed glass.

FIG. 2 is a graph showing luminescence spectra of boron tellurate glasses, each spectrum beingThree emission bands are respectively corresponding to blue light emission (with wavelengths of 482nm, 575nm and 663nm as centers)⁴F_9/2→⁶H_15/2Transition), yellow luminescence: (⁴F_9/2→⁶H_13/2Transition) and red luminescence: (⁴F_9/2→⁶H_11/2Transition). Where red luminescence is weak and blue and yellow luminescence are strong; the blue light has an intensity of about half that of the yellow light, and the combination of the two can be white light.

FIG. 3 is a plot of mass attenuation coefficient of a sample versus energy of incident gamma ray photons. The mass attenuation coefficient is one of the basic parameters for measuring the shielding gamma radiation. It can be seen that the mass attenuation coefficient decreases rapidly with increasing photon energy. The inset in fig. 3 shows the linear attenuation coefficient versus incident photon energy, also decreasing rapidly as photon energy increases.

As shown in fig. 4, the luminescence chromaticity coordinates of the boron tellurate glass prepared in the embodiment of the present invention all fall in the white region of the CIE (international commission on luminescence) 1931 chromaticity diagram, which confirms that the prepared boron tellurate glass has application prospects in white light emitting diodes.

FIG. 5 shows the composition of boron tellurate glass according to an embodiment of the present invention.

FIG. 6 shows the density, refractive index, etc. of glass samples according to examples of the present invention.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims

1. An anti-radiation boron tellurate luminescent glass and a preparation method thereof are characterized in that: the raw material of the luminescent glass is Nb₂O₅、TeO₂、H₃BO₃、CdF₂、SrCO₃Composition of, wherein TeO₂10-40％，Nb₂O₅1-20％，H₃BO₃5-40％，CdF₂5-15％，SrCO₃5-15％(ii) a The rare earth oxide is Dy₂O₃The mass percentage is 0.05-3%.

2. The anti-radiation boron tellurate luminescent glass and the preparation method thereof according to claim 1, characterized in that: the raw material of the luminescent glass is Nb₂O₅、TeO₂、H₃BO₃、CdF₂、SrCO₃Composition of, wherein TeO₂10-40％，Nb₂O₅1-20％，H₃BO₃5-40％，CdF₂5-15％，SrCO₃5 to 15 percent; the rare earth oxide is Dy₂O₃The mass percentage is 0.05-3%. Mixing the raw material Nb₂O₅、TeO₂、H₃BO₃、CdF₂、SrCO₃And Dy₂O₃Accurately weighing according to the stoichiometric ratio of the target product, and grinding in an agate mortar to uniformly mix the target product.

3. The anti-radiation boron tellurate luminescent glass and the preparation method thereof according to claim 2, characterized in that the melt quenching method is adopted, the glass premix is poured into a ceramic crucible which is cleaned in advance, the ceramic crucible is placed in a muffle furnace, the temperature is raised to 1000-1200 ℃ at the speed of 2-10 ℃/min, and then the heat is preserved for 1-5 hours, so that the raw materials are completely melted; and pouring the melt onto a copper template with the temperature of 400-500 ℃ to solidify into glass, keeping the temperature for 2-12 hours to eliminate thermal stress, and then cooling to room temperature at the speed of 1-5 ℃/min to prepare the anti-radiation boron tellurate luminescent glass.

4. The anti-radiation boron tellurate luminescent glass and the preparation method thereof according to claim 3, wherein the glass has high luminous efficiency, and the luminescence belongs to cold white light and can be used for manufacturing white light emitting diodes; has stronger attenuation and damping to gamma rays and can be used for preparing anti-radiation devices.