CN110357425B

CN110357425B - High-density barium germanium tellurate scintillation glass and preparation method thereof

Info

Publication number: CN110357425B
Application number: CN201910723879.5A
Authority: CN
Inventors: 孙心瑗; 邓昌滨; 周闽军; 蒋达国; 温玉锋; 杨庆梅
Original assignee: Jinggangshan University
Current assignee: Jinggangshan University
Priority date: 2019-08-07
Filing date: 2019-08-07
Publication date: 2022-05-13
Anticipated expiration: 2039-08-07
Also published as: CN110357425A

Abstract

The application relates to high-density barium germanium tellurate scintillation glass, which comprises the following raw materials: BaO: 0 to 45mol percent; GeO₂：0‑55mol％；TeO₂: 20-100 mol%; and a rare earth ion activator; wherein, BaO and GeO₂And TeO₂The sum of the three components is 100 mol%; wherein the external doping concentration of the rare earth ion activator is BaO and GeO₂And TeO₂0.1 to 10 mol% of the sum of the three components. The application also discloses a method for preparing the high-density barium germanium tellurate scintillation glass. The preparation temperature of the high-density barium tellurate scintillating glass does not exceed 1000 ℃, and the density is 4.616-5.293g/cm³And the method has wide application in X-ray medical imaging, industrial on-line detection, national security supervision and high-energy physical or nuclear physical experiments.

Description

High-density barium germanium tellurate scintillation glass and preparation method thereof

Technical Field

The invention relates to the technical field of scintillating materials. In particular to rare earth ion doped high-density barium germanium tellurate scintillation glass and a preparation method thereof.

Background

The scintillator is a light functional material which emits visible light or near ultraviolet light after absorbing high-energy rays, and is widely applied to the fields of high-energy physics, nuclear physics, celestial physics, geophysical physics, industrial flaw detection, medical imaging, safety detection and the like.

The scintillation glass is hopeful to replace commercial scintillation crystals due to the advantages of easy adjustment of chemical components, good optical uniformity, easy realization of large size, simple preparation method and the like. The scintillation glass has the greater advantages that the scintillation glass can be drawn into optical fibers and manufactured into an optical fiber panel, and therefore the detection efficiency of high-energy rays and the imaging resolution of devices are improved. Therefore, glass scintillators have evolved into an important branch of scintillating materials.

High light yield and high density are two important features of excellent scintillators, because high density scintillators have high stopping power and short irradiation length, which facilitates engineering (instrument) miniaturization and thus construction cost reduction, while high luminous intensity facilitates improved detection sensitivity and image resolution. Therefore, the high-density scintillator has important application value in high-energy physics and nuclear medicine imaging, and the development of high-density scintillation glass with reasonable price is more and more concerned by researchers.

The current general practice to increase the density of scintillating glasses is to do so in two ways. One aspect of increasing the density of the scintillating glass is to increase the content of rare earth (e.g., rare earth compound agent rich in gadolinium and lutetium ions) components in the scintillating glass as much as possible to improve the density and other properties of the scintillating glass.

Such as a rich Lu₂O₃Borosilicate scintillation glass (15 SiO)₂-25B₂O₃-5P₂O₅-15Ga₂O₃-38Lu₂O₃-2Tb₂O₃) Successfully prepared by japanese scientists (j.fu et al., j.lumin.,2009, 128: 99-104) with a maximum density of 6.56g/cm³And the light yield reaches 20 percent of BGO, and the glass is scintillating glass with application prospect.

Such as patent publication No. CN102826753A entitled "Gd-enriched₂O₃B-germanate scintillation glass, preparation method and application thereof₂O₃-GeO₂-Gd₂O₃High-density boron germanate scintillation glass activated by rare earth or transition ions as a main component. Disclosed Gd-rich₂O₃The boron germanate glass has good thermal stability and chemical stability, higher refractive index and excellent scintillation property, and the highest density is about 5.7g/cm³The scintillation glass is high-density scintillation glass with wide application prospect.

Meanwhile, rare earth fluoride and non-rare earth heavy metal fluoride may be introduced into the above boron germanate scintillation glass. The inventor previously disclosed in patent application No. 201410249441.5 entitled "a rare earth ion-doped high density oxyfluoride boron germanate scintillation glass and method for making same" a high radiance luminescence intensity with a maximum density of 6.75g/cm³The novel fluoxyboron germanate scintillation glass. Based on the research work of the high-density oxyfluoride boron germanate scintillation glass, the 'ultrahigh-density oxyfluoride boron tellurate scintillation glass' is successfully obtained by introducing a heavy network former, such as tellurium dioxideAnd a preparation method thereof (application number: 201810801477.8), the density of the scintillation glass breaks through 7.0g/cm for the first time³Has important application prospect.

Although rare earth-rich scintillating glass makes substantial breakthrough in the aspects of density, light yield and the like, the preparation cost of the scintillating material is greatly increased due to the large amount of expensive rare earth resources required in the scintillating material, so that the production cost of a large amount of scintillators required in the fields of high-energy physical engineering and nuclear medicine imaging is sharply increased, and the scale application of the scintillating material can be further limited.

Another aspect of increasing the density of the scintillation glass is to increase the heavy metal (e.g., lead, bismuth, tungsten, barium, etc.) compound reagent in the scintillation glass as much as possible to increase the density of the scintillation glass.

For example, patent publication No. CN1087066A entitled "high Density, radiation resistant fast flashing inorganic glass" discloses the use of PbO, Bi₂O₃Is the main component, the rest is the oxide component of the glass forming body, and the luminescent center is Pb²⁺And Bi³⁺High density scintillating glass. Because the scintillation glass contains 50 to 70mol percent of PbO, the glass density is between 7.5 and 8.1g/cm³And (3) a range.

For example, the invention patent with patent publication No. CN101913767A entitled "rare earth doped oxyfluoride tellurate scintillation glass and preparation method thereof" discloses the use of TeO₂、PbF₂、BaF₂And Gd₂O₃High-density scintillation glass as matrix glass and rare-earth ion as activator, and its composition contains 1-20 mol% of PbF₂And 65-85 mol% TeO₂The density of which is higher than 6.0g/cm³However, PbO is extremely toxic and pollutes the environment seriously, thus limiting the popularization and application of such scintillating glass.

For example, patent publication No. CN102775063A entitled "scintillation glass containing lead oxyfluoride and method for producing the same" discloses a scintillation glass containing PbF₂、PbO、SiO₂Or GeO₂As main component, Tb³⁺Scintillation glass with ion as activator, which contains 30-65 mol% PbF₂And 3-20 mol% of PbO, ensuring a density higher than 6.0g/cm³However, the glass composition contains a large amount of PbO and PbF₂It pollutes the environment seriously, so its practical application may be challenging.

All of the above patents require that the scintillation glass composition be disclosed as containing lead ions in an amount such that the density easily exceeds 6.0g/cm³Even up to 8.0g/cm³. In addition to the lead ions in scintillating glasses severely polluting the environment, the scintillating luminescence of these glasses under high energy radiation can also be severely quenched by these lead ions, sometimes even non-scintillating luminescence. In order to avoid the hazardous nature of lead ions in the scintillation glass, some high density scintillation glasses that do not contain lead ion chemicals are therefore produced. For example, the invention patent with the patent publication number of CN 201611206292.X and the name of "a high-density gadolinium tungsten borate scintillating glass and a preparation method thereof" discloses a method for scintillating gadolinium tungsten borate scintillating glass by Gd₂O₃-WO₃-B₂O₃Scintillating glass as main component, wherein the glass component must contain 40-60 mol% of WO₃Ensures that the density of the material is as high as 6.19g/cm³And the luminescence with certain intensity under the excitation of high-energy X-rays is also obtained. For example, the patent with patent publication No. CN201910573216X entitled "high density tungsten germanium tellurate scintillation glass and preparation method thereof" discloses the use of WO₃-GeO₂-TeO₂The scintillation glass as main component has glass density as high as 5.71g/cm³And the luminescence with certain intensity under the excitation of high-energy X-rays is obtained. The scintillation glass rich in heavy metal (such as lead, bismuth, tungsten and the like) chemical combination reagents can meet the practical application of 5.0g/cm in spite of the density³The minimum density of the fluorescent material, but the scintillation luminous intensity of the fluorescent material under the excitation of high-energy rays is still relatively weak.

Disclosure of Invention

Among the glasses reported, none of them disclose GeO as a very important glass network former₂And TeO₂To increase the density of the scintillation glass. GeO₂And TeO₂Firstly, the energy of phonon is low, which is beneficial to improving the radiation transition probability of the scintillation glass and further improving the luminescence thereofEfficiency. Second, GeO₂And TeO₂All are heavy metal oxides, which is beneficial to improving the density of the scintillation glass. Finally, their melting point is lower than that of conventional borosilicate, which is beneficial to reducing the preparation cost of glass. Based on the above consideration and in combination with the performance of the heavy metal oxide BaO, the inventor specially provides a high-density barium germanium tellurate scintillation glass and a preparation method thereof, so as to promote the practical process of the scintillation glass.

The invention aims to provide high-density barium germanium tellurate scintillation glass, wherein the high density refers to that the highest density of the glass can exceed 5.0g/cm³. In particular, GeO is used₂And TeO₂The heavy metal oxide is a network former, and BaO heavy metal oxide is introduced as a network modifier, so as to improve the density of the glass.

The application also aims to provide a method for preparing the high-density barium germanium tellurate scintillation glass.

In order to achieve the above object, the present application provides the following technical solutions:

in a first aspect, the present application provides a high-density barium germanium tellurate scintillating glass, which is characterized in that the scintillating glass comprises the following components:

BaO：0-45mol％；

GeO₂：0-55mol％；

TeO₂: 20-100 mol%; and

a rare earth ion activator;

wherein, BaO and GeO₂And TeO₂The sum of the three components is 100 mol%;

wherein the external doping concentration of the rare earth ion activator is BaO and GeO₂And TeO₂0.1-10 mol% of the sum of the three components.

In one embodiment of the first aspect, the starting materials for the scintillation glass comprise the following components:

BaO：10-40mol％；

GeO₂：10-35mol％；

TeO₂：30-60mol％(ii) a And

a rare earth ion activator;

wherein, BaO and GeO₂And TeO₂The sum of the three components is 100 mol%;

wherein the external doping concentration of the rare earth ion activator is BaO and GeO₂And TeO₂2-5 mol% of the sum of the three components.

In one embodiment of the first aspect, the rare earth ion activator comprises Ce³⁺、Pr³⁺、Nd³⁺、Pm³⁺、Sm³ ⁺、Eu³⁺(Eu²⁺)、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Er³⁺、Tm³⁺And/or Yb³⁺Ions.

In a second aspect, the present application provides a method for preparing a high-density barium germanium tellurate scintillation glass as described in the first aspect, wherein the method comprises the following steps:

s1, accurately weighing the raw materials according to the components of the scintillation glass, and uniformly mixing all the raw materials to obtain a first mixture;

s2: melting the first mixture into a uniform glass melt in a heat-resistant container, wherein the melting temperature is 900-1000 ℃ according to the glass components, the melting time is kept for 25-60min, and the melting atmosphere is air;

s3: after the uniform glass melt is cast and molded in a mold, carrying out constant-temperature annealing treatment to eliminate the internal stress of the glass, wherein the annealing temperature of the glass is 200-300 ℃, and the annealing time is 2-5 hours;

s4: and cutting, grinding and polishing the annealed scintillation glass initial product to obtain the high-density barium germanium tellurate scintillation glass.

In one embodiment of the second aspect, in step S1, GeO in the glass component₂And TeO₂The BaO is directly introduced, the BaO is introduced in the form of carbonate or nitrate, and the activator is introduced in the form of corresponding compounds such as rare earth oxide, rare earth fluoride, rare earth carbonate or rare earth nitrate.

In one embodiment of the second aspect, in step S2, the heat-resistant container comprises an alumina crucible or a platinum crucible.

In one embodiment of the second aspect, in step S3, the mold comprises a stainless steel mold;

the constant temperature annealing is carried out in a muffle furnace.

In a third aspect, the present application provides a scintillation screen or scintillation array made from the high density barium germanium tellurate scintillating glass of the first aspect.

In a fourth aspect, the present application provides an optical fiber drawn from the high density barium germanium tellurate scintillating glass of the first aspect.

In a fifth aspect, the present application provides the use of a high density barium germanium tellurate scintillating glass according to the first aspect in the field of radiation detection. The ray detection field comprises industrial on-line detection, national security supervision, high-energy physical and nuclear medicine imaging and the like.

Compared with the prior published high-density scintillation glass technology, the high-density barium germanium tellurate scintillation glass has the following remarkable characteristics. Firstly, the preparation process is simple, the chemical components are easy to adjust, the large size is easy to realize, the chemical stability is good, and the optical fiber can be further drawn. In particular, the melting temperature required for preparing the barium germanium tellurate glass does not exceed 1000 ℃, and the barium germanium tellurate glass has important significance for the production energy conservation and the safety of the scintillation glass. Secondly, the network formers in the barium germanium tellurate scintillating glass are all made of heavy metal GeO₂And TeO₂The BaO used as the network modifier is also a heavy metal oxide, which has good regulation effect on improving and optimizing the performances such as the density of the scintillation glass and the like, so that the scintillation glass can well meet the requirements of practical application. Finally, the variety and doping amount of the activator in the barium germanium tellurate scintillation glass have wide choice, and the emission wavelength and the attenuation time of the scintillation glass can be effectively regulated and controlled so as to meet the actual application requirements in the fields of high-energy physics and nuclear medicine imaging.

Drawings

FIG. 1 is a diagram of glass forming range of barium germanium tellurate scintillating glass. In fig. 1, a solid circle represents a glass forming point, a hollow circle represents a non-glass forming point, and a semi-solid circle represents a semi-glass forming point.

FIG. 2 is a graph of photoluminescence and X-ray excitation emission spectra of a scintillating glass prepared in example 1 of the present application.

FIG. 3 is a graph of photoluminescence and X-ray excitation emission spectra of a scintillating glass prepared in example 2 of the present application.

FIG. 4 is a graph of photoluminescence and X-ray excitation emission spectra of a scintillating glass prepared in example 3 of the present application.

FIG. 5 is a graph of photoluminescence and X-ray excitation emission spectra of a scintillating glass prepared in example 4 of the present application.

The ordinate from fig. 2 to fig. 5 is the relative intensity, which is in arbitrary units.

Detailed Description

Unless otherwise indicated, implied from the context, or customary in the art, the testing and characterization methods used are synchronized to the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are hereby incorporated by reference in their entirety, and the equivalent family of patents is also incorporated by reference, especially with respect to the definitions of those documents disclosed in the art with respect to synthetic techniques, products, and process designs, etc. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.

In one specific implementation, the application provides a high-density barium germanium tellurate scintillating glass which is characterized in that the scintillating glass comprises the following components:

BaO：0-45mol％；

GeO₂：0-55mol％；

TeO₂：20-100mol％；

wherein the sum of the components is 100 mol%.

Rare earth ions as luminescent centers (e.g. Tb)³⁺And Eu³⁺Ion) is 0.1-10 mol%.

In one embodiment, the scintillation glass comprises the following raw materials:

BaO：10-40mol％；

GeO₂：10-35mol％；

TeO₂：30-60mol％；

wherein the sum of the components is 100 mol%.

Rare earth ion (Ce) as luminescence center³⁺、Pr³⁺、Nd³⁺、Pm³⁺、Sm³⁺、Eu³⁺(Eu²⁺)、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Er³⁺、Tm³⁺And/or Yb³⁺Ion) is 2-5 mol%.

In a specific implementation, the application provides a preparation method of the high-density barium germanium tellurate scintillating glass, which is characterized in that the scintillating glass is prepared by adopting a traditional high-temperature melting method, namely, the glass is prepared by processes of fully mixing, melting, mold casting, annealing preparation and the like of glass raw materials. The method specifically comprises the following steps:

s1, firstly, accurately weighing the raw materials according to the components of the scintillation glass, and uniformly mixing all the raw materials. GeO in the glass component₂And TeO₂The raw materials are all directly introduced; BaO is introduced in the form of carbonate or nitrate; the rest of the rare earth raw materials can be introduced in the form of corresponding compounds such as rare earth oxides, rare earth fluorides, rare earth carbonates or nitrates; the purity of all raw materials is analytically pure or more;

s2: then, pouring the uniformly mixed raw materials into an alumina crucible or a platinum crucible to be melted into a uniform glass melt, wherein the melting temperature is 900-1000 ℃ according to the glass components, the melting time is kept for 25-60min, and the melting atmosphere is air;

s3: and thirdly, casting and molding the uniformly melted glass in a preheated stainless steel mold, and then rapidly placing the glass in a muffle furnace for constant-temperature annealing treatment to eliminate the internal stress of the glass. According to different glass components, the annealing temperature of the glass is 200-300 ℃, and the annealing time is 2-5 hours;

s4: and finally, cutting, grinding and polishing the annealed scintillation glass primary product to obtain the scintillation glass with the size specification.

In one embodiment, the network formers in the high density barium germanium tellurate scintillating glasses described herein are all heavy metal GeO₂And TeO₂The structure is low in phonon energy, and the network modifier BaO is also a heavy metal oxide, so that the performance of adjusting and optimizing the density of the scintillation glass and the like is facilitated.

In a specific implementation, the high-density barium germanium tellurate scintillating glass has a simple preparation process, the melting temperature required for preparing the barium germanium tellurate glass is not more than 1000 ℃, and the high-density barium germanium tellurate scintillating glass has important significance for the production energy conservation and the safety of scintillating glass.

In a specific implementation, the high-density barium germanium tellurate scintillating glass can be directly manufactured into a scintillating screen or a scintillating array, or further drawn into an optical fiber to manufacture an optical fiber panel, and can be widely applied to the field of radiation detection such as industrial on-line detection, national security supervision, high-energy physics and nuclear medicine imaging.

Examples

The present invention will be described in more detail with reference to examples. Unless otherwise indicated, the materials and equipment used in the examples were all commercially available and were operated under the direction of the specification.

First, we obtained a glass-forming range diagram of high-density barium germanium tellurate scintillating glass, as shown in fig. 1. All glass preparation processes are the same, namely sequentially through procedures of glass component proportioning, grinding, high-temperature melting, casting molding, annealing, cutting and polishing and the like. Wherein the high-temperature melting temperature and time are 1000 ℃ and 40min, and the annealing temperature and time are 300 ℃ and 3 hours.

In order to further embody the characteristics of the rare earth doped high-density barium germanium tellurate scintillating glass, Dy is used respectively³⁺、Tb³⁺、Eu³⁺And Ce³⁺The ions serve as activators to illustrate the specific implementation process.

Example 1

First, preparation process

As shown in Table 1, the specific formulation of example 1 of the present invention was 80TeO₂-10GeO₂10BaO, wherein the activator is Eu³ ⁺Ions, by Eu₂O₃Introducing the mixture, wherein the external doping concentration is 0.5 mol%. The melting atmosphere is air.

Eu in example 1³⁺The preparation method of the activated high-density barium germanium tellurate scintillation glass comprises the following steps:

the first step is as follows: according to Eu in Table 1³⁺Accurately weighing each component according to a formula for activating the high-density barium germanium tellurate scintillation glass, fully and uniformly mixing, pouring into an alumina crucible, and melting for 30min by a high-temperature melting method in an air atmosphere at 950 ℃;

the second step is that: pouring the uniform molten mass into a preheated stainless steel mold at 300 ℃ for casting molding, and naturally cooling to form glass; and

the third step: the glass was placed in a muffle furnace at 300 ℃ for 3 hours for annealing to obtain the scintillating glass according to example 1.

The fourth step: cutting glass into size of 15mm × 20mm × 2.5mm, and grinding and polishing the surface to obtain Eu³⁺Activating the high-density barium germanium tellurate scintillation glass.

TABLE 1 EXAMPLES 1-4 high Density barium germanium tellurate scintillating glasses compositions

Second, performance test

The density of the scintillation glass is obtained by using a precision balance for weighing and testing by using purified water as an immersion liquid according to an Archimedes principle. All photoluminescence spectra and X-ray excitation emission spectra of the scintillating glass were obtained by testing using an Edinburgh FLS980 fluorescence spectrometer (Ex slit 0.75nm, Em slit 0.75nm) and an X-ray excitation emission spectrometer (W target, 30kV,3 mA).

Eu of example 1³⁺The density of the activated barium germanium tellurate scintillating glass is 5.027g/cm³. Eu in example 1³⁺Photoluminescence and X-ray excitation emission spectra of the activated high density barium germanium tellurate scintillating glass are shown in fig. 2. As can be seen from FIG. 2, under excitation at 394nm, four emission peaks at 593, 613, 653nm and 702nm in the emission spectrum correspond to Eu, respectively³⁺Ion(s)⁵D₀→⁷F_J(J ═ 1, 2, 3, 4) optical transitions, where 613nm (C⁵D₀→⁷F₂) The wavelength emission intensity is maximum. Whereas the scintillation light output of the scintillating glass of example 1 is obtained under X-ray (W target, 30kV,3mA) excitation, Eu is clearly visible³⁺The feature emits light.

Third, application

The scintillation glass prepared by the method can be further prepared into a scintillation screen or a scintillation array; or the scintillation glass prepared by the method is further drawn into optical fiber, and has important application value in the radiation detection fields of X-ray real-time imaging, industrial on-line detection, scientific research, national security supervision and the like.

Example 2

The preparation process is substantially the same as that of example 1, except that the glass composition of example 2 is: is 60TeO₂-20GeO₂-20BaO, wherein the activator is Tb³⁺Ions through Tb₄O₇Introducing the mixture, wherein the external doping concentration is 0.5 mol%. The melting atmosphere is air.

Tb of example 2³⁺The density of the activated barium germanium tellurate scintillating glass is 4.954g/cm³. The photoluminescence spectrum and X-ray excitation emission spectrum of example 2 were obtained by testing with an Edinburgh FLS980 fluorescence spectrometer (Ex slit 0.75nm, Em slit 0.75nm) and an X-ray excitation emission spectrometer (W target, 30kV,3mA), as shown in FIG. 3. As can be seen from FIG. 3, under 378nm excitation, four luminescence peaks at 490, 545, 588nm and 624nm in the emission spectrum correspond to Tb respectively³⁺Ion(s)⁵D₄→⁷F_J(J-6, 5, 4, 3) optical transition at 545nm (C:)⁵D₄→⁷F₅) The wavelength emission intensity is maximum. While the scintillation light output of the scintillating glass of example 3 was obtained under X-ray (W target, 30kV,3mA) excitation, Tb was also clearly observed³⁺The strongest characteristic emission peak of the ion.

Example 3

The preparation process is substantially the same as that of example 1, except that the glass composition of example 3 is: is 40TeO₂-20GeO₂-40BaO, wherein Dy is the activator³⁺Ion through Dy₂O₃Introducing the mixture, wherein the external doping concentration is 0.5 mol%. The melting atmosphere is air.

Dy of example 3³⁺The density of the activated barium germanium tellurate scintillating glass is 5.243g/cm³. The photoluminescence spectrum and X-ray excitation emission spectrum of example 3 were obtained by testing with an Edinburgh FLS980 fluorescence spectrometer (Ex slit 0.75nm, Em slit 0.75nm) and an X-ray excitation emission spectrometer (W target, 30kV,3mA), as shown in FIG. 4. As can be seen from FIG. 4, three luminescence peaks at 483, 575nm and 667nm in the emission spectrum under excitation at 350nm correspond to Dy, respectively³⁺Ion(s)⁴F_9/2→⁶H_J(J-15/2, 13/2, and 11/2) wherein 575nm (b: (B) (R))⁴F_9/2→⁶H_13/2) The wavelength emission intensity is maximum. While the scintillation light output of the scintillating glass of example 3 was obtained under X-ray (W target, 30kV,3mA) excitation, Dy was also clearly observed³⁺The strongest characteristic emission peak of the ion.

Example 4

The preparation process is substantially the same as that of example 1, except that the glass composition of example 4 is: is 30TeO₂-30GeO₂-40BaO, wherein the activator is Ce³⁺Ion, through CeF₃Introducing the mixture, wherein the external doping concentration is 0.5 mol%. The melting atmosphere is air.

Ce of example 4³⁺The density of the activated barium germanium tellurate scintillating glass is 5.169g/cm³. Adopting Edinburgh FLS980 fluorescence spectrometer (Ex slit 0.75nm, Em slit 0.75nm) and X-ray excitation emissionThe photoluminescence spectrum and the X-ray excitation emission spectrum of example 4 were obtained from the spectrometer (W target, 30kV,3mA) test, as shown in fig. 4. As can be seen from FIG. 4, at 390nm excitation, a broad peak located between 400 and 650nm in the emission spectrum corresponds to Ce³⁺Nanosecond optical transition of ion 5d-4f with the strongest emission peak position near 450 nm. However, the X-ray excitation emission spectrum of the scintillating glass of example 4 was obtained under X-ray (W target, 30kV,3mA) excitation, and substantially no Ce was observed in the spectrum³⁺The characteristic emission peak of the ions is because the melting atmosphere of the scintillation glass of this example is an air atmosphere, the color of the glass appearance is dark yellow, and in the future research, it should be noted that the glass melts as much as possible under reducing conditions, so that the scintillation light output is possible.

Examples 5 to 10

Specific formulations of examples 5-10 of the present invention are given in Table 2, wherein the activator is Eu³⁺Ions, by Eu₂O₃Introducing the mixture, wherein the external doping concentration is 0.1 mol%. The melting atmosphere is air.

The preparation processes of examples 5-10 are substantially the same as those of example 1, specifically, according to Eu in Table 2³⁺Accurately weighing each component according to a formula for activating the high-density barium germanium tellurate scintillation glass, fully and uniformly mixing, pouring into a platinum crucible, and then melting for 50min by a high-temperature melting method in an air atmosphere at 1000 ℃; pouring the uniform molten mass into a preheated stainless steel mold at 340 ℃ for casting molding, and naturally cooling to form glass; the glass was annealed in a muffle furnace at 340 ℃ for 4 hours to obtain scintillating glass according to examples 5-10. Cutting glass into 15 × 20 × 2.5 specification, grinding and polishing the surface to obtain Eu³⁺Activating the high-density barium germanium tellurate scintillation glass.

TABLE 2 EXAMPLES 5-10 high Density barium germanium tellurate scintillating glasses compositions

Example No. 2	TeO₂	GeO₂	BaO	Eu₂O₃	Density of
						Example 5	50	50	0	0.1	4.616
Example 6	50	40	10	0.1	4.764
						Example 7	50	30	20	0.1	5.268
Example 8	50	25	25	0.1	5.104
						Example 9	50	20	30	0.1	5.015
Example 10	50	10	40	0.1	5.267

As shown in Table 2, the density of the barium germanium tellurate scintillating glass is dependent on the substitution of BaO for GeO₂Has increased density of 4.616, 4.764,5.268, 5.104, 5.015g/cm³Changed to 5.267g/cm³So that the scintillation glass can better meet the high-density requirement of practical application.

The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.

Claims

1. The high-density barium germanium tellurate scintillation glass is characterized in that the scintillation glass comprises the following raw materials:

BaO：10-40 mol%；

GeO₂：20-40 mol%；

TeO₂: 20-60 mol%; and

a rare earth ion activator;

wherein, BaO and GeO₂And TeO₂The sum of the three components is 100 mol%;

2. The high-density barium germanium tellurate scintillation glass according to claim 1, wherein the scintillation glass comprises the following raw materials in parts by weight:

BaO：10-40 mol%；

GeO₂：20-35 mol%；

TeO₂: 30-60 mol%; and

a rare earth ion activator;

wherein, BaO and GeO₂And TeO₂The sum of the three components is 100 mol%;

3. The high-density barium germanium tellurate scintillating glass of claim 1, wherein the rare earth ion activator comprises Ce³⁺、Pr³⁺、Nd³⁺、Pm³⁺、Sm³⁺、Eu³⁺、Gd³⁺、Tb³⁺、Dy³⁺、Ho³⁺、Er³⁺、Tm³⁺And/or Yb³⁺Ions.

4. The method for preparing the high-density barium germanium tellurate scintillation glass according to any one of claims 1 to 3, wherein the method comprises the following steps:

5. The method of claim 4, wherein in step S1, the GeO in the glass component₂And TeO₂Direct introduction, BaO is introduced in the form of carbonate or nitrate, and activator ions are introduced in the form of corresponding rare earth oxide, rare earth fluoride, rare earth carbonate or rare earth nitrate compound.

6. The method of claim 4, wherein in step S2, the heat-resistant container comprises an alumina crucible or a platinum crucible.

7. The method of claim 4, wherein in step S3, the mold comprises a stainless steel mold;

the constant temperature annealing is carried out in a muffle furnace.

8. A scintillation screen or scintillation array made from the high density barium germanium tellurate scintillating glass of any one of claims 1 to 3.

9. An optical fiber drawn from the high density barium germanium tellurate scintillating glass of any one of claims 1 to 3.

10. The use of the high-density barium germanium tellurate scintillating glass of any one of claims 1 to 3 in the field of radiation detection.