CN102153280A

CN102153280A - Method for preparing scintillation glass

Info

Publication number: CN102153280A
Application number: CN201010110055XA
Authority: CN
Inventors: 顾牡; 金鑫杰; 黄世明; 刘小林; 刘波; 倪晨
Original assignee: Tongji University
Current assignee: Tongji University
Priority date: 2010-02-11
Filing date: 2010-02-11
Publication date: 2011-08-17

Abstract

The invention provides a method for preparing scintillation glass. In the method, the scintillation glass is prepared by adding reducing agents such as semiconductor silicon, silicon monoxide, lithium, sodium, barium, cesium, lanthanum, yttrium or the like to a scintillation glass formula to be uniformly mixed, melting at a high temperature and annealing. The prepared scintillation glass increases Tb<4+>-to-Tb<3+> conversion rate in a glass system and effectively enhances the luminous intensity of the Tb<3+>-doped silicate scintillation glass. Moreover, in the method provided by the invention, the preparation cost and difficulty of the scintillation glass are reduced because the Tb<4+> is reduced to Tb<3+> without need of adopting a mode of introducing a reducing gas (such as H2 (Hydrogen), CO (Carbon Monoxide) and the like).

Description

A kind of preparation method of scintillation glass

Technical field

The invention belongs to field of light emitting materials, relate to scintillation glass, especially the preparation method of flicker glass of silicate activated by terbium.

Background technology

Scintillation material is a kind of optical function material that sends visible light behind the high-energy photon that absorbs, and has obtained in fields such as high energy physics, nuclear physics, astrophysics, earth physics, industrial flaw detection, medical imaging and safety detection in recent years using widely.

Scintillation crystal is to study maximum, most widely used scintillator at present, as Bi ₄Ge ₃O ₁₂(BGO), CeF ₃, PbWO ₄Deng.But scintillation crystal exists complicated process of preparation, growth cycle is long, cost is high and large size single crystal produces shortcomings such as difficulty is big, particularly traditional crystal sound field technology is difficult to guarantee the high density and the uniform distribution of dopant ion, and then can't realize the optical property optimization of material, this has limited its application greatly.And rear-earth-doped scintillation glass is easily transferred because of it has chemical composition, optical homogeneity is good, realize that easily characteristics such as large size and preparation method are simple have been subjected to people's extensive concern.At common rare earth (Ce ³⁺, Eu ³⁺, Tb ³⁺, Dy ³⁺Deng) in the doping scintillation glass, Tb ³⁺The doped silicate scintillation glass has the luminous intensity height, the transparency good, fluorescent emission mainly from ⁵D ₄Energy level produces the strong green fluorescence that is positioned at the 550nm arrowband, with the sensitive wave length coupling of CCD element.Therefore, Tb ³⁺The doped silicate scintillation glass is a research focus of rare earth scintillating materials always.

Further improve Tb ³⁺The luminous intensity of doping scintillation glass is the key that enlarges its range of application.For example: nineteen ninety-five, people such as Buchanan discover and add Gd ₂O ₃Can significantly improve Tb ³⁺The luminous intensity of doping scintillation glass (U.S.Patent5108959).2006, turn round and look at the male people of grade and find to improve Tb ³⁺Optimum doping concentration also can strengthen Tb ³⁺The luminous intensity of doping scintillation glass (CN200610118620.0).In addition, at Tb ³⁺In the doped silicate scintillation glass preparation process, Tb ³⁺Ion all is with Tb ₄O ₇Form is introduced, and therefore improves Tb ⁴⁺→ Tb ³⁺Efficiency of conversion also is to strengthen Tb ³⁺One of effective ways of doping scintillation glass luminous intensity.People adopt usually and feed reducing gas (as H at present ₂, CO etc.) mode to improve Tb ⁴⁺→ Tb ³⁺Efficiency of conversion strengthens Tb ³⁺Luminous intensity.But these class methods have not only increased the preparation difficulty of scintillation glass, have also improved the cost of glass preparation.Therefore, guaranteeing Tb ³⁺When doping scintillation glass preparation technology is simple, with low cost, improve Tb ⁴⁺→ Tb ³⁺Efficiency of conversion is the difficult problem that urgency is to be solved.

Summary of the invention

The object of the present invention is to provide a kind of preparation method of scintillation glass, it has improved Tb ⁴⁺→ Tb ³⁺Turnover ratio, strengthen Tb significantly ³⁺The flicker light intensity of doped silicate glasses.

For reaching above purpose, solution of the present invention is:

The preparation method of this scintillation glass comprises by adding and making after metal such as reductive agent such as semiconductor silicon, silicon monoxide or lithium, sodium, barium, caesium, lanthanum, yttrium and prescription mix.Wherein, the prescription of described scintillation glass is (by mass percentage):

SiO ₂ 35-60wt％

B ₂O ₃ 0-10wt％

P ₂O ₅ 0-10wt％

Al ₂O ₃ 0.5-3wt％

MgO 0-20wt％

CaO 0-30wt％

SrO 0-45wt％

BaO 5-50wt％

Li ₂O 0-10wt％

Na ₂O 0-25wt％

K ₂O 0-25wt％

Rb ₂O 0-25wt％

Cs ₂O 0-25wt％

Y ₂O ₃ 0-20wt％

La ₂O ₃ 0-20wt％

Gd ₂O ₃ 1-15wt％

Tb ₄O ₇ 5-20wt％

It specifically may further comprise the steps:

The first step: carry out proportioning according to prescription,

Second step: add reductive agent, reductive agent is for mixing 0.2-5wt% outward;

The 3rd step: reductive agent and prescription thorough mixing were evenly founded 3-5 hour with scorification under 1500-1550 ℃ in the air atmosphere of back;

The 4th step: the 3rd glass metal that make of step poured in the good mould of thermal pretreatment finalize the design;

The 5th step: anneal was carried out in insulation in 2-4 hour under 500-650 ℃ in retort furnace.

Preferably, described prescription and reductive agent ratio are specially (by mass percentage):

SiO ₂ 46.3wt％

Al ₂O ₃ 1.5wt％

BaO 8.15wt％

Cs ₂O 8.15wt％

Na ₂O 2.8wt％

Li ₂O 4.0wt％

K ₂O 1.3wt％

Gd ₂O ₃ 12.5wt％

Tb ₄O ₇ 15.3wt％

Reductive agent (mixing outward) 1.5wt%

Owing to adopted such scheme, the present invention to have following characteristics:

1, preparation technology is simple, chemical composition is easily transferred, easily realize large size, chemical stability is good, can be drawn into optical fiber;

2, need not to adopt the feeding reducing gas (as H ₂, CO etc.) mode reduce Tb ⁴⁺→ Tb ³⁺, reduced the preparation cost and the difficulty of scintillation glass, guaranteeing Tb ³⁺When doping scintillation glass preparation technology is simple, with low cost, improved Tb in the glass system ⁴⁺→ Tb ³⁺Efficiency of conversion has strengthened Tb effectively ³⁺The luminous intensity of doped silicate scintillation glass;

3, emission peak is positioned near the most responsive 550nm of human eye, can well mate with the spectral response of charge-coupled device (CCD), aspects such as X ray biomedical imaging, nuclear technological applications is had important use be worth and realistic meaning.

Description of drawings

Fig. 1 is the comparison of the scintillation glass luminous intensity under excitation of X-rays before and after the interpolation reductive agent.

Embodiment

The present invention is further illustrated below in conjunction with the accompanying drawing illustrated embodiment.

Embodiment 1

One, preparation technology

The first step: prescription (by mass percentage)

SiO ₂ 48.3wt％

Al ₂O ₃ 1.5wt％

BaO 9.9wt％

Cs ₂O 9.9wt％

Na ₂O 2.8wt％

Li ₂O 2.0wt％

K ₂O 1.3wt％

Gd ₂O ₃ 9.0wt％

Tb ₄O ₇ 15.3wt％

S _iO (mixing outward) 0.5wt%

Second step: the thorough mixing of will filling a prescription was evenly founded 3-5 hour with scorification under 1500-1550 ℃ in the air atmosphere of back;

The 3rd step: second glass metal that make of step poured in the good mould of thermal pretreatment finalize the design;

The 4th step: anneal was carried out in insulation in 2-4 hour under 500-650 ℃ in retort furnace.

Two, test

The glass cutting that makes is become the sample of 25mm * 10mm * 5mm, test excitation of X-rays emission spectrum 80kV after polishing, 4mA (as shown in Figure 1).

Three, use

Scintillation glass by above method makes has important value to X ray real time imagery, Application of Nuclear Technology.

Embodiment 2

Other are all identical with embodiment 1, just the prescription difference among the preparation technology.

Prescription (by mass percentage)

SiO ₂ 48.3wt％

Al ₂O ₃ 1.5wt％

BaO 9.9wt％

Cs ₂O 9.9wt％

Na ₂O 2.8wt％

Li ₂O 2.0wt％

K ₂O 1.3wt％

Gd ₂O ₃ 9.0wt％

Tb ₄O ₇ 15.3wt％

S _iO (mixing outward) 1.5wt%

Embodiment 3

Prescription (by mass percentage)

SiO ₂ 48.3wt％

Al ₂O ₃ 1.5wt％

BaO 9.9wt％

Cs ₂O 9.9wt％

Na ₂O 2.8wt％

Li ₂O 2.0wt％

K ₂O 1.3wt％

Gd ₂O ₃ 9.0wt％

Tb ₄O ₇ 15.3wt％

S _iO (mixing outward) 2.5wt%

The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.

Claims

1. the preparation method of a scintillation glass is characterized in that: add reductive agent and carry out high-temperature fusion in the prescription of scintillation glass, make after anneal.

2. the preparation method of scintillation glass as claimed in claim 1, it is characterized in that: it specifically may further comprise the steps:

1) prescription according to scintillation glass carries out proportioning;

2) add reductive agent;

3) reductive agent and prescription thorough mixing were evenly founded 3-5 hour with scorification under 1500-1550 ℃ in the air atmosphere of back;

4) glass metal that makes in the step 3) is poured in the good mould of thermal pretreatment finalized the design;

5) in retort furnace, be incubated 2-4 hour under 500-650 ℃ and carry out anneal.

3. the preparation method of scintillation glass as claimed in claim 1 or 2, it is characterized in that: described reductive agent is semiconductor silicon, silicon monoxide, lithium, sodium, barium, caesium, lanthanum or yttrium.

4. the preparation method of scintillation glass as claimed in claim 3 is characterized in that: the prescription of scintillation glass is (note by mass percentage):

SiO ₂ 35-60wt％

B ₂O ₃ 0-10wt％

P ₂O ₅ 0-10wt％

Al ₂O ₃ 0.5-3wt％

MgO 0-20wt％

CaO 0-30wt％

SrO 0-45wt％

BaO 5-50wt％

Li ₂O 0-10wt％

Na ₂O 0-25wt％

K ₂O 0-25wt％

Rb ₂O 0-25wt％

Cs ₂O 0-25wt％

Y ₂O ₃ 0-20wt％

La ₂O ₃ 0-20wt％

Gd ₂O ₃ 1-15wt％

Tb ₄O ₇ 5-20wt％

5. the preparation method of scintillation glass as claimed in claim 4 is characterized in that: the formula optimization of described scintillation glass is (note by mass percentage):

SiO ₂ 46.3wt％

Al ₂O ₃ 1.5wt％

BaO 8.15wt％

Cs ₂O 8.15wt％

Na ₂O 2.8wt％

Li ₂O 4.0wt％

K ₂O 1.3wt％

Gd ₂O ₃ 12.5wt％

Tb ₄O ₇ 15.3wt％

6. the preparation method of scintillation glass as claimed in claim 3, it is characterized in that: the mass percent of described reductive agent is for mixing 0.2-5% outward.

7. the preparation method of scintillation glass as claimed in claim 6, it is characterized in that: the mass percent of described reductive agent is preferably 1.5%.