CN100336754C - Organic blended lead-tin-fluorine-phosphate flash glass and its preparing method - Google Patents
Organic blended lead-tin-fluorine-phosphate flash glass and its preparing method Download PDFInfo
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- CN100336754C CN100336754C CNB2004100665459A CN200410066545A CN100336754C CN 100336754 C CN100336754 C CN 100336754C CN B2004100665459 A CNB2004100665459 A CN B2004100665459A CN 200410066545 A CN200410066545 A CN 200410066545A CN 100336754 C CN100336754 C CN 100336754C
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Abstract
The present invention discloses organic plumbum-tin doped fluorine-phosphate scintillation glass and a preparation method thereof. The organic plumbum-tin doped fluorine-phosphate scintillation glass is prepared from the components of the molar percentage: 52.2% of SnF2, 10.5% of SnO, 5.1% of PbF2, 32.1% of NH4H2PO4, 0.089% of stilbene 420 and 0.066% of p-TP. The preparation method comprises: the SnF2, the SnO, the PbF2 and the NH4H2PO4 used as raw materials are mixed, evenly milled, put in a crucible and put in a furnace to be melted; when a small amount of white smoke is given out, the stilbene 420 is added; the furnace is covered, and the raw materials are evenly mixed and then evenly mixed with the p-TP; the crucible is put in a vacuum drying oven, kept at the temperature and taken out; a fused mass is put in a mould, and the mould is cooled to the room temperature so as to obtain the transparent subnanosecond ultrafast PTFP scintillation glass doped with the p-TP and the stilbene 420. The one-step fusion method adopted by the present invention has the advantages of simple and convenient operation, etc., reduces the cost and enhances the transmissivity of scintillation glass.
Description
Technical field
The present invention relates to a kind of scintillation glass and preparation method thereof, relate in particular to a kind of organic blended lead-tin-fluorine-phosphate flash glass and preparation method thereof.
Background technology
Along with the fast development of high energy physics, nuclear physics and Application of Nuclear Technology, inorganic scintillation crystal commonly used will be difficult to satisfy the needs of superelevation counting rate in measuring, and various countries are actively developing the research of novel fast flashing body in recent years for this reason.In conjunction with the ultrafast fall time of organic scintillator, the output of high light and the high-density of inorganic scintillation glass, the advantage of good resistance radiation damage, to obtain novel fast flashing glass, this is a research focus of present scintillation material preparation field.For example, the people such as C.Smith of U.S. Lawrence Livermore National Laboratory in 1994 are at Mat.Res.Soc.Proc., 1994, Vol.348, the article of delivering on the P209 is to be matrix with low-melting lead-Xi-fluorophosphate (PTFP), organic activators such as doping stilbene, POPOP, stilbene 420 use open glass carbon crucible, prepare the compound scintillation glass of organic and inorganic by a step scorification.These glass have the decay of luminescence speed (less than 1ns) that is exceedingly fast, but luminous a little less than.The domestic Zhao Hong of Northwestern Polytechnical University gives birth to and waits the people at Nucl.Instr.and Meth.A, 2000, Vol.448, P550 and Northwestern Polytechnical University's journal, 2000, Vol.18, No.2, the article of delivering on the P225 is to use uncovered ceramic crucible, also develops some organic activators (as p-TP, p-QP and POPOP etc.) doped P TFP organic and inorganic compound glass in succession by two step scorifications.But its fall time, about 5ns showed the Weak-luminescence characteristic.
Up to now, domestic also not about the report of fall time in the organic blended fast flashing glass preparation of subnanosecond level.
Summary of the invention
One of purpose of the present invention is to provide a kind of organic blended lead-tin-fluorine-phosphate flash glass;
Another object of the present invention is to provide the preparation method of this scintillation glass.
Goal of the invention of the present invention is achieved by the following technical solution:
In order to obtain the fast flashing material of fall time in the subnanosecond level, the present invention adopts p-terphenyl (p-TP) and 420 pairs of stilbenes to mix preparation PTFP (lead-tin-fluorine-phosphate) fast flashing glass.The prepared glass that goes out reaches 0.48ns fall time, is better than the fastest inorganic scintillator commonly used---BaF at present on luminescence decay time
2Crystal (its luminous fast, composition fall time be 0.6ns).And the density height of this kind glass is (greater than 4g/cm
3), chemical stability is good.
Select for use analytically pure p-TP and stilbene 420 to be doping agent, analytically pure SnF
2, SnO, PbF
2, NH
4H
2PO
4Be the raw material of preparation PTFP host glass, the mol ratio of various compositions is: 52.2SnF
210.5SnO5.1PbF
232.1NH
4H
2PO
40.089 stilbene 4200.066p-TP adopts and adds a cover the fast flashing glass that a step scorification is prepared the subnanosecond level.
The preparation method is as follows: by the SnF of above-mentioned given mol ratio
2, SnO, PbF
2, NH
4H
2PO
4Raw material mixes and grinds evenly.Earlier, allow crucible naturally cool to after the room temperature again with the preheating 10～15 minutes under 300～350 ℃ temperature of plated film high purity graphite crucible.To join through the abrasive of drying treatment in the crucible, crucible places 400 ℃ stove melt processed 0.5～1 hour.From stove, take out crucible, open crucible cover, do not add stilbene 420 when a large amount of white cigarettes are emerged, and the level of adding a cover shakes up, then crucible is placed 245 ℃ loft drier constant temperature to handle 5～20 minutes when having.Take out crucible once more from stove, adding p-TP also shakes up, and crucible is placed 245 ℃ vacuum drying oven, is incubated and takes out crucible after 3～5 minutes.Melt is injected the copper mould of 60 ℃ of insulations, treated to send into after melt solidifies in 60 ℃ of baking ovens insulation 10 minutes, mold cools down to room temperature, is obtained transparent ultrafast p-TP of subnanosecond level and 420 pairs of stilbenes and mixes the PTFP scintillation glass.
Adopt the prepared glass that goes out of the present invention, exciting down relatively at gamma-rays, light output is about 0.9% of plastic scintillator ST401; Aspect decay of luminescence speed, be better than at present the fastest commonly used inorganic scintillator for reaching 0.48ns the fall time of this kind glass
BaF
2Crystal (its luminous fast composition fall time be 0.6ns).This kind glass has also that melt temperature is low, density is high (greater than 4g/cm simultaneously
3), and series of advantages such as good optical performance and chemical stability.Therefore this p-TP and 420 pairs of stilbenes are mixed the big irradiation dose that PTFP glass is specially adapted to fields such as high energy physics, nuclear physics and nuclear technique, the measurement in the superelevation counting rate.
Aspect preparation technology, adopt and to add a cover plated film high purity graphite crucible, prepare the ultrafast p-TP of subnanosecond level and 420 pairs of stilbenes are mixed the PTFP scintillation glass by a step scorification.A step scorification that is adopted has simple, convenient advantage.Scintillation glass is founded and is carried out vacuum heat-preserving in the process, has improved the transmissivity of glass in ultraviolet-visible region.Crucible is added a cover in use, is convenient to reduce the component volatilization in the glass smelting process, can also be with NH
4H
2PO
4The ammonia that thermal degradation produces is founded black SnO and the yellow PbO that generates because of oxidation in the process as the restitutive protection's gas in the glass smelting process with minimizing, reaches the purpose that improves the scintillation glass transmissivity.The plated film high purity graphite crucible that is adopted helps increasing the compactness of plumbago crucible, avoids graphite on the sidewall of crucible to come off and the impurity introduced; Because fluorine and phosphorus in the PTFP glass are extremely strong to the corrosive nature of crucible, with respect to the vitreous carbon crucible, plumbago crucible is more cheap, thereby can reduce the preparation cost of glass.
Embodiment
How further specify this civilization below in conjunction with specific embodiment realizes:
Embodiment
Raw materials used is analytically pure SnF
2, SnO, PbF
2, NH
4H
2PO
4, stilbene 420 and p-TP, 52.2SnF in molar ratio
210.5SnO5.1PbF
232.1NH
4H
2PO
4Take by weighing each constituent element, make its gross weight be about 15 grams.
Raw material mixing and grinding is even.Earlier about 10 minutes, allow crucible naturally cool to after the room temperature in preheating under 300 ℃ the temperature again in plated film high purity graphite crucible.To join through the abrasive of drying treatment in the crucible, crucible places 400 ℃ stove melt processed 45 minutes.Take out crucible from stove, open crucible cover, when there not being the stilbene 420 that adds 0.5 milligram when a large amount of white cigarettes are emerged, and the level of adding a cover shakes up, and then crucible placed 245 ℃ loft drier constant temperature to handle 10 minutes.From stove, take out crucible once more, add 24 milligrams p-TP and shake up, crucible is placed 245 ℃ vacuum drying oven, be incubated and take out crucible after 3 minutes.Melt is injected the copper mould of 60 ℃ of insulations, treated to send into after melt solidifies in 60 ℃ of baking ovens insulation 10 minutes, mold cools down to room temperature, is obtained transparent ultrafast p-TP of subnanosecond level and 420 pairs of stilbenes and mixes the PTFP scintillation glass.
Claims (4)
1, a kind of organic blended lead-tin-fluorine-phosphate flash glass, the mol ratio of its composition and composition is: SnF
2: SnO: PbF
2: NH
4H
2PO
4: stilbene 420: p-TP=52.2: 10.5: 5.1: 32.1: 0.089: 0.066.
2, at the preparation method of the described a kind of organic blended lead-tin-fluorine-phosphate flash glass of claim 1, step is as follows:
A, by the analytically pure SnF of given mol ratio
2, SnO, PbF
2, NH
4H
2PO
4Raw material mixes and also to grind evenly, earlier with the preheating of plated film high purity graphite crucible, allow crucible naturally cool to room temperature again after, will join through the abrasive of drying treatment in the crucible, crucible places 400 ℃ stove melt processed 0.5～1 hour;
B, from stove, take out crucible, open crucible cover, do not add stilbene 420 when a large amount of white cigarettes are emerged, and the level of adding a cover shakes up, then crucible is placed 245 ℃ loft drier constant temperature to handle 5～20 minutes when having;
C, from stove, take out crucible once more, add analytically pure p-TP and shake up, crucible is placed 245 ℃ vacuum drying oven, be incubated and take out crucible after 3～5 minutes;
D, melt is injected the copper mould of 60 ℃ of insulations, treat to send into after melt solidifies in 60 ℃ of baking ovens after the insulation, mold cools down to room temperature, is obtained transparent ultrafast p-TP of subnanosecond level and 420 pairs of stilbenes and mixes lead-tin-fluorine-phosphate flash glass.
3, the preparation method of a kind of organic blended lead-tin-fluorine-phosphate flash glass according to claim 2 is characterized in that: the preheating temperature of the plated film high purity graphite crucible in the described A step is 300～350 ℃.
4, the preparation method of a kind of organic blended lead-tin-fluorine-phosphate flash glass according to claim 2 is characterized in that: send into behind the melt solidifying in the described D step that soaking time is 10 minutes in 60 ℃ of baking ovens.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100665459A CN100336754C (en) | 2004-09-21 | 2004-09-21 | Organic blended lead-tin-fluorine-phosphate flash glass and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100665459A CN100336754C (en) | 2004-09-21 | 2004-09-21 | Organic blended lead-tin-fluorine-phosphate flash glass and its preparing method |
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| Publication Number | Publication Date |
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| CN1587141A CN1587141A (en) | 2005-03-02 |
| CN100336754C true CN100336754C (en) | 2007-09-12 |
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| CN104099095A (en) * | 2013-04-09 | 2014-10-15 | 海洋王照明科技股份有限公司 | Neodymium-and-ytterbium-codoped stannic fluoride glass up-conversion luminescent material, and preparation method and application thereof |
| CN106324658B (en) * | 2015-06-30 | 2019-04-23 | 中国辐射防护研究院 | The method adulterated the plastic scintillant of neutron-sensitive substance cadmium and its measure thermal neutron |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087066A (en) * | 1992-11-17 | 1994-05-25 | 浙江大学 | High-density, radiotolerant fast flash inorganic glass |
| CN1246452A (en) * | 1998-09-02 | 2000-03-08 | 西北工业大学 | Lead halophosphate glass |
| CN1400193A (en) * | 2001-07-30 | 2003-03-05 | 通用电气公司 | Flashing agent composite of alkali metal and rare earth metal tungstate |
-
2004
- 2004-09-21 CN CNB2004100665459A patent/CN100336754C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087066A (en) * | 1992-11-17 | 1994-05-25 | 浙江大学 | High-density, radiotolerant fast flash inorganic glass |
| CN1246452A (en) * | 1998-09-02 | 2000-03-08 | 西北工业大学 | Lead halophosphate glass |
| CN1400193A (en) * | 2001-07-30 | 2003-03-05 | 通用电气公司 | Flashing agent composite of alkali metal and rare earth metal tungstate |
Non-Patent Citations (3)
| Title |
|---|
| 掺杂p-TP和POPOP的闪烁玻璃的研究 朱冬梅，赵宏生，周万城，西北工业大学学报，第19卷第2期 2001 * |
| 掺杂对三联苯的铅-锡-氟磷酸盐闪烁玻璃的研究 赵宏生，周万城，西北工业大学学报，第18卷第2期 2000 * |
| 闪烁玻璃的研究进展 赵宏生，周万城，材料导报，第15卷第1期 2001 * |
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|---|---|
| CN1587141A (en) | 2005-03-02 |
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