CN113846379B - Compound bismuth cadmium phosphate and bismuth cadmium phosphate scintillation crystal, and preparation method and application thereof - Google Patents
Compound bismuth cadmium phosphate and bismuth cadmium phosphate scintillation crystal, and preparation method and application thereof Download PDFInfo
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- CN113846379B CN113846379B CN202010594736.1A CN202010594736A CN113846379B CN 113846379 B CN113846379 B CN 113846379B CN 202010594736 A CN202010594736 A CN 202010594736A CN 113846379 B CN113846379 B CN 113846379B
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- cadmium
- bismuth
- cdo
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- phosphate
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- 239000013078 crystal Substances 0.000 title claims abstract description 151
- -1 Compound bismuth cadmium phosphate Chemical class 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 60
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 80
- 229910003069 TeO2 Inorganic materials 0.000 claims description 56
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 56
- 229910000011 cadmium carbonate Inorganic materials 0.000 claims description 50
- 239000002994 raw material Substances 0.000 claims description 40
- 238000001816 cooling Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 33
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 32
- 229910052797 bismuth Inorganic materials 0.000 claims description 28
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 28
- 229910052793 cadmium Inorganic materials 0.000 claims description 27
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 27
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 claims description 26
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 20
- GKDXQAKPHKQZSC-UHFFFAOYSA-L cadmium(2+);carbonate Chemical compound [Cd+2].[O-]C([O-])=O GKDXQAKPHKQZSC-UHFFFAOYSA-L 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 16
- TXKAQZRUJUNDHI-UHFFFAOYSA-K bismuth tribromide Chemical compound Br[Bi](Br)Br TXKAQZRUJUNDHI-UHFFFAOYSA-K 0.000 claims description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 15
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 14
- 229940036348 bismuth carbonate Drugs 0.000 claims description 14
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 claims description 14
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 14
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 13
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 13
- XAEZALCLBRUCLR-UHFFFAOYSA-K bismuth;hydrogen carbonate Chemical compound [Bi+3].OC([O-])=O.OC([O-])=O.OC([O-])=O XAEZALCLBRUCLR-UHFFFAOYSA-K 0.000 claims description 13
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 13
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 13
- ODYFKJUYWXSYJA-UHFFFAOYSA-L cadmium(2+);carbonic acid;carbonate Chemical compound [Cd+2].OC([O-])=O.OC([O-])=O ODYFKJUYWXSYJA-UHFFFAOYSA-L 0.000 claims description 13
- RMCKOIXJLDOSOT-UHFFFAOYSA-L cadmium(2+);oxalate Chemical compound [Cd+2].[O-]C(=O)C([O-])=O RMCKOIXJLDOSOT-UHFFFAOYSA-L 0.000 claims description 13
- FIMTUWGINXDGCK-UHFFFAOYSA-H dibismuth;oxalate Chemical compound [Bi+3].[Bi+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O FIMTUWGINXDGCK-UHFFFAOYSA-H 0.000 claims description 13
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 13
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 13
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 13
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 10
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000007689 inspection Methods 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 238000009206 nuclear medicine Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000003384 imaging method Methods 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 229940049676 bismuth hydroxide Drugs 0.000 claims description 3
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 claims 19
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims 7
- 150000001621 bismuth Chemical class 0.000 claims 3
- 150000001661 cadmium Chemical class 0.000 claims 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims 3
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims 2
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims 1
- 239000003814 drug Substances 0.000 claims 1
- 230000005251 gamma ray Effects 0.000 claims 1
- 229910000464 lead oxide Inorganic materials 0.000 claims 1
- 239000003129 oil well Substances 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 150000003017 phosphorus Chemical class 0.000 claims 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000463 material Substances 0.000 description 23
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 16
- 239000000843 powder Substances 0.000 description 15
- 239000004570 mortar (masonry) Substances 0.000 description 14
- 235000021317 phosphate Nutrition 0.000 description 12
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 11
- 238000002083 X-ray spectrum Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- KOHRTFCSIQIYAE-UHFFFAOYSA-N cadmium;carbonic acid Chemical compound [Cd].OC(O)=O KOHRTFCSIQIYAE-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000000137 annealing Methods 0.000 description 6
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 6
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 5
- YAMPQRWRFJYHJN-UHFFFAOYSA-N [Cd].[Bi] Chemical compound [Cd].[Bi] YAMPQRWRFJYHJN-UHFFFAOYSA-N 0.000 description 5
- 229910000423 chromium oxide Inorganic materials 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000008646 thermal stress Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- LVEULQCPJDDSLD-UHFFFAOYSA-L cadmium fluoride Chemical compound F[Cd]F LVEULQCPJDDSLD-UHFFFAOYSA-L 0.000 description 2
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 229910052702 rhenium Inorganic materials 0.000 description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229940075417 cadmium iodide Drugs 0.000 description 1
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000001959 radiotherapy Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000012856 weighed raw material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/14—Phosphates
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/02—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method without using solvents
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- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/14—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method characterised by the seed, e.g. its crystallographic orientation
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- C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
- C30B15/34—Edge-defined film-fed crystal-growth using dies or slits
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- C30B33/00—After-treatment of single crystals or homogeneous polycrystalline material with defined structure
- C30B33/02—Heat treatment
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- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
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- C30B9/00—Single-crystal growth from melt solutions using molten solvents
- C30B9/04—Single-crystal growth from melt solutions using molten solvents by cooling of the solution
- C30B9/08—Single-crystal growth from melt solutions using molten solvents by cooling of the solution using other solvents
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Abstract
The invention relates to a compound of cadmium bismuth phosphate, a scintillation crystal of cadmium bismuth phosphate, a preparation method and application thereof, wherein the chemical formulas of the compound and the crystal are Bi35‑xCdxP10O(155‑x)/2Wherein x =0-35, the crystal belongs to monoclinic system, space group C2, and the unit cell parameter is
Z＝2，
The molecular weight is 5204.09-8864g/mol, and the crystal density is 4.476-8.529g/cm3. The method is characterized in that a solid-phase reaction method is adopted to synthesize a compound of cadmium bismuth phosphate, a high-temperature molten salt method, a Czochralski method, a top-seeded method, a Bridgman-Stockbarge method, a hydrothermal method, a temperature gradient method, a floating zone method or a guided mode method is adopted to grow cadmium bismuth phosphate scintillation crystals, and the cadmium bismuth phosphate crystals are used as scintillation crystals.
Description
Technical Field
The invention relates to a chemical formula of a compound bismuth cadmium phosphate and a bismuth cadmium phosphate scintillation crystal both of which have Bi35- xCdxP10O(155-x)/2Wherein x =0-35. The invention relates to the field of crystals, in particular to a bismuth cadmium phosphate compound, a bismuth cadmium phosphate scintillation crystal, a preparation method and application thereof.
Background
The scintillating material is a material which can absorb high-energy particles or rays and emit visible photons, wherein the ultrafast scintillating material refers to a material with the response time less than 4ns (10 ns)-9s) scintillator material. The material plays a role in prop in Pulsed radiation detection, solar neutron detection, reaction kinetics, inertial confinement nuclear fusion and cosmic ray research. Although different applications may impose different requirements on the scintillation crystal, the scintillation crystal is used in most applications for detecting ionizing radiation, so that the scintillation crystal is required to have a high capability of blocking ionizing radiation, i.e. the scintillation crystal is required to have a high density and to contain elements with large atomic numbers. The principle of X-ray, CT, nuclear medicine radionuclide imaging, environmental radiation monitoring and high-energy ray detection is that photon flow is used as a ray source, rays penetrate through a human body or a substance and then are emitted from the human body or the substance or are directly received by a detector to form an image, so that the receiving degree of the detector system to the rays becomes one of the key factors, and an inorganic scintillation crystal is the most commonly used core component of the detector system. The scintillation crystal generates a fluorescence pulse under the excitation of a high-energy ray or a radioactive particle when the ray or the particle passes through the scintillation crystal. After the exploration, research and development of the inorganic scintillation crystal for nearly 100 years, the inorganic scintillation crystal is widely applied to the fields of high-energy physics, nuclear medicine (such as XCT and PET), industrial nondestructive inspection, geological exploration, petroleum logging and the like.
Common halide scintillation crystals include NaI: TI, csI: TI, and BaF2And rare earth halide crystals. The NaI/TI crystal has the advantages of high light yield, high photoelectric conversion efficiency, stable chemical performance, easy growth, etc. and is one scintillator with excellent comprehensive performanceThe defects of short solution and irradiation length, slightly poor ray-stopping capability and the like are gradually replaced by bismuth germanate (Bi) in the high-energy physical field4Ge3O12) Crystal substitution. As a conventional scintillation crystal, bi4Ge3O12The crystals also have problems such as long decay time and GeO in the starting material2The components are expensive, and the production and the use of the material are restricted. Therefore, both from the viewpoint of performance and cost, bi is actively sought4Ge3O12A substitute for the crystal. In addition, the common tungstate scintillation crystals are mainly PbWO4、GdWO4、CdWO4And so on. Due to PbWO4The crystals have a high density (about 8.3 g/cm)3) Short irradiation length (about 0.89 cm), fast decay time (90% of luminescence decay time is less than 20 ns), low price and the like, and is selected by the European Nuclear research Center (CERN) as a scintillating material for an electromagnetic energy meter (ECAL) in a Large Hadron Collider (LHC). However, pbWO4The disadvantage of low light yield of crystals limits its application beyond the field of high-energy physics. Therefore, it is still a challenge to find new scintillating crystals that have relatively high luminous efficiency, high energy resolution, strong resistance to radiation damage, high material density, no deliquescence, high mechanical hardness, easy cutting, polishing, and storage, and low cost.
Disclosure of Invention
The invention aims to provide a compound of cadmium bismuth phosphate and a scintillation crystal of cadmium bismuth phosphate, wherein the chemical formulas of the compounds are Bi35- xCdxP10O(155-x)/2Wherein x =0-35.
The invention also aims to provide a method for synthesizing the compound of cadmium bismuth phosphate by adopting a solid-phase reaction method and a method for preparing the cadmium bismuth phosphate scintillation crystal by adopting a high-temperature molten salt method, a pulling method, a top-seeded method, a Bridgman-Stockbarge method, a hydrothermal method, a temperature gradient method, a floating zone method or a guided mode method.
The invention further aims to provide the bismuth cadmium phosphate scintillation crystal prepared by the method for preparing the bismuth cadmium phosphate scintillation crystal, which can be used in the technical fields of detection of x rays, gamma rays, neutrons and other high-energy particles, nuclear medicine imaging, radiation medical treatment, industrial nondestructive inspection, safety inspection, petroleum logging, nuclear prospecting, high-energy physics and space physics.
The technical scheme of the invention is as follows:
the chemical formula of the bismuth cadmium phosphate compound provided by the invention is Bi35-xCdxP10O(155-x)/2X =0-35, which is a solid phase reaction method for preparing a cadmium bismuth phosphate compound according to the following chemical reaction formula, wherein x =0-35,
1)(35-x)/2Bi2O3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑
2)(35-x)/2(BiO)2CO3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35-x)/2CO2↑
3)(35-x)Bi(OH)3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+((105-3x)/2+15)H2O↑
4)(35-x)Bi(NO3)3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(105-3x)NO2↑
5)(35-x)BiI3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(105-3x)/2I2↑
6)(35-x)BiBr3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(105-3x)/2Br2↑
7)(35-x)BiOCl+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35-x)/2Cl2↑
8)(35-x)/2Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2↑
9)(35-x)/2Bi2O3+xCdI2+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xI2↑
10)(35-x)/2Bi2O3+xCdSO4+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xSO2↑
11)(35-x)/2(BiO)2CO3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35+x)/2CO2↑
12)(35-x)/2(BiO)2CO3+xCdI2+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35-x)/2CO2↑+xI2↑
13)(35-x)/2(BiO)2CO3+xCdF2+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35-x)/2CO2↑+xF2↑
14)(35-x)/2(BiO)2CO3+xCdSO4+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35-x)/2CO2↑+xSO2↑
15)(35-x)Bi(OH)3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+((105-3x)/2+15)H2O↑+xCO2↑
16)(35-x)Bi(OH)3+3CdI2+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+((105-3x)/2+15)H2O↑↑+xI2↑
17)(35-x)Bi(OH)3+3CdF2+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+((105-3x)/2+15)H2O↑+xF2↑
18)(35-x)Bi(OH)3+xCdSO4+10NH4H2PO4→Bi32Cd3P10O(155-x)/2+10NH3↑+((105-3x)/2+15)H2O↑+xSO2↑
the compound bismuth cadmium phosphate and the bismuth cadmium phosphate scintillation crystal provided by the invention are characterized in that the chemical formulas of the crystal are Bi35-xCdxP10O(155-x)/2Wherein x =0-35, the crystal belongs to monoclinic system, space group C2, does not have symmetry center, and has unit cell parameter of
The molecular weight is 5204.09-8864g/mol, and the crystal density is 4.476-8.529g/cm3
The preparation method of the bismuth cadmium phosphate scintillation crystal provided by the invention adopts a high-temperature molten salt method or a Czochralski method or a top seed crystal method or a Bridgman-Stockbarge method or a hydrothermal method or a temperature gradient method or a floating zone method or a guided mode method to grow the bismuth cadmium phosphate scintillation crystal, and the specific operation is carried out according to the following steps:
a. mixing single-phase polycrystalline powder of a bismuth cadmium phosphate compound or the single-phase polycrystalline powder of the bismuth cadmium phosphate compound with a fluxing agent, uniformly grinding, heating the mixture to 500-1400 ℃ at a heating rate of 0.5-80 ℃/h, keeping the temperature for 3-80 hours to obtain a mixed melt, and cooling to 300-800 ℃, wherein the molar ratio of the single-phase polycrystalline powder of the bismuth cadmium phosphate compound to the fluxing agent is 1;
or directly heating the mixture of the bismuth-containing compound, the cadmium-containing compound and the phosphorus-containing compound or the mixture of the bismuth-containing compound, the cadmium-containing compound and the phosphorus-containing compound with the fluxing agent at the temperature rise rate of 0.5-80 ℃/h to the temperature of 500-1400 ℃, keeping the temperature for 3-80 hours to obtain a mixed melt, and then cooling to the temperature of 300-800 ℃, wherein the molar ratio of the bismuth-containing compound, the cadmium-containing compound and the phosphorus-containing compound to the fluxing agent is (35-x): 0.1-20, and x =0-35;
the fluxing agent being essentially a self-fluxing agent, such as Bi2O3、(BiO)2CO3、Bi(OH)3、Bi(NO3)3、BiI3、BiOCl、BiBr3、CdO、CdCO3、CdI2、CdF2、CdSO4、NaH2PO4·2H2O、NaH2PO4、NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5Etc. and other complex fluxes, e.g. Bi2O3-CdO、(BiO)2CO3-CdO、Bi(OH)3-CdO、Bi(NO3)3-CdO、BiI3-CdO、BiBr3-CdO、Bi2O3-CdCO3、(BiO)2CO3-CdCO3、Bi(OH)3-CdCO3、Bi(NO3)3-CdCO3、BiI3-CdCO3、BiBr3-CdCO3、Bi2O3-TeO2、(BiO)2CO3-TeO2、Bi(OH)3-TeO2、Bi(NO3)3-TeO2、BiI3-TeO2、BiBr3-TeO2、Bi2O3-NH4H2PO4、(BiO)2CO3-NH4H2PO4、Bi(OH)3-NH4H2PO4、Bi(NO3)3-NH4H2PO4、BiI3-NH4H2PO4Or BiBr3-NH4H2PO4And the like.
The compound bismuth cadmium phosphate single-phase polycrystalline powder is prepared by a solid-phase synthesis method, and comprises the following steps: mixing a bismuth-containing compound, a cadmium-containing compound and a phosphorus-containing compound to prepare the compound bismuth cadmium by a solid-phase reaction method, wherein the molar ratio of bismuth in the bismuth-containing compound to cadmium in the cadmium-containing compound to phosphorus in the phosphorus-containing compound is (35-x): 10, x =0-35, uniformly mixing the raw materials of the bismuth-containing compound, the cadmium-containing compound and the phosphorus-containing compound, grinding, putting the mixture into a muffle furnace, presintering to remove water and gas in the raw materials, cooling to room temperature, taking out the mixture, grinding, putting the mixture into the muffle furnace to calcine, heating to 500-900 ℃, keeping the temperature for 5-60 hours, cooling to room temperature, taking out, and grinding to obtain the bismuth cadmium single-phase polycrystalline powder.
b. Preparing a bismuth cadmium phosphate seed crystal: slowly cooling the mixed melt obtained in the step a to room temperature at the speed of 0.5-10 ℃/h, and spontaneously crystallizing to obtain bismuth cadmium phosphate seed crystals;
the fluxing agent Bi2O3Bi in-CdO system2O3The molar ratio of the compound to CdO is 0.1-3; (BiO)2CO3CdO system (BiO)2CO3The mol ratio of the compound to CdO is 0.1-3; biI3BiI in CdO System3The mol ratio of the compound to CdO is 0.1-3; biBr3BiBr in-CdO system3The mol ratio of the compound to CdO is 0.1-3; bi2O3-CdCO3In the system Bi2O3With CdCO3The molar ratio of (A) is 0.1-9; (BiO)2CO3-CdCO3In the system (BiO)2CO3With CdCO3The molar ratio of (A) is 0.1-10; bi2O3-TeO2In the system Bi2O3And TeO2The molar ratio of (a) is 0.1-55；(BiO)2CO3-TeO2In the system (BiO)2CO3And TeO2The molar ratio of (A) is 0.1-6; bi (OH)3-TeO2In the system Bi (OH)3And TeO2The molar ratio is 0.1-10; bi (NO)3)3-TeO2In the system Bi (NO)3)3And TeO2The molar ratio is 0.1-9; biI3-TeO2BiI in the system3And TeO2The molar ratio is 0.1-6; biBr3-TeO2BiBr in the system3And TeO2The molar ratio is 0.1-5; bi2O3-NH4H2PO4In the system Bi2O3And NH4H2PO4The molar ratio is 0.2-5; (BiO)2CO3-NH4H2PO4In the system (BiO)2CO3And NH4H2PO4The molar ratio is 0.1-8; bi (OH)3-NH4H2PO4In the system Bi (OH)3And NH4H2PO4The molar ratio is 0.1-10; bi (NO)3)3-NH4H2PO4In the system Bi (NO)3)3And NH4H2PO4The molar ratio is 0.1-8; biI3-NH4H2PO4BiI in the system3And NH4H2PO4The molar ratio is 0.2-5; bi2O3-CdO-TeO2In the system Bi2O3CdO and TeO2The molar ratio is 0.2-5; (BiO)2CO3-CdO-TeO2In the system (BiO)2CO3CdO and TeO2The molar ratio is 0.2-5; bi (OH)3-CdO-TeO2In the system Bi (OH)3CdO and TeO2The molar ratio is 0.2-5; bi (NO)3)3-CdO-TeO2In the system Bi (NO)3)3CdO and TeO2The molar ratio is 0.2-5.
Because of growing the bismuth cadmium phosphate scintillation crystalIn the process, use is made of, for example, bi2O3、(BiO)2CO3、Bi(OH)3、Bi(NO3)3、BiI3、BiOCl、BiBr3、CdO、CdCO3、CdI2、CdF2、CdSO4、NaH2PO4·2H2O、NaH2PO4、NH4H2PO4、(NH4)2HPO4、H3PO4Or P2O5Isofluxing agents and additives such as Bi2O3-CdO、(BiO)2CO3-CdO、Bi(OH)3-CdO、Bi(NO3)3-CdO、BiI3-CdO、BiBr3-CdO、Bi2O3-CdCO3、(BiO)2CO3-CdCO3、Bi(OH)3-CdCO3、Bi(NO3)3-CdCO3、BiI3-CdCO3、BiBr3-CdCO3、Bi2O3-TeO2、(BiO)2CO3-TeO2、Bi(OH)3-TeO2、Bi(NO3)3-TeO2、BiI3-TeO2、BiBr3-TeO2、Bi2O3-NH4H2PO4、(BiO)2CO3-NH4H2PO4、Bi(OH)3-NH4H2PO4、Bi(NO3)3-NH4H2PO4、BiI3-NH4H2PO4Or BiBr3-NH4H2PO4And other composite cosolvents, the product purity is high, the crystal is easy to grow and is transparent without wrapping, and the method has the advantages of higher growth speed, low cost, easy obtainment of larger-size crystals and the like; the obtained crystal has the advantages of fast decay time, large density, high hardness, good mechanical property, difficult cracking and deliquescence, easy processing and storage, and the like. The bismuth cadmium phosphate scintillation crystal can be used for detecting X-rays, gamma rays, neutrons and other high-energy particles, nuclear medicine imaging, radiotherapy and engineeringNondestructive inspection, safety inspection, petroleum logging, nuclear exploration, high-energy physics and space physics.
Drawings
FIG. 1 shows Bi of the present invention35-xCdxP10O(155-x)/2X = X-ray diffraction pattern of powder from 0 to 35.
FIG. 2 shows Bi of the present invention35-xCdxP10O(155-x)/2And x = fluorescence decay time of 0-35 crystal test.
Detailed Description
The invention is described in detail below with reference to the drawings and examples, but the invention is not limited thereto, and any modification made on the basis of the invention will not depart from the spirit of the invention. The raw materials or equipment used in the present invention, unless otherwise specified, are commercially available:
example 1:
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O ↓ [ O ] synthesized Bi35-xCdxP10O(155-x)/2And x =0-35.
Adding Bi2O3、CdO、NH4H2PO4Weighing, placing into a mortar, mixing, finely grinding, placing into an open corundum crucible with the diameter of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 500 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 750 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, grinding for the third time, placing into the muffle furnace, keeping the temperature for 48 hours at 750 ℃, taking out, grinding to obtain single-phase polycrystalline powder of the bismuth cadmium phosphate compound, carrying out X-ray analysis on the product, and carrying out X-ray analysis on the obtained X-ray spectrogram and the bismuth cadmium Bi phosphate35-xCdxP10O(155-x)/2(X = 0-35) the X-ray spectra obtained for the single crystal structure are consistent;
(2) High-temperature molten-salt growth of Bi35-xCdxP10O(155-x)/2X =0-35 crystal
The obtained bismuth cadmium bismuth phosphate Bi35-xCdxP10O(155-x)/2X =0-35, compound single-phase polycrystalline powder and flux Bi2O3CdO in molar ratio Bi35-xCdxP10O(155-x)/2:Bi2O3-CdO =1, wherein Bi2O3The molar ratio of the mixed solution to CdO is 3:5, the mixed solution is mixed and filled into an opening platinum crucible with the diameter phi of 80mm multiplied by 80mm, the platinum crucible is heated to 850 ℃ at the temperature rise rate of 30 ℃/h, and the temperature is kept for 15 hours, thus obtaining the mixed solution. Slowly cooling to room temperature at the speed of 0.5 ℃/h, and spontaneously crystallizing to obtain the bismuth cadmium phosphate seed crystal. Bi to be obtained35-xCdxP10O(155-x)/2And x =0-35, the seed crystal is fixed on a seed crystal rod, the seed crystal is placed from the top of the crystal growth furnace, the seed crystal is preheated on the surface of the mixed melt for 10 minutes and is immersed in the liquid level, the seed crystal is melted back in the mixed melt, the temperature is kept for 30 minutes, and the temperature is rapidly reduced to the saturation temperature of 650 ℃. Then the temperature is reduced at the speed of 2 ℃/day, the seed rod is rotated at the rotating speed of 10rpm, after the crystal growth is finished, the crystal is separated from the liquid surface, the temperature is reduced to the room temperature at the speed of 10 ℃/hour, and the Bi with the size of 56mm multiplied by 40mm multiplied by 30mm can be obtained35-xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the chromium oxide can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 2:
(1) According to the reaction formula: (35-x/2) (BiO)2CO3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(35-x)/2CO2×) synthetic Bi35-xCdxP10O(155-x)/2And x =0-35.
Will (BiO)2CO3、CdO、NH4H2PO4Weighing, placing into a mortar, mixing, finely grinding, placing into an open corundum crucible with the diameter of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 600 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, placing into the muffle furnace after the second grinding, heating to 750 ℃, keeping the temperature for 24 hours, cooling to room temperature, taking out, placing into the muffle furnace after the third grinding, keeping the temperature for 48 hours at 750 ℃, taking out, grinding to obtain single-phase polycrystalline powder of the bismuth cadmium phosphate compound, carrying out X-ray analysis on the product, and carrying out X-ray analysis on the obtained X-ray spectrogram and the bismuth cadmium Bi phosphate35-xCdxP10O(155-x)/2X =0-35, the X-ray spectra obtained for the single crystal structure are consistent;
(2) High-temperature molten-salt growth of Bi35-xCdxP10O(155-x)/2X =0-35 crystal
Will (BiO)2CO3、CdO、NH4H2PO4Directly weighing raw materials according to the molar ratio (35-x)/2 x2O3CdO is compounded in a molar ratio of 1:4, where Bi is present2O3The molar ratio of the mixed solution to CdO is 3:5, the mixed solution is put into an open platinum crucible with the diameter of 80mm multiplied by 80mm, the temperature is raised to 1000 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the mixed melt is cooled to 650 ℃;
slowly cooling to room temperature at the rate of 1.5 ℃/h, and spontaneously crystallizing to obtain Bi35-xCdxP10O(155-x)/2X =0-35 seed; bi to be obtained35-xCdxP10O(155-x)/2Fixing the seed crystal with x =0-35 on a seed crystal rod, preheating the seed crystal on the surface of the mixed melt for 10 minutes from the top of the crystal growing furnace, immersing the seed crystal below the liquid level, melting the seed crystal in the mixed melt back, keeping the temperature for 30 minutes, and rapidly cooling to the saturation temperature of 600 ℃;
then the temperature is 1 DEG CSlowly cooling at a speed of one day, not rotating a seed rod, lifting the crystal from the surface of the melt after the crystal grows to a required size, cooling to room temperature at a speed of 20 ℃/h, and taking out the crystal from a hearth to obtain Bi with the size of 36mm multiplied by 22mm multiplied by 15mm35-xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth carbonate in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the chromium oxide can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 3:
(1) According to the reaction formula: (35-x) Bi (OH)3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+((105-3x)/2+15)H2O ↓ [ O ] synthesized Bi35-xCdxP10O(155-x)/2And x =0-35.
Bi (OH)3、CdO、NH4H2PO4Weighing, placing into a mortar, mixing, grinding finely, placing into an open corundum crucible with the diameter of 100mm multiplied by 100mm, placing into a muffle furnace, slowly heating to 600 ℃, keeping the temperature for 14 hours, cooling to room temperature, taking out, grinding for the second time, placing into the muffle furnace, heating to 750 ℃, keeping the temperature for 34 hours, cooling to room temperature, taking out, grinding for the third time, placing into the muffle furnace, keeping the temperature for 48 hours at 750 ℃, taking out, grinding to obtain single-phase polycrystalline powder of the bismuth cadmium phosphate compound, carrying out X-ray analysis on the product, and carrying out X-ray analysis on the obtained X-ray spectrogram and the bismuth cadmium Bi phosphate35-xCdxP10O(155-x)/2X =0-35, the X-ray spectra obtained for the single crystal structure are consistent.
(2) Growth of Bi by top seed crystal method35-xCdxP10O(155-x)/2X =0-35 crystal
Bi (OH)3、CdO、NH4H2PO4Directly weighing raw materials according to a molar ratio (35-x) of x:10 and x =0-35, and mixing the weighed raw materials with a fluxing agent CdO-TeO2Mixing according to the molar ratio of 1:3, wherein CdO and TeO2The molar ratio is 3:1, the mixture is put into a platinum crucible with a diameter of 80mm multiplied by 80mm, the temperature is raised to 1200 ℃, the temperature is kept for 60 hours, mixed melt is obtained, and the temperature is lowered to 620 ℃;
slowly cooling to room temperature at the speed of 3.5 ℃/h, and spontaneously crystallizing to obtain Bi35-xCdxP10O(155-x)/2And x =0-35 seed crystal. Bi to be obtained35-xCdxP10O(155-x)/2Fixing x =0-35 seed crystals on a seed crystal rod, preheating the seed crystals on the surface of the mixed melt for 15 minutes from the top of a crystal growing furnace, immersing the seed crystals below the liquid level, melting the seed crystals in the mixed melt, keeping the temperature for 30 minutes, and rapidly cooling to 615 ℃ of saturation temperature;
slowly cooling at the speed of 3 ℃/day, rotating the seed crystal crucible at the rotating speed of 5rpm, lifting the crystal from the surface of the melt after the crystal grows to the required size, cooling to room temperature at the speed of 1 ℃/h, and taking out the crystal from a hearth to obtain Bi with the size of 25mm multiplied by 24mm multiplied by 10mm35-xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth hydroxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the chromium oxide can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 4
(1) According to the reaction formula: (35-x) BiI3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(105-3x)/2I2×) synthetic Bi35-xCdxP10O(155-x)/2And x =0-35 compound.
(2) Water (W)Thermal method for growing Bi35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
The prepared compound Bi35-xCdxP10O(155-x)/2X =0-35 polycrystalline powder or BiI3、CdO、NH4H2PO4Directly weighing raw materials according to a molar ratio of (35-x) x:10 and x =0-35, dissolving the raw materials in deionized water, performing ultrasonic treatment on the incompletely dissolved mixture at 60 ℃ to fully mix and dissolve the mixture, and using H to dissolve the mixture3PO4Adjusting the pH value to 3-6; transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23mL, and screwing and sealing the reaction kettle; placing the high-pressure reaction kettle in a constant temperature box, heating to 500-550 ℃, keeping the temperature for 10-14 days, and cooling to room temperature at a cooling rate of 3-5 ℃/day to obtain Bi of 3mm multiplied by 2mm35-xCdxP10O(155-x)/2And x =0-35 scintillation crystals.
The raw material bismuth iodide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the chromium oxide can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 6
(1) According to the reaction formula: (35-x) BiI3+xCdO+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+(105-3x)/2I2↓ synthetic Bi35-xCdxP10O(155-x)/2And x =0-35.
(2) Hydrothermal growth of Bi35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
The prepared compound Bi35-xCdxP10O(155-x)/2X =0-35 polycrystalline powder or BiI3、CdO、NH4H2PO4Directly weighing raw materials and a fluxing agent Bi according to a molar ratio (35-x) of x:10 and x =0-352O3-TeO2Mixing according to a molar ratio of 12O3And TeO2Dissolving in deionized water at a molar ratio of 4:1, ultrasonic treating the incompletely dissolved mixture at 60 deg.C to make it fully mixed and dissolved, and dissolving with H3PO4Adjusting the pH value to 3-6; transferring the obtained mixed solution into a clean pollution-free lining of a high-pressure reaction kettle with the volume of 23mL, and screwing and sealing the reaction kettle; placing the high-pressure reaction kettle in a constant temperature box, heating to 500-550 ℃, keeping the temperature for 10-14 days, and cooling to room temperature at a cooling rate of 6-10 ℃/day to obtain Bi of 4mm multiplied by 2mm35-xCdxP10O(155-x)/2And x =0-35 scintillation crystals.
The raw material bismuth iodide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the chromium oxide can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 7
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2×) synthetic Bi35-xCdxP10O(155-x)/2And x =0-35.
Adding Bi2O3、CdCO3、NH4H2PO4Placing the mixture into a mortar according to the mol ratio of (35-x)/2 x, namely 10, x =0-35, mixing, finely grinding, then placing the mixture into an open corundum crucible with the diameter of 100mm multiplied by 100mm, compacting the mixture, placing the compacted mixture into a muffle furnace, slowly heating the mixture to the temperature of 700 ℃, keeping the temperature for 4-10 hours, taking out the crucible after cooling, taking out the sample which is loose, taking out the sample, grinding the sample uniformly again, placing the sample into the crucible, keeping the temperature for 48 hours again at the temperature of 750 ℃ in the muffle furnace,taking out the mixture, putting the mixture into a mortar to be smashed and ground to obtain Bi35-xCdxP10O(155-x)/2X =0-35, subjecting the product to X-ray analysis, obtaining an X-ray spectrum and Bi35-xCdxP10O(155-x)/2X =0-35 the X-ray spectra obtained for the single crystal structure were consistent.
(2) Growth of Bi by Bridgman method35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Bi to be synthesized35-xCdxP10O(155-x)/2Placing the polycrystalline powder raw material with x =0-35 into a graphite crucible, charging into a furnace, vacuumizing, filling high-purity argon as protective atmosphere, heating to 890 ℃ at the temperature rise rate of 20-30 ℃/h, keeping the temperature for 1-2 hours until the raw material is completely melted, and using pure Bi35-xCdxP10O(155-x)/2And x =0-35 single crystal is used as seed crystal for growth. After the growth is finished, slowly cooling and taking out the crystal to obtain the Bi with the size of 30mm multiplied by 22mm multiplied by 15mm32Cd3P10O(155-x)/2And (4) crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium iodide or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 8
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2↓ synthetic Bi35-xCdxP10O(155-x)/2Compounds with x =0-35
Adding Bi2O3、CdCO3、NH4H2PO4Placing into a mortar at a molar ratio of (35-x)/2 x of 10,x =0-35, mixing and finely grinding, and then charging into a containerCompacting the corundum crucible with an opening of phi 100mm multiplied by 100mm, putting the corundum crucible into a muffle furnace, slowly heating to 780 ℃, keeping the temperature constant for 4-8 hours, taking out the crucible after cooling, taking out the sample which is loose, taking out the sample, grinding the sample uniformly again, putting the sample into the crucible, keeping the temperature constant for 48 hours again in the muffle furnace at 850 ℃, taking out the sample, putting the sample into a mortar, smashing and grinding to obtain Bi35-xCdxP10O(155-x)/2X =0-35, subjecting the product to X-ray analysis, obtaining an X-ray spectrum and Bi35-xCdxP10O(155-x)/2X =0-35, the X-ray spectra obtained for the single crystal structure are consistent;
(2) Bridgman method for growing Bi35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Adding Bi2O3、CdCO3、NH4H2PO4Placing the mixture into a mortar according to the molar ratio (35-x)/2 x2O3-CdCO3-TeO2Mixing according to a molar ratio of 1:1, wherein Bi2O3、CdCO3And TeO2And (2) filling the mixture into a graphite crucible according to a molar ratio of 235-xCdxP10O(155-x)/2And x =0-35 single crystal is used as seed crystal for growth. After the growth is finished, slowly cooling and taking out the crystal to obtain the Bi with the size of 25mm multiplied by 22mm multiplied by 15mm35-xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 9
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2×) synthetic Bi35-xCdxP10O(155-x)/2And x =0-35.
(2) Temperature gradient method for growing Bi35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Adding Bi2O3、CdCO3、NH4H2PO4Putting the raw materials into a mortar according to the mol ratio (35-x)/2 x2O3-CdCO3-TeO2Mixing according to a molar ratio of 12O3、CdCO3And TeO2And (3) pressing the mixture into a material cake by using an isostatic press according to the molar ratio of 6. The temperature of the sintering material is 600-1000 ℃, the constant temperature is kept for 2 hours, and the temperature rising and reducing speed is 20-30 ℃/h. The raw materials are put into a rhenium metal crucible, the inoculating temperature of the seed crystal is 800-850 ℃, and pure Ar gas is adopted for protection. Raising the temperature to 1000 ℃ and beginning to reduce the temperature, and when the temperature is reduced to about 870 ℃, crystals begin to form and continue to grow. The growth process is divided into two stages, and the growth time of the high-temperature zone is 80-100 hours. Then, the crystal lattice enters an in-situ annealing stage, and the dislocation and the thermal stress in the crystal lattice are fully eliminated after 80-100 hours of annealing. After the growth is finished, slowly cooling and taking out the crystal to obtain the Bi with the size of 25mm multiplied by 22mm multiplied by 15mm35-xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 10
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2↓ synthetic Bi35-xCdxP10O(155-x)/2And x =0-35 compound.
(2) Floating zone method for growing Bi35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Adding Bi2O3、CdCO3、NH4H2PO4Putting the raw materials into a mortar according to the molar ratio (35-x)/2 x2O3-CdCO3-TeO2Mixing according to a molar ratio of 1:2, wherein Bi2O3、CdCO3And TeO2And (3) filling the mixture into strip-shaped balloons, pressing the mixture into a material rod by using an isostatic press, wherein the isostatic pressure is 220MPa, filling the material rod into an alumina ceramic crucible, and putting the material rod into a muffle furnace for sintering, wherein the molar ratio is 6. The temperature of the sintering material is 600-890 ℃, the constant temperature is kept for 8-12 hours, and the temperature rising and reducing speed is 75 ℃/h. After the material bar is calcined at high temperature or bent to a certain degree, the material bar needs to be polished until no bending occurs. The isostatic pressure is 100Mpa, and the mixture is put into an alumina ceramic crucible and put into a muffle furnace for sintering. Loading raw materials into a high-temperature floating zone furnace, increasing power until material rods are melted, and finishing growth through technical processes of butt joint, diameter reduction, diameter expansion, diameter equalization, pull-off and the like. The growth rate is 5mm/h, the rotating speed of the feeding and discharging bars is 5rad/s, and the total growth time is 10 hours. And taking out the crystal, putting the crystal into a muffle furnace for annealing to eliminate stress, and annealing for 6-12 hours to fully eliminate dislocation and thermal stress in the crystal lattice. After the growth is finished, slowly cooling, taking out the crystal to obtain the Bi with the size of 30mm multiplied by 25mm multiplied by 13mm35-xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 11
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2×) synthetic Bi35-xCdxP10O(155-x)/2And x =0-35.
(2) Growth of Bi by descent method35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Bi2O3、CdCO3、NH4H2PO4Putting the raw materials into a mortar according to the molar ratio (35-x)/2 x2O3-CdCO3-TeO2Mixing according to a molar ratio of 1:3, wherein Bi2O3、CdCO3And TeO2And (3) filling the mixture into strip-shaped balloons, pressing the mixture into a material rod by using an isostatic press, wherein the isostatic pressure is 200Mpa, putting the material rod into an alumina ceramic crucible, and putting the alumina ceramic crucible into a muffle furnace for sintering. The temperature of the sintering material is 800-920 ℃, the constant temperature is kept for 12 hours, and the temperature rising and reducing speed is 60 ℃/h. After the material bar is calcined at high temperature or bent to a certain degree, the material bar needs to be polished until no bending occurs. The isostatic pressure is 100Mpa, and the mixture is put into an alumina ceramic crucible and put into a muffle furnace for sintering. The raw materials are put into a rhenium metal crucible, the inoculating temperature of the seed crystal is 900 ℃, and pure Ar gas is adopted for protection. Raising the temperature to 1000 ℃ and beginning to reduce the temperature, and when the temperature is reduced to about 860 ℃, crystals begin to form and continue to grow. The growth process is divided into two stages, the growth time of the high-temperature area is 100 hours, and the descending rate is 0.1mm/h. Then, the crystal lattice enters an in-situ annealing stage, and dislocation and thermal stress in the crystal lattice are fully eliminated after 48 hours of annealing. After the growth is finished, slowly cooling and taking out the crystal to obtain the sizeBi of 30mm × 25mm × 13mm35- xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 12
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2×) synthetic Bi35-xCdxP10O(155-x)/2Compounds with x =0-35
Adding Bi2O3、CdCO3、NH4H2PO4Putting the mixture into a mortar according to the molar ratio (35-x)/2 x35-xCdxP10O(155-x)/2X =0-35, subjecting the product to X-ray analysis, obtaining an X-ray spectrum and Bi35-xCdxP10O(155-x)/2X =0-35, the X-ray spectra obtained for the single crystal structure are consistent.
(2) Growing Bi by die-guided method35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Will synthesize single-phase Bi35-xCdxP10O(155-x)/2And x =0-35 polycrystalline powder is pressed into a block blank by an oil press. Sintering at a temperature rising rate of 20-30 ℃/h to 800-1000 ℃ and a constant temperature of 10-15h, placing 200-350g of the block raw material sintered at a high temperature into a tungsten crucible, and growing in a guide mold furnace, wherein pure Bi is used35- xCdxP10O(155-x)/2And the x =0-35 single crystal is used as seed crystal for growth, the growth rate is 6-8mm/h, when the seed crystal, the center of the tungsten crucible and the center of the coil are positioned on the same vertical line, a rotary lifting rod is adopted, and the amplitude of oscillation of the seed crystal is set to be not more than 1mm, preferably 0-0.5mm.
Vacuumizing in a guide die furnace to 2.5-10Pa, filling high-purity nitrogen as protective atmosphere, heating to 5-10KW within 2h, keeping the temperature for 1-3h until the raw materials are completely melted, and growing, wherein the growth process mainly comprises the following steps: seeding, shouldering and isodiametric, wherein the pulling speed of the seed rod is 5mm/h, the pulling speed of the seed rod is 3mm/h when the isodiametric is adopted, the crystal is pulled quickly to be separated from the liquid level after the growth is finished, the crystal is taken out after the slow cooling, and Bi with the size of about 28mm multiplied by 20mm multiplied by 13mm can be obtained35- xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
Example 13
(1) According to the reaction formula: (35-x)/2 Bi2O3+xCdCO3+10NH4H2PO4→Bi35-xCdxP10O(155-x)/2+10NH3↑+15H2O↑+xCO2×) synthetic Bi35-xCdxP10O(155-x)/2Compounds with x =0-35
Adding Bi2O3、CdCO3、NH4H2PO4Placing into a mortar at a molar ratio of (35-x)/2 x of 10,x =0-35, mixing and finely grinding, and thenLoading into an open corundum crucible of phi 100mm x 100mm, compacting, placing into a muffle furnace, slowly heating to 500-850 deg.C, holding at constant temperature for 4 hr, cooling, taking out the crucible, loosening the sample, taking out the sample, grinding, placing into the crucible, holding at 950 deg.C for 48 hr, taking out, placing into a mortar, and grinding to obtain Bi35-xCdxP10O(155-x)/2X =0-35, subjecting the product to X-ray analysis, obtaining an X-ray spectrum and Bi35-xCdxP10O(155-x)/2X =0-35, the X-ray spectra obtained for the single crystal structure are consistent.
(2) Growing Bi by guided mode method35-xCdxP10O(155-x)/2X =0-35 scintillation crystal
Will synthesize single-phase Bi35-xCdxP10O(155-x)/2X =0-35 polycrystalline powder and flux Bi2O3-CdCO3-TeO2Mixing according to a molar ratio of 2:1, wherein Bi2O3、CdCO3And TeO2And (3) pressing the mixture into a blocky blank by using an oil press, wherein the molar ratio is 5. Sintering at a temperature rising rate of 20-30 ℃/h to 500-1000 ℃ and a constant temperature of 10-15h, placing 200-350g of the block raw material sintered at a high temperature into a tungsten crucible, and growing in a guide mold furnace, wherein pure Bi is used35- xCdxP10O(155-x)/2And x =0-35 monocrystal is used as seed crystal for growth, the growth rate is 6-8mm/h, when the seed crystal, the center of the tungsten crucible and the center of the coil are positioned on the same vertical line, a rotary lifting rod is adopted, and the swing amplitude of the seed crystal is set to be not more than 1mm, preferably 0-0.5mm.
Vacuumizing in a guide die furnace to 2.5-10Pa, filling high-purity nitrogen as protective atmosphere, heating to 6-10KW within 2h, keeping the temperature for 1-3h until the raw materials are completely melted, and growing, wherein the growth process mainly comprises the following steps: seeding, shouldering and isodiametric, wherein the pulling speed of the seed rod is 5mm/h, the pulling speed of the seed rod is 3mm/h when the isodiametric is adopted, the crystal is quickly pulled to be separated from the liquid level after the growth is finished, the crystal is taken out after the slow cooling, and the ruler can be obtainedBi with dimensions of about 28mm multiplied by 20mm multiplied by 13mm35- xCdxP10O(155-x)/2And x =0-35 crystals.
The raw material bismuth oxide in the reaction formula can be replaced by bismuth chloride or bismuth bromide or bismuth nitrate or bismuth oxalate or bismuth carbonate or bismuth bicarbonate or bismuth sulfate and other bismuth-containing salts, the cadmium carbonate can be replaced by cadmium chloride or cadmium bromide or cadmium nitrate or cadmium oxalate or cadmium carbonate or cadmium bicarbonate or cadmium sulfate and other cadmium-containing salts, and the ammonium dihydrogen phosphate can be replaced by other phosphates.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The compound cadmium bismuth phosphate is characterized in that the chemical formula is Bi35-xCdxP10O(155-x)/2Wherein 0 is<x<35。
2. The method for preparing the compound of cadmium bismuth phosphate according to claim 1, comprising the following steps: mixing a bismuth-containing compound, a cadmium-containing compound and a phosphorus-containing compound to prepare the compound bismuth cadmium phosphate by a solid-phase reaction method, wherein the molar ratio of bismuth in the bismuth-containing compound to cadmium in the cadmium-containing compound to phosphorus in the phosphorus-containing compound is (35-x): x:10, wherein 0-x-n-35 is adopted, uniformly mixing the raw materials of the bismuth-containing compound, the cadmium-containing compound and the phosphorus-containing compound, grinding the raw materials, putting the ground raw materials into a muffle furnace, presintering the raw materials to remove moisture and gas in the raw materials, cooling the raw materials to room temperature, taking out the ground raw materials, and putting the ground raw materials into the muffle furnace to calcine to prepare the compound bismuth cadmium phosphate.
3. The method for preparing the compound cadmium bismuth phosphate according to claim 2, wherein the bismuth-containing compound comprises at least one of bismuth hydroxide, bismuth oxide, bismuth salt;
the cadmium-containing compound comprises at least one of cadmium oxide, cadmium hydroxide and cadmium salt;
the phosphorus-containing compound is at least one of phosphorus oxide, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphate.
4. The method for preparing the compound cadmium bismuth phosphate according to claim 3, wherein the bismuth salt comprises at least one of bismuth chloride, bismuth bromide, bismuth nitrate, bismuth oxalate, bismuth carbonate, bismuth bicarbonate, bismuth sulfate;
the cadmium salt comprises at least one of cadmium chloride, cadmium bromide, cadmium nitrate, cadmium oxalate, cadmium carbonate, cadmium bicarbonate and cadmium sulfate.
5. The bismuth cadmium phosphate scintillation crystal is characterized in that the chemical formula of the crystal is Bi35-xCdxP10O(155-x)/2 Wherein 0 is<x<35, the crystal belongs to monoclinic system, space groupC2, no center of symmetry, unit cell parameters a =19.2-19.7 a, b =11.1-11.6 a, c =16.2-16.9 a, Z =2,v =3452.544-3861.988 a3The molecular weight is 5204.09-8864g/mol, and the crystal density is 4.476-8.529g/cm 3.
6. A preparation method of the bismuth cadmium phosphate scintillation crystal of claim 5, characterized in that the bismuth cadmium phosphate scintillation crystal is grown by a high-temperature molten salt method, a Czochralski method, a top-seeded method, a Bridgman-Stockbarge method, a hydrothermal method, a temperature gradient method, a floating zone method or a guided mode method.
7. The method of claim 6, wherein the specific operations are performed by:
heating the mixture of the compound of cadmium bismuth phosphate in claim 1 or the compound of cadmium bismuth phosphate in claim 1 and a fluxing agent to melt to obtain a mixed melt, and cooling or growing at constant temperature to prepare a cadmium bismuth phosphate scintillation crystal;
or directly heating the bismuth-containing compound, the mixture of the cadmium-containing compound and the phosphorus-containing compound or the mixture of the bismuth-containing compound, the cadmium-containing compound, the phosphorus-containing compound and the fluxing agent to melt to obtain a mixed solution, and cooling or growing at constant temperature to prepare the bismuth cadmium phosphate scintillation crystal.
8. The method of claim 7, wherein the molar ratio of the compound cadmium bismuth phosphate to the flux is 1; or wherein the molar ratio of bismuth-containing compounds, cadmium-containing compounds and phosphorus-containing compounds to flux is (35-x) x:10 from 0.1 to 20,0<x<35; the fluxing agent comprises single fluxing agent or composite fluxing agent, wherein the single fluxing agent comprises at least one of bismuth hydroxide, cadmium hydroxide, phosphorus hydroxide, bismuth oxide, cadmium oxide, phosphorus pentoxide, bismuth salt, cadmium salt, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphorus salt and lead oxide, and the composite fluxing agent comprises Bi2O3-CdO、Bi2O3-TeO2、BiF3-CdO、BiF3-TeO2、CdO-TeO2、Bi2O3-TeO2-CdO、Bi2O3-PbO、NH4H2PO4-PbO、NH4H2PO4- Bi2O3、NH4H2PO4-CdO、BiF3-PbO、CdO-PbO、Bi2O3-one or more of PbO-CdO.
9. The method of claim 8, wherein the composite flux is Bi2O3Bi in-CdO system2O3The molar ratio of the compound to CdO is 0.1-3; cdO-TeO2CdO and TeO in the system2The molar ratio is 0.1-3; biF3BiF in-CdO system3The molar ratio of the compound to CdO is 0.1-6; bi2O3-TeO2In the system Bi2O3And TeO2The molar ratio is 0.1-6; biF3- TeO2In the system BiF3And TeO2The molar ratio is 0.2-5; bi2O3-TeO2Bi in-CdO system2O3CdO and TeO20.2-5, 0.1-62O3Bi in the-PbO System2O3The molar ratio of the compound to PbO is 0.1-3; the molar ratio of CdO to PbO in the CdO-PbO system is 0.1-3; biF3BiF in the-PbO System3The molar ratio of the PbO to the PbO is 0.1-6; bi2O3Bi in-PbO-CdO system2O3The molar ratio of CdO to PbO is 0.2-5; NH (NH)4H2PO4NH in the-PbO System4H2PO4The molar ratio of the compound to PbO is 0.2-7; NH (NH)4H2PO4-Bi2O3NH in the system4H2PO4And Bi2O3The molar ratio is 0.1-7; NH (NH)4H2PO4NH in CdO system4H2PO4The mol ratio of the compound to CdO is 0.1-8.
10. The use of the cadmium bismuth phosphate scintillation crystal according to claim 5, characterized in that it can be used in the fields of x-ray, gamma-ray, neutron or energetic particle detection or nuclear medicine imaging, radio-medicine, industrial nondestructive inspection, safety inspection, oil well logging, nuclear exploration, high-energy physics, space physics.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173859A (en) * | 2011-12-20 | 2013-06-26 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN104141170A (en) * | 2013-05-08 | 2014-11-12 | 中国科学院新疆理化技术研究所 | Method for growth of compound cadmium sodium borate crystal |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103173859A (en) * | 2011-12-20 | 2013-06-26 | 中国科学院新疆理化技术研究所 | Cadmium sodium borophosphate compound, cadmium sodium borophosphate nonlinear optical crystal, preparation methods of compound and crystal, and use of crystal |
| CN104141170A (en) * | 2013-05-08 | 2014-11-12 | 中国科学院新疆理化技术研究所 | Method for growth of compound cadmium sodium borate crystal |
Non-Patent Citations (2)
| Title |
|---|
| Bi3+/M2+ Oxyphosphate: A Continuous Series of Polycationic Species from the 1D Single Chain to the 2D Planes. Part 2: Crystal Structure of Three Original Structural Types Showing a Combination of New Ribbonlike;Colmont Marie，et al.;《Inorganic Chemistry》;20060725;6612-6621 * |
| Inorganic Polar Blocks into Controlled Acentric Assemblies;Endara D，et al.;《Inorganic Chemistry》;20120821;9557-9562 * |
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