CN106057260B - A kind of powerful X-ray radiation protection rubber composite based on more metal composite compounds - Google Patents
A kind of powerful X-ray radiation protection rubber composite based on more metal composite compounds Download PDFInfo
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- CN106057260B CN106057260B CN201610342918.3A CN201610342918A CN106057260B CN 106057260 B CN106057260 B CN 106057260B CN 201610342918 A CN201610342918 A CN 201610342918A CN 106057260 B CN106057260 B CN 106057260B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 41
- 239000002905 metal composite material Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 13
- 230000005855 radiation Effects 0.000 title abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 150000003891 oxalate salts Chemical class 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 84
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 83
- 235000006408 oxalic acid Nutrition 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910052772 Samarium Inorganic materials 0.000 claims description 7
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 239000000945 filler Substances 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 238000009510 drug design Methods 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 238000010057 rubber processing Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 150000002910 rare earth metals Chemical class 0.000 abstract 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 7
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical class Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 6
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 6
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical class Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 5
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 4
- 150000001805 chlorine compounds Chemical class 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical class Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical class Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 description 2
- 229940075613 gadolinium oxide Drugs 0.000 description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910001954 samarium oxide Inorganic materials 0.000 description 1
- 229940075630 samarium oxide Drugs 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 tenor metal oxide Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F1/00—Shielding characterised by the composition of the materials
- G21F1/02—Selection of uniform shielding materials
Abstract
The compounding design and its rubber-based composite shielding material of more metal composite compounds of X ray different-energy section radiation protection requirement can be met the invention discloses one kind, more metal composite compounds, it is a kind of brand-new structure obtained by the more metal Oxalate Complexes of high temperature sintering, shares four kinds of metals including two kinds of rare earth metals.More metal composite compounds of the present invention reduce the content of oxygen element or other nonmetalloids in rubber-based composite shielding material, dosage reduces during rubber processing, can be in the filler number that processing conditions is limited, reach more excellent shield effectiveness, it rational design can synthesize as needed, effectively lift the bulk shielding efficiency of radiation proof material.
Description
Technical field
The invention belongs to X-ray radiation protective materials field, and in particular to be that one kind can meet X ray different-energy section
The compounding design and its rubber-based composite shielding material of more metal composite compounds of radiation protection requirement.
Background technology
X-ray shield is mainly absorbed by shielding material to ray energy.Thing is leaned in absorption of the material to ray energy
The interaction of matter and ray is completed.The K layers that the quality of shielding material photoelectric absorption ability depends mainly on shielding material absorb
Side, when the K layers ABSORPTION EDGE of shielding material can cover X-ray energy, the shield effectiveness that will obtain.The K layers of different elements
ABSORPTION EDGE is different, and the energy absorption band of ray is also very different.Therefore multiple element compounding is often selected, to reach
The preferable shield effectiveness of more broad energy spectrum.
Current rubber-based shielding material be mostly by one or more metal oxides (or other nonmetallic compounds) or
Metal powder mixes, and is added in the form of filler in rubber, the number increase of addition, its poor processability, therefore it adds number
Amount has a limiting value.For most oxides, play shielding action to ray is the metal in compound structure
Element, the presence of oxygen (or other nonmetalloids) are restricted the effective content of metal, therefore, reduce oxygen element or other
The content of nonmetalloid composition, increases metallic element absolute content, is that raising shielding compound and rubber-based shielding are compound
The effective ways of the shield effectiveness of material.
The content of the invention
It is an object of the present invention to be directed to x-ray photon energy, more metal composite compounds are synthesized by designing, are dashed forward
Break in the prior art, metal ratio is few in metal oxide or other common compounds, the utilization rate of metallic shield ray
The problem of low, significantly improve the shield effectiveness of shielding material of main part used in rubber-base composite material.
More metal composite compounds that the present invention mentions, it is that the one kind obtained by high temperature sintering multi-metal complex is complete
New structure.It is characterized in that：More metal composite compounds refer to containing two in rare-earth elements of lanthanum, cerium, samarium, europium, gadolinium, ytterbium
Two kinds in kind and iron, tin, antimony, bismuth metal, its general structure is as follows：
(AxByMzNm)Ok, in formula
A, B represents the two kinds of metallic elements differed in lanthanum, cerium, samarium, europium, gadolinium, ytterbium respectively.
M, N represents the two kinds of metallic elements differed in iron, tin, antimony, bismuth respectively.
O is oxygen element.
Wherein, x=0.01~1.6, y=0.01~1.6, z=0.01~1.6, m=0.01~1.6, k=3, wherein, x+
y+z+m>2
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
(1) metal A, B soluble salt are dissolved in 20~40 DEG C of solution respectively, metal M, N chloride are dissolved in 20~40
DEG C solution in, oxalic acid is dissolved in 20~40 DEG C of ethanol solution；
(2) solution of obtained in above-mentioned steps four kinds of metal salts is sufficiently mixed, the ethanol solution of oxalic acid is slowly added dropwise,
20 DEG C~40 DEG C are reacted 10~18 hours, obtain the presoma oxalate precipitation of composite oxide；
(3) oxalates, which is cleaned, filters；
(4) oxalates is placed in calcination in high temperature, temperature is 700~1200 DEG C, and the time is 8~16 hours.
Described metal A, B salt dissolve in ethanol, and A, B salt are preferably chloride such as lanthanum chloride, samarium trichloride, gadolinium chloride.
Described metal A, B, M, N salt dissolve in multi-solvents, and metal A, B salt preferred solvent are ethanol, metal M, N's
Chloride preferred solvent is ethanol, and adds appropriate hydrochloric acid and prevent from hydrolyzing.
The dosage of the oxalic acid is established according to the total content of metal ion.
The multi-metal complex that the oxalates is formed by four metal ion species with oxalic acid coordination, a kind of structure therein
May be as follows
More metal composite compounds of the present invention have good shielding properties.
The content of oxygen element is less than in corresponding proportion metal oxide in more metal composite compounds of the present invention
Oxygen element content, the purpose for reducing screener dosage, improving shield effectiveness can be reached in rubber.
More metal composite compounds of the present invention can be directed to specific x-ray source and carry out compounding design, with rubber
Composite after matrix mixing can efficient radiation proof, the utilization rate of metal is improved in shielding material, allows resource to obtain
Utilized to effective.
Addition of the more metal composite compounds of the present invention in rubber reduces, and reduces oxide particle institute
The fault of construction of formation, the mechanical property of rubber can be improved accordingly.
It is of the invention compared with domestic and international prior art, there is following advantage：
(1) more metal composite compounds of the invention reduce oxygen element or the content of other nonmetalloids, in rubber
Dosage reduces in glue process.
(2) present invention can reach more compared with conventional shielding material in the filler number that processing conditions is limited
Excellent shield effectiveness.
(3) preparation of more metal composite compounds is rational design synthesis as needed, saves materials, economizes on resources,
Targetedly, the bulk shielding efficiency of metal is effectively lifted.
(4) more metal composite compounds are added during rubber processing, can effectively reduce charging sequence, increase rubber
Glue process safety.
(5) present invention can improve the mechanical performance of rubber-base composite material by a relatively large margin while materials are saved.
Brief description of the drawings
The more metal composite compounds and its XRD spectra of presoma that Fig. 1 is produced by the embodiment of the present invention 8.
The scanning electron microscope (SEM) photograph for more metal composite compounds that Fig. 2 is produced by the embodiment of the present invention 8.
The high-resolution-ration transmission electric-lens figure for more metal composite compounds that Fig. 3 is produced by the embodiment of the present invention 8.
Embodiment
With reference to instantiation, the present invention will be described in detail, protection scope of the present invention include but is not limited to
Lower example.
The elastomeric compound of preparation is to vulcanize tabletting under the conditions of 143 DEG C.
Embodiment 1
1.6mol lanthanum chlorides, 1.6mol cerium chlorides are dissolved in 20 DEG C of ethanol solution respectively, 0.01mol stannic chlorides and
0.01mol bismuth chlorides are dissolved in 40 DEG C of ethanol solution respectively, oxalic acid are dissolved in 40 DEG C of ethanol solution；By lanthanum chloride, chlorine
Change cerium, stannic chloride, the solution of bismuth chloride to be sufficiently mixed, the ethanol solution of oxalic acid is slowly added dropwise, 40 DEG C are reacted 18 hours, are answered
The presoma oxalate precipitation of mould assembly oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, temperature 1200
DEG C, the time is 8 hours, as target product.
Embodiment 2
1.2mol lanthanum chlorides, 0.8mol cerium chlorides are dissolved in 40 DEG C of ethanol solution respectively, 1.6mol antimony trichlorides and
1.6mol stannic chlorides are dissolved in 20 DEG C of ethanol solution, oxalic acid are dissolved in 20 DEG C of ethanol solution；By lanthanum chloride, cerium chloride,
Stannic chloride, the solution of antimony trichloride are sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 20 DEG C are reacted 10 hours, are obtained compound
The presoma oxalate precipitation of type oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, temperature 700
DEG C, the time is 16 hours, as target product.
Embodiment 3
1.6mol Europium chlorides, 1.6mol gadolinium chlorides are dissolved in 20 DEG C of ethanol solution respectively, 1.6mol ferric trichlorides,
1mol bismuth chlorides are dissolved in 40 DEG C of ethanol solution, oxalic acid are dissolved in 40 DEG C of ethanol solution；By Europium chloride, gadolinium chloride, three
Iron chloride, the solution of bismuth chloride are sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 40 DEG C are reacted 18 hours, are obtained compound
The presoma oxalate precipitation of oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, and temperature is 1200 DEG C,
Time is 16 hours, as target product.
Embodiment 4
0.01mol lanthanum chlorides, 0.01 ytterbium chloride are dissolved in 30 DEG C of ethanol solution respectively, 1.4mol antimony trichlorides,
1.2mol stannic chlorides are dissolved in 30 DEG C of ethanol solution, oxalic acid are dissolved in 40 DEG C of ethanol solution；By lanthanum chloride, ytterbium chloride,
Antimony trichloride, the solution of stannic chloride are sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 40 DEG C are reacted 16 hours, are obtained compound
The presoma oxalate precipitation of type oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, temperature 1000
DEG C, the time is 16 hours, as target product.
Embodiment 5
0.01mol lanthanum chlorides, 1.6mol samarium trichlorides are dissolved in 20 DEG C of ethanol solution respectively, 0.01mol ferric trichlorides,
1.6mol bismuth chlorides are dissolved in 40 DEG C of ethanol solution, oxalic acid are dissolved in 40 DEG C of ethanol solution；By lanthanum chloride, samarium trichloride,
Ferric trichloride, the solution of bismuth chloride are sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 40 DEG C are reacted 18 hours, are obtained compound
The presoma oxalate precipitation of type oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, and temperature is 900 DEG C,
Time is 12 hours, as target product.
Embodiment 6
0.01mol samarium trichlorides, 0.01 gadolinium chloride are dissolved in 20 DEG C of ethanol solution respectively, 1.4mol stannic chlorides, 1.6 3
Antimony chloride is dissolved in 40 DEG C of ethanol solution, oxalic acid is dissolved in 40 DEG C of ethanol solution；By samarium trichloride, gadolinium chloride, stannic chloride,
The solution of antimony trichloride is sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 40 DEG C are reacted 18 hours, obtain composite oxide
Presoma oxalate precipitation.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, and temperature is 1200 DEG C, the time 8
Hour, as target product.
Embodiment 7
0.01mol Europium chlorides, 1.6mol ytterbium chlorides are dissolved in 20 DEG C of ethanol solution respectively, 0.01mol antimony trichlorides,
1.6mol ferric trichlorides are dissolved in 40 DEG C of ethanol solution, oxalic acid are dissolved in 40 DEG C of ethanol solution；By lanthanum chloride, chlorination
Samarium, ferric trichloride, the solution of stannic chloride are sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 30 DEG C are reacted 10 hours, are answered
The presoma oxalate precipitation of mould assembly oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, temperature 1100
DEG C, the time is 10 hours, as target product.
Embodiment 8
1.2mol samarium trichlorides, 1.2mol gadolinium chlorides are dissolved in 20 DEG C of ethanol solution respectively, 0.01mol ferric trichlorides,
0.01mol antimony trichlorides are dissolved in 40 DEG C of ethanol solution, oxalic acid are dissolved in 40 DEG C of ethanol solution；By samarium trichloride, chlorination
Gadolinium, ferric trichloride, the solution of antimony trichloride are sufficiently mixed, and the ethanol solution of oxalic acid is slowly added dropwise, and 40 DEG C are reacted 18 hours, are obtained
The presoma oxalate precipitation of composite oxide.Oxalates, which is cleaned, to be filtered, and oxalates is placed in into calcination in high temperature, temperature is
950 DEG C, the time is 15 hours, as target product.
The XRD diffraction patterns of its presoma oxalates and target product as shown in Figure 1, scanning electron microscope (SEM) photograph as shown in Figure 2,
High-resolution-ration transmission electric-lens figure is as shown in Figure 3.
Embodiment 9
Elementary analysis
The target product produced to embodiment 1~8 carries out elementary analysis, and sample is abbreviated as embodiment 1~8, as a result seen
Table one.
Table one
Oxygen element content balance described in table, refer to containing with the more metal composite compound metal content phases produced
The content of oxygen element in corresponding metal oxide mixture.
The reference of the oxygen element content is calculated as follows, every in final product according to elementary analysis by taking embodiment 8 as an example
There are samarium 34.56mol, gadolinium 30.53mol, iron 0.3mol, antimony 0.3mol, oxygen 34.31mol in 100mol, and it is identical in tenor
Samarium oxide 34.56mol, gadolinium oxide 30.53mol, di-iron trioxide 0.3mol, antimony oxide 0.3mol mixture in,
Oxygen element shares 98.54mol, and 60.00% is accounted in the atom of mixture.
As can be seen from Table I, more metal composite compounds that embodiment 1~8 is produced compared with the existing technology,
Oxygen element content is greatly lowered.
Embodiment 10
The more metal composite compounds produced to embodiment 1~8 produce rubber-based shielding material, the formula of elastomeric compound
As shown in Table 2, elastomeric compound is prepared using two-roll mill according to a conventional method.
Table two
| NR | ZnO | SA | Antioxidant 4010 | Accelerant CZ | Shield filler | S | |
| Embodiment 1-8 | 100 | 5 | 3 | 5 | 2 | 500 | 3 |
| The blank of embodiment 8 | 100 | 5 | 3 | 5 | 2 | 550 | 3 |
In the blank of embodiment 8, shielding filler is the tenor metal oxide corresponding with embodiment 8
Samarium, gadolinium oxide, iron oxide, the mixture of antimony oxide.The performance of elastomeric compound is as shown in Table 3.
Table three
It can be seen that, embodiment 1-8 can meet X ray different-energy section radiation protection requirement from above test result；
Embodiment 8 can effectively illustrate what more metal composite compounds of the invention were reduced in dosage with the contrast of its blank assay
In the case of, radiation proof is more efficient, and mechanical performance is more excellent.
Presently preferred embodiments of the present invention is illustrated above, but the present invention is not limited to the embodiment,
Those skilled in the art can also make a variety of equivalent modifications on the premise of without prejudice to spirit of the invention or replace
Change, such as the preparation of its presoma can also use citric acid etc.；General structure (AxByMzNm)OkIn A be applied to group of the lanthanides, B
Suitable for other suitable elements, such as titanium, boron, O is also applied for other elements or part, such as Cl, CO3 2-Deng.These are equivalent
Modification or replacement are all contained in the application claim limited range.And can also in rubber-base composite material preparation
Add simple metal element (without being prepared into compound form again), such as tungsten, lead, to enrich the design of shielding properties and material.
Claims (3)
- A kind of a kind of 1. brand-new more metal composite compounds obtained by high temperature sintering multi-metal complex, it is characterised in that Its general structure is as follows：(AxByMzNm)Ok, in formulaA, B represents the two kinds of metallic elements differed in lanthanum, cerium, samarium, europium, gadolinium, ytterbium respectively,M, N represents the two kinds of metallic elements differed in iron, tin, antimony, bismuth respectively,O is oxygen element,X=0.01~1.6, y=0.01~1.6, z=0.01~1.6, m=0.01~1.6, k=3, wherein, x+y+z+m>2；The preparation method of brand-new more metal composite compounds, comprises the following steps：(1) metal A, B soluble salt are dissolved in 20~40 DEG C of solution respectively, metal M, N chloride are dissolved in 20~40 DEG C In solution, oxalic acid is dissolved in 20~40 DEG C of ethanol solution；(2) solution of obtained in above-mentioned steps four kinds of metal salts is sufficiently mixed, is slowly added dropwise the ethanol solution of oxalic acid, 20 DEG C ~40 DEG C are reacted 10~18 hours, obtain the presoma oxalate precipitation of composite oxide；(3) oxalates, which is cleaned, is filtered, and oxalates is placed in into calcination in high temperature, and temperature is 700~1200 DEG C, and the time is 8~16 small When.
- 2. prepare a kind of a kind of brand-new more metal composites obtained by high temperature sintering multi-metal complex described in claim 1 The method of compound, it is characterised in that comprise the following steps：(1) metal A, B soluble salt are dissolved in 20~40 DEG C of solution respectively, metal M, N chloride are dissolved in 20~40 DEG C In solution, oxalic acid is dissolved in 20~40 DEG C of ethanol solution；(2) solution of obtained in above-mentioned steps four kinds of metal salts is sufficiently mixed, is slowly added dropwise the ethanol solution of oxalic acid, 20 DEG C ~40 DEG C are reacted 10~18 hours, obtain the presoma oxalate precipitation of composite oxide；(3) oxalates, which is cleaned, is filtered, and oxalates is placed in into calcination in high temperature, and temperature is 700~1200 DEG C, and the time is 8~16 small When；A kind of general structure of brand-new more metal composite compounds is as follows：(AxByMzNm)Ok, in formulaA, B represents the two kinds of metallic elements differed in lanthanum, cerium, samarium, europium, gadolinium, ytterbium respectively,M, N represents the two kinds of metallic elements differed in iron, tin, antimony, bismuth respectively,O is oxygen element,X=0.01~1.6, y=0.01~1.6, z=0.01~1.6, m=0.01~1.6, k=3, wherein,x+y+z+m>2。
- 3. according to the method for claim 2, it is characterised in that：In step (1), metal M, N chloride is dissolved in molten Liquid is ethanol, and adds appropriate hydrochloric acid and prevent from hydrolyzing.
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| CN1748263A (en) * | 2002-12-17 | 2006-03-15 | 兰爱克谢斯德国有限责任公司 | Lead-free mixture used as an additive for shielding radiation |
| CN101572129A (en) * | 2009-06-15 | 2009-11-04 | 北京化工大学 | Overall lead-free X-ray shielding plastic compound material |
| CN105482225A (en) * | 2015-12-30 | 2016-04-13 | 上海师范大学 | Nuclear radiation prevention rare earth composite material and preparation method thereof |
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| US9412476B2 (en) * | 2011-11-03 | 2016-08-09 | Elwha Llc | Systems, devices, methods, and compositions including fluidized x-ray shielding compositions |
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| CN1748263A (en) * | 2002-12-17 | 2006-03-15 | 兰爱克谢斯德国有限责任公司 | Lead-free mixture used as an additive for shielding radiation |
| CN101572129A (en) * | 2009-06-15 | 2009-11-04 | 北京化工大学 | Overall lead-free X-ray shielding plastic compound material |
| CN105482225A (en) * | 2015-12-30 | 2016-04-13 | 上海师范大学 | Nuclear radiation prevention rare earth composite material and preparation method thereof |
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| 氧化钇微粉的研究;邓汝富;《南方冶金学院学报》;19960630;第218-236页 * |
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