CN106057260A - Highly-efficient X-ray radiation protection rubber composite material based on polymetallic composite compound - Google Patents
Highly-efficient X-ray radiation protection rubber composite material based on polymetallic composite compound Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 230000005855 radiation Effects 0.000 title abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 80
- 235000006408 oxalic acid Nutrition 0.000 claims description 23
- 150000003891 oxalate salts Chemical class 0.000 claims description 22
- 239000002905 metal composite material Substances 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- -1 compound compound Chemical class 0.000 claims 1
- 150000005324 oxide salts Chemical class 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 238000013461 design Methods 0.000 abstract description 6
- 238000010057 rubber processing Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 2
- 230000003471 anti-radiation Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 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
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 9
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 8
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 8
- 229910003317 GdCl3 Inorganic materials 0.000 description 7
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 description 7
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 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 compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-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
- 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 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000004223 radioprotective effect Effects 0.000 description 2
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 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
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 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
- 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
- 238000005987 sulfurization reaction Methods 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 invention discloses a synthetic design of a polymetallic composite compound capable of meeting the requirements for radiation protection of X-ray in different energy sections, and a rubber-based composite shielding material of the polymetallic composite compound. The polymetallic composite compound has a completely novel structure obtained by high-temperature calcination of a polymetallic oxalate complex and comprises four metals, wherein two rare earth metals are included. The polymetallic composite compound provided by the invention reduces the contents of an oxygen element or non-metallic elements in the rubber-based composite shielding material, is reduced in usage amount in the process of rubber processing, can achieve a better shielding effect in a limited amount of a filling material in parts under processing conditions, can realize directional design synthesis according to needs, and effectively enhances overall shielding efficiency of an anti-radiation material.
Description
Technical field
The invention belongs to X-radiation protective material field, particularly relate to a class and can meet the compounding design of many metal composites compound and the rubber-based composite shielding material thereof of X-ray different-energy section radiation protection requirement.
Background technology
Ray energy is mainly absorbed by X-ray shield by shielding material.Material absorbs the interaction by material with ray to ray energy to be completed.The quality of shielding material photoelectric absorption ability depends mainly on the K layer ABSORPTION EDGE of shielding material, when the K layer ABSORPTION EDGE of shielding material can cover X-ray energy, and the shield effectiveness that will have obtained.The K layer ABSORPTION EDGE of different elements is different, is also very different the energy absorption band of ray.The most often select multiple element to compound, reach the preferable shield effectiveness of the broadest energy spectrum.
Current rubber-based shielding material mostly is and one or more metal-oxides (or other nonmetallic compounds) or metal powder is mixed, add in rubber with the form of filler, the number added increases, its poor processability, and therefore it adds quantity a ultimate value.From the point of view of most oxides, it is the metallic element in compound structure that ray rises shielding action, the existence of oxygen (or other nonmetalloids) makes the effective content of metal be restricted, therefore, reduce oxygen element or the content of other nonmetalloids composition, make metallic element absolute content increase, be the effective ways of the shield effectiveness improving shielding compound and rubber-based shielding composite.
Summary of the invention
It is an object of the invention to, for x-ray photon energy, by design synthesis many metal composites compound, break through in prior art, in metal-oxide or other common compounds, metal ratio is few, the problem that the utilization rate of metallic shield ray is low, significantly improves the shield effectiveness of shielding material of main part used in rubber-base composite material.
Many metal composites compound that the present invention mentions, is a kind of brand-new structure obtained by high temperature sintering multi-metal complex.It is characterized in that: described many metal composites compound refers to that its general structure is as follows containing two kinds in rare-earth elements of lanthanum, cerium, samarium, europium, gadolinium, ytterbium two kinds and ferrum, stannum, antimony, bismuth metal:
(AxByMzNm)Ok, in formula
A, B represent the two kinds of metallic elements differed in lanthanum, cerium, samarium, europium, gadolinium, ytterbium respectively.
M, N represent the two kinds of metallic elements differed in ferrum, stannum, 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) being dissolved in respectively in the solution of 20～40 DEG C by metal A, B soluble salt, the chloride of metal M, N is dissolved in the solution of 20～40 DEG C, is dissolved in by oxalic acid in the ethanol solution of 20～40 DEG C；
(2) being sufficiently mixed by the solution of obtain in above-mentioned steps four kinds of slaines, be 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 cleans sucking filtration；
(4) oxalates being placed in calcination in high temperature, temperature is 700～1200 DEG C, and the time is 8～16 hours.
The salt of described metal A, B dissolves in ethanol, and the salt of A, B is preferably chloride such as lanthanum chloride, samarium trichloride, Gadolinium trichloride.
The salt of described metal A, B, M, N dissolves in multi-solvents, and the salt preferred solvent of metal A, B is ethanol, and the chloride preferred solvent of metal M, N is ethanol, and adds appropriate hydrochloric acid precaution of hydrolysis.
The consumption of described oxalic acid is established according to the total content of metal ion.
Described oxalates is coordinated the multi-metal complex formed by four metal ion species with oxalic acid, and a kind of structure therein may be as follows
The many metal composites compound that the present invention relates to has good shielding properties.
In the many metal composites compound that the present invention relates to, the content of oxygen element is less than oxygen element content in corresponding proportion metal-oxide, can reduce screener consumption, the purpose of raising shield effectiveness in rubber.
The many metal composites compound that the present invention relates to can carry out compounding design for specific x-ray source, the composite after mixing with rubber matrix can efficiently radioprotective, in shielding material, the utilization rate of metal is improved, and allows resource be utilized effectively.
The many metal composites compound that the present invention relates to addition in rubber reduces, and decreases the fault of construction that oxide particle is formed, can improve the mechanical property of rubber accordingly.
The present invention, compared with domestic and international prior art, has the advantage that
(1) many metal composites compound of the present invention reduces the content of oxygen element or other nonmetalloids, and during rubber processing, consumption reduces.
(2) present invention is compared with conventional shielding material, can reach more excellent shield effectiveness in the filler number that processing conditions is limited.
(3) preparation of many metal composites compound is rational design synthesis as required, saves materials, economizes on resources, and targetedly, the bulk shielding efficiency of metal is effectively promoted.
(4) during rubber processing, add many metal composites compound, can effectively reduce charging sequence, increase rubber processing safety.
(5) present invention is while saving materials, can improve the mechanical performance of rubber-base composite material by a relatively large margin.
Accompanying drawing explanation
Many metal composites compound that Fig. 1 is produced by the embodiment of the present invention 8 and the XRD spectra of presoma thereof.
The scanning electron microscope (SEM) photograph of many metal composites compound that Fig. 2 is produced by the embodiment of the present invention 8.
The high-resolution-ration transmission electric-lens figure of many metal composites compound that Fig. 3 is produced by the embodiment of the present invention 8.
Detailed description of the invention
Below in conjunction with instantiation, the present invention will be described in detail, and protection scope of the present invention includes but not limited to following instance.
The elastomeric compound of preparation is sulfuration tabletting under the conditions of 143 DEG C.
Embodiment 1
1.6mol lanthanum chloride, 1.6mol cerium chloride being dissolved in respectively in the ethanol solution of 20 DEG C, 0.01mol stannic chloride and 0.01mol bismuth chloride are dissolved in the ethanol solution of 40 DEG C respectively, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Lanthanum chloride, cerium chloride, stannic chloride, the solution of bismuth chloride being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 40 DEG C are reacted 18 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 1200 DEG C, and the time is 8 hours, is target product.
Embodiment 2
1.2mol lanthanum chloride, 0.8mol cerium chloride being dissolved in respectively in the ethanol solution of 40 DEG C, 1.6mol Butter of antimony. and 1.6mol stannic chloride are dissolved in the ethanol solution of 20 DEG C, are dissolved in by oxalic acid in the ethanol solution of 20 DEG C；Lanthanum chloride, cerium chloride, stannic chloride, the solution of Butter of antimony. being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 20 DEG C are reacted 10 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 700 DEG C, and the time is 16 hours, is target product.
Embodiment 3
1.6mol Europium chloride, 1.6mol Gadolinium trichloride being dissolved in respectively in the ethanol solution of 20 DEG C, 1.6mol ferric chloride, 1mol bismuth chloride are dissolved in the ethanol solution of 40 DEG C, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Europium chloride, Gadolinium trichloride, ferric chloride, the solution of bismuth chloride being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 40 DEG C are reacted 18 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 1200 DEG C, and the time is 16 hours, is target product.
Embodiment 4
0.01mol lanthanum chloride, 0.01 Ytterbium trichloride being dissolved in respectively in the ethanol solution of 30 DEG C, 1.4mol Butter of antimony., 1.2mol stannic chloride are dissolved in the ethanol solution of 30 DEG C, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Lanthanum chloride, Ytterbium trichloride, Butter of antimony., the solution of stannic chloride being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 40 DEG C are reacted 16 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 1000 DEG C, and the time is 16 hours, is target product.
Embodiment 5
0.01mol lanthanum chloride, 1.6mol samarium trichloride being dissolved in respectively in the ethanol solution of 20 DEG C, 0.01mol ferric chloride, 1.6mol bismuth chloride are dissolved in the ethanol solution of 40 DEG C, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Lanthanum chloride, samarium trichloride, ferric chloride, the solution of bismuth chloride being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 40 DEG C are reacted 18 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 900 DEG C, and the time is 12 hours, is target product.
Embodiment 6
0.01mol samarium trichloride, 0.01 Gadolinium trichloride being dissolved in respectively in the ethanol solution of 20 DEG C, 1.4mol stannic chloride, 1.6 Butter of antimony. are dissolved in the ethanol solution of 40 DEG C, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Samarium trichloride, Gadolinium trichloride, stannic chloride, the solution of Butter of antimony. being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 40 DEG C are reacted 18 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 1200 DEG C, and the time is 8 hours, is target product.
Embodiment 7
0.01mol Europium chloride, 1.6mol Ytterbium trichloride being dissolved in respectively in the ethanol solution of 20 DEG C, 0.01mol Butter of antimony., 1.6mol ferric chloride are dissolved in the ethanol solution of 40 DEG C, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Lanthanum chloride, samarium trichloride, ferric chloride, the solution of stannic chloride being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 30 DEG C are reacted 10 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 1100 DEG C, and the time is 10 hours, is target product.
Embodiment 8
1.2mol samarium trichloride, 1.2mol Gadolinium trichloride being dissolved in respectively in the ethanol solution of 20 DEG C, 0.01mol ferric chloride, 0.01mol Butter of antimony. are dissolved in the ethanol solution of 40 DEG C, are dissolved in by oxalic acid in the ethanol solution of 40 DEG C；Samarium trichloride, Gadolinium trichloride, ferric chloride, the solution of Butter of antimony. being sufficiently mixed, be slowly added dropwise the ethanol solution of oxalic acid, 40 DEG C are reacted 18 hours, obtain the presoma oxalate precipitation of composite oxide.Oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 950 DEG C, and the time is 15 hours, is target product.
As shown in Figure 1, as shown in Figure 2, high-resolution-ration transmission electric-lens figure is as shown in Figure 3 for scanning electron microscope (SEM) photograph for the XRD diffraction pattern of its presoma oxalates and target product.
Embodiment 9
Elementary analysis
The target product producing embodiment 1～8 carries out elementary analysis, and sample is abbreviated as embodiment 1～8, and result sees table one.
Table one
Oxygen element content balance described in table, refers to containing the content of oxygen element in the metal oxide mixture corresponding with the many metal composites compound metal content produced.
The reference of described oxygen element content is calculated as follows, as a example by embodiment 8, according to elementary analysis, end product there are samarium 34.56mol, gadolinium 30.53mol, ferrum 0.3mol, antimony 0.3mol, oxygen 34.31mol in every 100mol, and the identical Disamarium trioxide 34.56mol of tenor, Gadolinia. 30.53mol, iron sesquioxide 0.3mol, antimony oxide 0.3mol mixture in, oxygen element has 98.54mol, accounts for 60.00% in the atom of mixture.
As can be seen from Table I, compared with the existing technology, oxygen element content is greatly lowered many metal composites compound that embodiment 1～8 is produced.
Embodiment 10
The many metal composites compound being produced embodiment 1～8 produces rubber-based shielding material, and the formula of elastomeric compound as shown in Table 2, uses two-roll mill to prepare elastomeric compound according to a conventional method.
Table two
| NR | ZnO | SA | Antioxidant 4010 | Accelerant CZ | Shielding filler | S | |
| Embodiment 1-8 | 100 | 5 | 3 | 5 | 2 | 500 | 3 |
| Embodiment 8 blank | 100 | 5 | 3 | 5 | 2 | 550 | 3 |
In embodiment 8 blank, shielding filler is the tenor metal oxide samarium corresponding with embodiment 8, Gadolinia., ferrum oxide, the mixture of stibium oxide.The performance of elastomeric compound is as shown in Table 3.
Table three
It will be seen that embodiment 1-8 can meet X-ray different-energy section radiation protection requirement from above test result；Embodiment 8 with the contrast of its blank experiment, can effectively illustrate many metal composites compound of the present invention in the case of consumption reduces, radioprotective is in hgher efficiency, and mechanical performance is more excellent.
Below presently preferred embodiments of the present invention is illustrated, but the present invention is not limited to described embodiment, those of ordinary skill in the art can also make modification or the replacement of all equivalents on the premise of spirit of the present invention, and the preparation of such as its presoma can also use citric acid etc.；General structure (AxByMzNm)OkIn A be applicable to group of the lanthanides, B be also applied for other be suitable for element, such as titanium, boron etc., O is also applied for other element or part, such as Cl, CO3 2-Deng.Modification or the replacement of these equivalents are all contained in the application claim limited range.And rubber-base composite material preparation can also add simple metal element (without being prepared as compound form again), such as tungsten, lead etc., with abundant shielding properties and the design of material.
Claims (3)
1. the one brand-new many metal composites compound obtained by high temperature sintering multi-metal complex, it is special
Levying and be, its general structure is as follows:
(AxByMzNm)Ok, in formula
A, B represent the two kinds of metallic elements differed in lanthanum, cerium, samarium, europium, gadolinium, ytterbium respectively,
M, N represent the two kinds of metallic elements differed in ferrum, stannum, 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。
2. described in preparation claim 1, a kind of one obtained by high temperature sintering multi-metal complex is golden
The method belonging to compound compound, it is characterised in that comprise the following steps:
(1) metal A, B soluble salt is dissolved in the solution of 20～40 DEG C respectively, the chlorination of metal M, N
Thing is dissolved in the solution of 20～40 DEG C, is dissolved in by oxalic acid in the ethanol solution of 20～40 DEG C；
(2) solution of obtain in above-mentioned steps four kinds of slaines is sufficiently mixed, is slowly added dropwise the ethanol of oxalic acid
Solution, 20 DEG C～40 DEG C are reacted 10～18 hours, obtain the presoma oxalic acid of composite oxide
Salt precipitates；
(3) oxalates cleans sucking filtration, and oxalates is placed in calcination in high temperature, and temperature is 700～1200 DEG C, time
Between be 8～16 hours.
Method the most according to claim 2, it is characterised in that: in step (1), metal M, N
The solution that is dissolved in of chloride be ethanol, and add appropriate hydrochloric acid precaution of hydrolysis.
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