CN113897526A - Neutron deceleration composite material - Google Patents

Neutron deceleration composite material Download PDF

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Publication number
CN113897526A
CN113897526A CN202111126416.4A CN202111126416A CN113897526A CN 113897526 A CN113897526 A CN 113897526A CN 202111126416 A CN202111126416 A CN 202111126416A CN 113897526 A CN113897526 A CN 113897526A
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powder
composite
neutron
mixed material
neutron moderating
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胡志良
梁天骄
傅世年
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Institute of High Energy Physics of CAS
Spallation Neutron Source Science Center
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Institute of High Energy Physics of CAS
Spallation Neutron Source Science Center
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Priority to CN202111126416.4A priority Critical patent/CN113897526A/en
Publication of CN113897526A publication Critical patent/CN113897526A/en
Priority to PCT/CN2022/094087 priority patent/WO2023045367A1/en
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/10X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61NELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00Radiation therapy
    • A61N5/10X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy
    • A61N2005/1085X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy characterised by the type of particles applied to the patient
    • A61N2005/109Neutrons

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  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
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  • Mechanical Engineering (AREA)
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Abstract

The invention discloses a neutron deceleration composite material, which comprises a mixed material and contains 0.1-5 wt% of the mixed material6Li element material and Cu accounting for 0.1-5% of the weight of the mixed material, wherein the mixed material comprises Al and MgF2、AlF3A mixture of one or more of the materials in (a); the mixed material comprises the following components in percentage by mass: pure aluminum powder: 10-95%; aluminum fluoride powder: 20-80%; magnesium fluoride powder: 0.1-15%; said composition contains6The material of Li element is6LiF powder; the mixed material also comprises pure magnesium powder, and the mass percent of the pure magnesium powder is 0.1-5%. The invention can reduce the radioactivity of the material to the level below the exemption level in a short time when the material is retired at the end of the device or equipment, and is used as a radioactive waste disposal methodThe method and the economic advantage are obvious.

Description

Neutron deceleration composite material
Technical Field
The invention relates to the technical field of metal-based composite materials, in particular to a neutron deceleration composite material for a BNCT boron neutron capture treatment device to obtain neutron beams in a specific energy band.
Background
Neutron energy spectrums generated by various radiation sources such as a reactor neutron source, an accelerator neutron generating device, an isotope neutron source and the like in China are basically continuous energy spectrums with absolutely superior fast neutron components, and are widely applied to the fields of national defense, nuclear power, nuclear medical treatment and the like. In the field of Boron Neutron Capture Therapy (BNCT), neutron beams with specific energy sections are needed for therapy, for example, thermal neutrons (En less than 0.5eV) are used for body surface cancer therapy, and epithermal neutrons (En less than or equal to 0.5eV less than or equal to 10KeV) have higher energy, can penetrate human tissues with a certain depth and are used for deep tumor therapy of human bodies. Fast neutrons (En > 10KeV) have great harm to human bodies and strong penetrating power, and are generally not considered in medical treatment, or are abandoned, or the component proportion of the fast neutrons is reduced as much as possible, so that a neutron retarding material is needed for moderating and filtering neutrons, and screening neutrons in a specific energy band for tumor treatment.
The Chinese patent application with the publication number of CN105732047A discloses a neutron filtering material and a preparation method thereof, wherein at least one of tungsten powder, aluminum powder, titanium powder, boron carbide, titanium oxide, lithium fluoride, aluminum fluoride, gadolinium oxide, gadolinium fluoride, boron nitride, boron oxide, zirconium boride, titanium boride and lithium oxide powder is prepared by adopting press forming, sintering and hot isostatic pressing forming processes to obtain the filtering material, but the filtering material has more powder elements, contains a plurality of heavy metal elements which are easy to generate induced radioactivity and is difficult to meet the physical design index of a boron neutron capture treatment device.
The Chinese patent application with the publication number of CN107921273B discloses a beam shaper for neutron capture therapy, wherein the retarder decelerates neutrons generated from the target material to a super-thermal neutron energy region, and the material of the retarder comprises PbF4、Al2O3、AlF3、CaF2Or MgF2And (b) one or more of the mixed materials containing PbF4 and Al2O3、AlF3、CaF2Or MgF20.1-5 wt% of one or more mixed materials6LiThe materials of the elements are mixed, wherein the materials of the retarder body are changed into blocks from powder or powder pressed compact through a powder sintering process by a powder sintering device.
The above-disclosed patents suffer from the following drawbacks:
(1) the components of the material are too much, part of the material is not common, and the material is processed or produced and manufactured without good economy;
(2) the material component contains high-Z element, and after neutron activation, nuclide with long half-life period, such as45Ca(Hf=162.7d),205Pb(Hf=1.5e+Ty),185W(Hf=75.1d),93Zr(Hf=1.61e+6y),95Zr (Hf ═ 64.03d), detrimental to decommissioned radioactive solid waste disposal;
(3) some of the materials being extremely toxic, e.g. PbF4The difficulty of production and processing is high;
(4) and partial nuclides have large neutron absorption cross sections in the super-thermal energy region.
The invention provides a neutron deceleration composite material, aiming at solving the technical problems in the background technology.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a neutron deceleration composite material to overcome the problems of poor economic performance, large induced radioactivity caused by long-time neutron irradiation, environmental friendliness and the like.
The invention provides a neutron deceleration composite material, which comprises: the mixed material comprises 0.1-5 wt% of the mixed material6Li element material and Cu accounting for 0.1-5% of the weight of the mixed material, wherein the mixed material comprises Al and MgF2、AlF3The mixture of one or more materials in (b), the mixed material comprises, by mass:
pure aluminum powder: 10-95%;
aluminum fluoride powder: 20-80%;
magnesium fluoride powder: 0.1-15%;
in a specific embodiment, the composition comprises6The material of Li element is6LiF powder.
In a specific embodiment, the mixed material further comprises pure magnesium powder, and the mass percentage of the pure magnesium powder is 0.1-5%.
In a specific embodiment, the aluminum fluoride powder has a particle size of 0.5 to 75 μm.
In one embodiment, the magnesium fluoride powder has a particle size of: 0.5 to 50 μm.
In one embodiment, the pure aluminum powder has a particle size of: 0.1 to 100 μm.
In one embodiment, the lithium fluoride powder has a particle size of: 0.5 to 50 μm.
In one embodiment, the pure magnesium powder has a particle size of: 0.1 to 100 μm.
The invention also provides a manufacturing method of the metal matrix composite material base material, which comprises the neutron deceleration composite material, and the processing technology of the metal matrix composite material base material comprises the following steps:
s1, fully stirring and uniformly mixing a plurality of raw materials with different powder particle sizes, placing the raw materials in a sealed sheath, continuously exhausting air at the temperature of 400-600 ℃ until the air pressure is less than 10-3 Pa, keeping the air pressure for 1 hour, and stopping;
s2, placing the sheath into a hot isostatic pressing machine to start hot isostatic pressing, wherein the pressing process lasts for 2-6 hours, the temperature is maintained at 700-950 ℃, the pressure is 80-150 MPa, and the metal matrix composite substrate is obtained after pressing.
The invention has the beneficial effects that:
1. when the deceleration material at the end stage of a device or equipment is retired, the radioactivity of the neutron deceleration composite material can be attenuated to the level of exemption or below in a short time, and the neutron deceleration composite material has obvious advantages in the treatment method and the economy of radioactive waste;
2. the neutron deceleration composite material provided by the invention has no harm or little harm to a human body;
3. according to the neutron deceleration composite material provided by the invention, the absorption cross section of main nuclides in a super-thermal neutron energy region is smaller, and the elastic scattering cross section is larger, namely the nuclides are more favorable for neutron deceleration, and simultaneously absorb neutrons as little as possible and generate unnecessary gamma rays as little as possible;
4. although the absorption cross section of the Cu adopted by the invention is larger than that of Mg and Al, the elastic scattering cross section of the Cu adopted by the invention is far larger than that of the absorption cross section in a super-heat energy area, and meanwhile, the atomic number of the Cu is higher, so that the absorption effect on gamma is better.
Drawings
For a better understanding of the invention, embodiments thereof will be described with reference to the following drawings:
FIG. 1 is a general reaction cross-sectional view of the first embodiment;
FIG. 2 is a cross-sectional view of the elastic scattering of the first embodiment;
FIG. 3 is a (n, γ) absorption cross-sectional view of example one;
FIG. 4 is a general reaction cross-sectional view of example two;
FIG. 5 is a cross-sectional view of the second embodiment of elastic scattering;
FIG. 6 is an (n, γ) absorption cross-sectional view of example two.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the present invention is further described in detail with reference to the following embodiments; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention; reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example one
A neutron moderating composite comprising, in weight percent, Al (wt%): 28.0 MgF2(wt%):1.0、AlF3(wt%):69.0、6LiF (wt%): 1.0, Cu (wt%): 1.0, and forming a moderating block by crushing the powder or the powder through a powder sintering process by using a powder sintering device.
In the material, nuclides such as aluminum, fluorine, magnesium and the like have small neutron (n, gamma) absorption cross sections and large elastic scattering cross sections in a super-thermal energy region, so that fast neutrons are favorably moderated to the super-thermal energy region; natural lithium is divided into6Li and7two nuclides of Li, the atomic numbers of the two nuclides are small, and the nuclides have good slowing or decelerating capacity and simultaneously6Li has a large neutron absorption cross section in a hot area and an energy area below the hot area, can absorb thermal neutrons and is convenient for beam shaping in the boron neutron capture treatment device; the Cu has higher atomic number and better gamma absorption capacity, and simultaneously, the elastic scattering cross section in the super-thermal energy area is far larger than the absorption cross section, thereby being beneficial to moderating fast neutrons, and the activated product has short half-life period and is convenient for radioactive waste disposal.
Example two
The embodiment provides a neutron moderating composite material, which comprises, by weight, Al (wt%): 28.5 MgF2(wt%):2.0、AlF3(wt%):66.0、6LiF (wt%): 1.0, Cu (wt%): 0.5, Mg (wt%): 2.0, and crushing the powder or the powder to form a moderating mass by a powder sintering process through a powder sintering device.
The rest is the same as the first embodiment.
Therefore, the addition of the pure magnesium powder in the embodiment can still realize the moderation of fast neutrons to the epithermal region, and achieve the purposes of small neutron (n, gamma) absorption cross section and large elastic scattering cross section in the epithermal region.
EXAMPLE III
The present example provides a neutron moderating composite material, which is different from the first example in terms of weight percentage, in that the neutron moderating composite material includes Al (wt%): 28.0 Mg (wt%): 1.0, AlF3(wt%):69.0、6LiF(wt%):1.0、Cu(wt%):1.0;
The rest is the same as the first embodiment.
Example four
The present example provides a neutron moderating composite material, which is different from the first example in terms of weight percentage, in that the neutron moderating composite material includes Al (wt%): 29.0 MgF2(wt%):2.0、AlF3(wt%):67.5、6LiF(wt%):1.0、Cu(wt%):0.5;
The rest is the same as the first embodiment.
EXAMPLE five
The present example provides a neutron moderating composite material, which is different from the first example in terms of weight percentage, in that the neutron moderating composite material includes Al (wt%): 29.0, Mg (wt%): 1.0, AlF3(wt%):67.5、6LiF(wt%):1.0、Cu(wt%):1.5;
The rest is the same as the first embodiment.
EXAMPLE six
The present example provides a neutron moderating composite material, which is different from the first example in terms of weight percentage, in that the neutron moderating composite material includes Al (wt%): 28.5 MgF2(wt%):1.0、AlF3(wt%):68.0、6LiF(wt%):1.0、Cu(wt%):0.5、Mg(wt%):1.0;
The rest is the same as the first embodiment.
EXAMPLE seven
The present example provides a neutron moderating composite material, which is different from the first example in terms of weight percentage, in that the neutron moderating composite material includes Al (wt%): 31.0 MgF2(wt%):5.5、AlF3(wt%):62.0、6LiF(wt%):1.0、Cu(wt%):0.5;
The rest is the same as the first embodiment.
That is, regardless of whether pure magnesium powder is added or not, or whether the material is calculated according to a certain weight percentage range value, the first to seventh embodiments can still realize the slowing of fast neutrons to the epithermal region, and achieve the purposes of small neutron (n, γ) absorption cross section and large elastic scattering cross section in the epithermal region.
Example eight
The embodiment provides a neutron moderating composite material which comprises aluminum fluoride powder, magnesium fluoride powder, pure aluminum powder, lithium fluoride powder, pure magnesium powder and copper, wherein the powders are micron-sized powders, and raw materials are easy to obtain and low in price. The particle size of the aluminum fluoride powder is 0.5-75 μm, and the particle size of the magnesium fluoride powder is: 0.5-50 μm, and the pure aluminum powder has the granularity: 0.1-100 μm, and the particle size of lithium fluoride powder is: 0.5-50 μm, and the pure magnesium powder has the granularity: 0.1 to 100 μm. Preferably:
the particle size of the aluminum fluoride powder is preferably: 0.5-10 μm, 10-25 μm, 25-44 μm, 44-58 μm, 58-75 μm, more specifically the particle size values are: 0.5 μm, 10 μm, 25 μm, 44 μm, 58 μm, 75 μm;
the particle size of the magnesium fluoride powder is preferably: 0.5-10 μm, 10-30 μm, 30-50 μm, more specifically the particle size values are: 0.5 μm, 10 μm, 30 μm, 50 μm;
the particle size of the pure aluminum powder is preferably: 0.1-40 μm, 40-75 μm, 75-100 μm, more specifically the particle size values are: 0.1 μm, 40 μm, 75 μm, 100 μm;
the particle size of the lithium fluoride powder is preferably: 0.5-10 μm, 10-30 μm, 30-50 μm, more specifically the particle size values are: 0.5 μm, 10 μm, 30 μm, 50 μm;
the particle size of the pure magnesium powder is preferably: 0.1-40 μm, 40-75 μm, 75-100 μm, more specifically the particle size values are: 0.1 μm, 40 μm, 75 μm, 100 μm.
This embodiment has realized: the same powder adopts the combination of multiple granularity, is favorable to reducing the gap between the powder, promotes material density greatly when processing in production for the whole density of the moderator who processes out through adopting hot isostatic pressing method is big, more is favorable to the speed reduction of neutron, can absorb the neutron less simultaneously and produce the gamma ray that does not need less.
In the process of the embodiment, the neutron moderating composite material is processed into a moderating body, a retarding body and other metal matrix composite material base materials which can be used for neutron moderation, and a manufacturing method of the metal matrix composite material base material is also provided, and the main processing technology steps are as follows:
s1, fully stirring and uniformly mixing a plurality of raw materials with different powder particle sizes, placing the raw materials in a sealed sheath, continuously exhausting air at the temperature of 400-600 ℃ until the air pressure is less than 10-3 Pa, keeping the air pressure for 1 hour, and stopping;
s2, placing the sheath into a hot isostatic pressing machine to start hot isostatic pressing, wherein the pressing process lasts for 2-6 hours, the temperature is maintained at 700-950 ℃, the pressure is 80-150 MPa, and the metal matrix composite substrate is obtained after pressing.
The invention has the beneficial effects that:
1. when the deceleration material at the end stage of a device or equipment is retired, the radioactivity of the neutron deceleration composite material can be attenuated to the level of exemption or below in a short time, and the neutron deceleration composite material has obvious advantages in the treatment method and the economy of radioactive waste;
2. the neutron deceleration composite material provided by the invention has no harm or little harm to a human body;
3. according to the neutron deceleration composite material provided by the invention, the absorption cross section of main nuclides in a super-thermal neutron energy region is smaller, and the elastic scattering cross section is larger, namely the nuclides are more favorable for neutron deceleration, and simultaneously absorb neutrons as little as possible and generate unnecessary gamma rays as little as possible;
4. although the absorption cross section of the Cu adopted by the invention is larger than that of Mg and Al, the elastic scattering cross section of the Cu adopted by the invention is far larger than that of the absorption cross section in a super-heat energy area, and meanwhile, the atomic number of the Cu is higher, so that the absorption effect on gamma is better.
The above embodiments are only specific embodiments of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications are possible without departing from the inventive concept, and such obvious alternatives fall within the scope of the invention.

Claims (9)

1. A neutron moderating composite characterized by: the composite material comprises a mixed material and is 0.1-5 wt% of the mixed material6Li element material and Cu accounting for 0.1-5% of the weight of the mixed material, wherein the mixed material comprises Al and MgF2、AlF3The mixture of one or more materials in (b), the mixed material comprises, by mass:
pure aluminum powder: 10-95%;
aluminum fluoride powder: 20-80%;
magnesium fluoride powder: 0.1 to 15 percent.
2. The neutron moderating composite of claim 1, wherein: said composition contains6The material of Li element is6LiF powder.
3. The neutron moderating composite of claim 1, wherein: the mixed material also comprises pure magnesium powder, and the mass percent of the pure magnesium powder is 0.1-5%.
4. The neutron moderating composite of claim 1, wherein: the aluminum fluoride powder has a particle size of 0.5-75 μm.
5. The neutron moderating composite of claim 1, wherein: the particle size of the magnesium fluoride powder is as follows: 0.5 to 50 μm.
6. The neutron moderating composite of claim 1, wherein: the pure aluminum powder has the granularity as follows: 0.1 to 100 μm.
7. The neutron moderating composite of claim 2, wherein: the particle size of the lithium fluoride powder is as follows: 0.5 to 50 μm.
8. The neutron moderating composite of claim 3, wherein: the pure magnesium powder has the granularity as follows: 0.1 to 100 μm.
9. A method for manufacturing a metal matrix composite substrate is characterized in that: the neutron moderating composite material of claims 1-8, wherein the metal matrix composite substrate is processed by the following steps:
s1, fully stirring and uniformly mixing a plurality of raw materials with different powder particle sizes, placing the raw materials in a sealed sheath, continuously exhausting air at the temperature of 400-600 ℃ until the air pressure is less than 10-3 Pa, keeping the air pressure for 1 hour, and stopping;
s2, placing the sheath into a hot isostatic pressing machine to start hot isostatic pressing, wherein the pressing process lasts for 2-6 hours, the temperature is maintained at 700-950 ℃, the pressure is 80-150 MPa, and the metal matrix composite substrate is obtained after pressing.
CN202111126416.4A 2021-09-26 2021-09-26 Neutron deceleration composite material Pending CN113897526A (en)

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CN116375473A (en) * 2023-03-30 2023-07-04 山东亚赛陶瓷科技有限公司 Magnesium fluoride-based composite neutron moderating material and preparation method thereof

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CN116375473A (en) * 2023-03-30 2023-07-04 山东亚赛陶瓷科技有限公司 Magnesium fluoride-based composite neutron moderating material and preparation method thereof

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