CN112895621B - Anti-radiation gradient composite material and preparation method and application thereof - Google Patents

Anti-radiation gradient composite material and preparation method and application thereof Download PDF

Info

Publication number
CN112895621B
CN112895621B CN202110199269.7A CN202110199269A CN112895621B CN 112895621 B CN112895621 B CN 112895621B CN 202110199269 A CN202110199269 A CN 202110199269A CN 112895621 B CN112895621 B CN 112895621B
Authority
CN
China
Prior art keywords
radiation
composite material
powder
parts
becq
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110199269.7A
Other languages
Chinese (zh)
Other versions
CN112895621A (en
Inventor
何浏
任婕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuhan Shakanar Technology Co ltd
Original Assignee
Wuhan Shakanar Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuhan Shakanar Technology Co ltd filed Critical Wuhan Shakanar Technology Co ltd
Priority to CN202110199269.7A priority Critical patent/CN112895621B/en
Publication of CN112895621A publication Critical patent/CN112895621A/en
Application granted granted Critical
Publication of CN112895621B publication Critical patent/CN112895621B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/048—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material made of particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder
    • 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
    • C30B29/16—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/212—Electromagnetic interference shielding

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a radiation-proof gradient composite material as well as a preparation method and application thereof. The radiation-proof gradient composite material comprises the following components in parts by weight: 30-40 parts of core layer composite crystal, 35-50 parts of BECQ powder and 20-35 parts of polyethylene glycol. The radiation-proof gradient composite material comprises an inner layer of BECQ powder and an outer layer of core layer composite crystals. The radiation-proof gradient composite material is prepared by adding a core layer composite crystal layer on the basis of BECQ powder, wherein the main component of the core layer composite crystal layer is MoO 3 The crystal has good shielding property, the outer core layer composite crystal can absorb and attenuate radiation rays, the inner layer BECQ powder can further attenuate and absorb the attenuated radiation rays, and the radiation rays can be efficiently shielded through the synergistic effect between the outer layer BECQ powder and the inner layer BECQ powder, so that the crystal has a certain application prospect in the field of materials.

Description

Anti-radiation gradient composite material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a radiation-proof gradient composite material as well as a preparation method and application thereof.
Background
Electromagnetic waves are mainly classified into radio waves, microwaves, infrared rays, visible light, ultraviolet rays, X-rays, λ rays, and the like, according to their frequencies from small to large. Any kind of electromagnetic wave brings certain harm while providing convenience for human beings. The damage mode of the electromagnetic wave to the human body can be divided into two types, wherein one type is that the temperature of the organism can be raised because the organism is forced to generate a heat effect and the redundant heat can not be released in time, and when the temperature exceeds a certain limit, the organism can be damaged because the temperature in the organism is too high and cannot be borne; the other is to disturb the weak inherent magnetic field in human body to affect the normal operation of blood and lymph, change the cellular protoplasm, cause the pathological changes of tissue, cause the immunity to decline, cause the symptoms of insomnia, hypodynamia and the like, and further induce the generation of leukemia and cancer. The health care product is quite unfavorable for human bodies when people live in an environment with intensive electromagnetic waves frequently, and the mood of people can fluctuate due to the long-time contact of the intensive electromagnetic waves, so that the people can suffer from headache, tinnitus, fatigue, hypodynamia, insomnia and dreaminess. Even memory loss and the like, so-called electromagnetic radiation hypersensitivity syndrome (EHS), may increase the risk of cancer such as parkinson's disease and senile dementia. For the protection of ionizing radiation, besides reasonably developing and utilizing electromagnetic resources and keeping away from radioactive sources and the environment with dense electromagnetic waves, the development of protective materials is very important.
For the field of X-ray protection of medium and low energy, such as medical diagnosis, the best effect is the composite material made of rare earth elements, and for the preparation of the rare earth composite material, three preparation methods of physical blending, chemical blending and combination of the two are mainly available. The resin/nano lead composite material and the resin/nano lead sulfate composite material are shielding materials with better effect at present, and have the characteristics of low density, low lead content and strong X-ray shielding capability.
The research provides certain reference and reference for preparing the lead-less or lead-free protective material, and simultaneously has a plurality of problems: the preparation process or the formula is too complex and difficult to repeat and carry out industrial production; the microstructure of the material is not designed and regulated for radiation protection, and the comprehensive radiation protection performance is different from the traditional lead protection performance; the existing research shows that the small-size effect, the surface and interface effect, the quantum size effect and the like of the nano material have good promotion effects on improving the physical properties and the shielding effect of the material, and the nano material is applied to the preparation of the shielding material to a certain extent and has good effects, but the comprehensive benefits of the nano material are further utilized to greatly improve the performance of the radiation-proof material, further research is needed, and how to enable the material to have the performances of light weight, no toxicity, small volume, wide shielding range, long-lasting shielding performance and the like is a difficult point of research and is not solved essentially.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a radiation-proof gradient composite material, a preparation method and application thereof, and solves the problems that the traditional radiation-proof material cannot have light weight, no toxicity, small volume, wide shielding range, lasting shielding performance and the like.
One object of the present invention is to provide a radiation protective gradient composite.
The radiation-proof gradient composite material comprises the following components in parts by weight: 30-40 parts of core layer composite crystal, 35-50 parts of BECQ powder and 20-35 parts of polyethylene glycol.
Preferably, the radiation protective gradient composite material comprises an inner layer of BECQ powder and an outer layer of core composite crystals.
Preferably, the specification model of the polyethylene glycol is PEG-600.
Preferably, the core layer composite crystal comprises MoO as a main component 3 And (4) crystals.
Preferably, the BECQ core comprises the following components in parts by weight: 15-30 parts of iron source ion precursor, 25-35 parts of silver source ion precursor, 20-35 parts of rare earth cerium source ion precursor and 2-5 parts of dispersing agent, wherein the BECQ shell comprises 25-40 parts of samarium source ion precursor.
More preferably, the iron source ion precursor is one of ferric nitrate and ferric sulfate, the silver source ion precursor is one of silver nitrate and silver acetate, the rare earth cerium source ion precursor is one of cerium acetate and cerium nitrate, the dispersing agent is polyvinyl alcohol, and the samarium source ion precursor is samarium nitrate.
According to the invention, the BECQ powder is a multi-element micron particle, and the inventor finds that through a large amount of experimental optimization, an iron source ion precursor, a silver source ion precursor, a rare earth cerium source ion precursor and a dispersing agent are weighed according to a certain proportion and mixed, and then the mixture is subjected to high-temperature sintering, airflow crushing and screening to obtain hollow spherical powder, wherein the hollow spherical powder has a hollow structure and can effectively shield high-energy radiation rays, and further, a samarium source ion precursor is added according to a certain proportion, and a chemical vapor deposition method is used for carrying out chemical vapor deposition on the hollow spherical powderCoating the hollow spherical powder to prepare BECQ powder with a core-shell structure, wherein the BECQ powder can enable incident energy to generate eddy current loss on one hand, and a samarium source ion precursor shell on the surface of the BECQ powder can have a certain shielding effect on rays; adding a core layer composite crystal layer on the basis of the BECQ powder with the core-shell structure, wherein the main component of the core layer composite crystal layer is MoO 3 A crystal having excellent shielding characteristics; when incident energy irradiates on the radiation-proof gradient composite material, the outer core layer composite crystal layer can absorb a part of incident energy, the attenuated incident energy enters the inner BECQ powder, then the BECQ powder shell further absorbs a part of incident energy, so that the re-attenuated incident energy enters BECQ powder cores and is shielded and absorbed through eddy current loss.
The invention also aims to provide a preparation method of the radiation-proof gradient composite material.
The preparation method comprises the following steps:
s1, BECQ powder preparation: weighing an iron source ion precursor, a silver source ion precursor, a rare earth cerium source ion precursor and a dispersing agent according to a ratio, mixing, performing high-temperature sintering, airflow crushing and screening to obtain hollow spherical powder, adding a samarium source ion precursor according to a ratio, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare the BECQ powder with a core-shell structure;
s2, preparation of core layer composite crystal: putting carbon powder into a molybdenum wire resistance furnace, introducing a mixed solution containing ethanol and boric acid into a working cavity of the molybdenum wire resistance furnace by a control device, introducing a certain amount of argon gas as a protective gas, starting a heating device to heat the molybdenum wire resistance furnace, controlling the temperature to be 1000-1200 ℃, and reacting for a period of time to obtain MoO 3 A core layer composite crystal;
s3, preparing the radiation-proof gradient composite material: mixing 35-50 parts by weight of BECQ powder prepared in the step S1, 30-40 parts by weight of core layer composite crystal and 20-35 parts by weight of polyethylene glycol, performing ultrasonic dispersion for 2-3 hours, sintering in a vacuum furnace at 500-600 ℃ for 6-8 hours, cooling, performing air flow crushing, and screening and grading to obtain the radiation-proof gradient composite material.
Preferably, in the step S1, a chemical vapor deposition method is used to coat the hollow sphere-shaped powder, and the method includes: firstly, adding the samarium source ion precursor into a hollow spherical powder reaction container, then introducing a certain amount of hydrogen into the reaction container, introducing the hydrogen at a flow rate of 120ml/min, carrying out reduction reaction at a temperature of 900-1000 ℃, simultaneously introducing a certain amount of argon as a protective gas at a flow rate of 180ml/min, and obtaining a metal nickel coating shell on the surface of the hollow spherical powder after 70min of heat preservation reaction.
Preferably, in the step S2, the mass fraction of the ethanol in the mixed solution of the ethanol and the boric acid is 25%, the mass fraction of the boric acid is 75%, the flow rate of introducing the argon gas is 150ml/min, the heating rate is 10 ℃/min, and the reaction is carried out for 3 hours.
The invention finally aims to provide the application of the radiation-proof gradient composite material in preparing the foam material.
Compared with the prior art, the invention has the following advantages:
1) according to the invention, the BECQ powder is a multi-element micron particle and has a core-shell structure, so that high-energy radiation rays can be effectively shielded, on one hand, the BECQ powder can enable incident energy to generate eddy current loss, and meanwhile, samarium source ion precursors on the surface of the BECQ powder can have a certain shielding effect on the rays;
2) the radiation-proof gradient composite material is prepared by adding a core layer composite crystal layer on the basis of BECQ powder, wherein the main component of the core layer composite crystal layer is MoO 3 The crystal has good shielding property, the outer core layer composite crystal can absorb and attenuate radiation rays, the inner layer BECQ powder further attenuates and absorbs the attenuated radiation rays, and the two have synergistic effectAnd the radiation rays can be efficiently shielded, so the material has a certain application prospect in the field of materials.
Drawings
FIG. 1 is a flow chart of the preparation process of the radiation-proof gradient composite material of the present invention;
FIG. 2 is a schematic structural view of the radiation-proof gradient composite material of the present invention, wherein 1 is an inner layer of BECQ powder, and 2 is an outer layer of composite crystal of a core layer;
FIG. 3 is an FESEM spectrum of a core layer composite crystal, wherein spectrum (A) is a crystal morphology at a resolution of 1 μm, spectrum (B) is a crystal morphology at a resolution of 10 μm, and spectrum (C) and spectrum (D) are crystal morphologies at a resolution of 200 nm;
fig. 4 is a characteristic diagram of the core layer composite crystal, wherein diagram (a) is an XRD diffractogram of the crystal, diagram (B) is a raman spectroscopic scan of the crystal, and diagram (C) and diagram (D) are HRTEM images of the core layer composite crystal.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention is clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention.
Boric acid (mass fraction greater than 99.99%) and ethanol (mass fraction greater than 99.8%) used in the present invention were purchased from Aladdin corporation; other conventional chemical reagents and instrumentation, unless otherwise specified, are commercially available.
Example 1
The preparation method of the radiation-proof gradient composite material comprises the following steps:
s1, BECQ powder preparation: weighing 15 parts of ferric nitrate, 25 parts of silver nitrate, 20 parts of cerium acetate and 2 parts of polyvinyl alcohol according to a proportion, mixing, sintering at a high temperature, carrying out air flow crushing, and screening to obtain hollow spherical powder, then adding 25 parts of samarium nitrate according to a proportion, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare BECQ powder with a core-shell structure; the chemical vapor deposition method comprises the following specific processes: introducing hydrogen into the reaction container at a flow rate of 120ml/min and argon at a flow rate of 180ml/min, performing reduction reaction at a temperature of 900 ℃, and performing heat preservation reaction for 70min to obtain a metal samarium coating on the surface of the hollow spherical powder;
s2, preparation of core layer composite crystal: putting carbon powder in a molybdenum wire resistance furnace, introducing a mixed solution containing ethanol and boric acid into a working cavity of the molybdenum wire resistance furnace by a control device, wherein the mass fraction of the ethanol in the mixed solution of the ethanol and the boric acid is 25 percent, the mass fraction of the boric acid is 75 percent, introducing a certain amount of argon gas as a protective gas, introducing the flow of the argon gas is 150ml/min, finally starting a heating device to heat the molybdenum wire resistance furnace, the heating rate is 10 ℃/min, controlling the temperature at 1000 ℃, and reacting for 3 hours to obtain MoO 3 A core layer composite crystal;
s3, preparing the radiation-proof gradient composite material: mixing 35 parts by weight of BECQ powder prepared in the step S1, 30 parts by weight of core layer composite crystal and 20 parts by weight of polyethylene glycol, ultrasonically dispersing for 2 hours, sintering for 6 hours in a vacuum furnace at 500 ℃, cooling, and carrying out airflow crushing and screening grading to obtain the radiation-proof gradient composite material.
Example 2
The preparation method of the radiation-proof gradient composite material comprises the following steps:
s1, BECQ powder preparation: weighing 23 parts of ferric sulfate, 23 parts of silver acetate, 28 parts of cerium nitrate and 3 parts of polyvinyl alcohol according to a proportion, mixing, sintering at a high temperature, carrying out air flow crushing, and screening to obtain hollow spherical powder, adding 32 parts of samarium nitrate according to a proportion, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare BECQ powder with a core-shell structure; the chemical vapor deposition method comprises the following specific processes: introducing hydrogen into the reaction container at a flow rate of 120ml/min and argon at a flow rate of 180ml/min, performing reduction reaction at a temperature of 950 ℃, and performing heat preservation reaction for 70min to obtain a metal samarium coating on the surface of the hollow spherical powder;
s2, preparation of core layer composite crystal: putting carbon powder in a molybdenum wire resistance furnace, introducing a mixed solution containing ethanol and boric acid into a working cavity of the molybdenum wire resistance furnace by a control device, wherein the mass fraction of the ethanol in the mixed solution of the ethanol and the boric acid is 25 percent, the mass fraction of the boric acid is 75 percent, introducing a certain amount of argon gas as a protective gas, introducing the flow of the argon gas is 150ml/min, finally starting a heating device to heat the molybdenum wire resistance furnace, the heating rate is 10 ℃/min, controlling the temperature at 1100 ℃, and reacting for 3 hours to obtain MoO 3 A core layer composite crystal;
s3, preparing the radiation-proof gradient composite material: and (3) mixing 42 parts by weight of BECQ powder prepared in the step S1, 35 parts by weight of core layer composite crystal and 28 parts by weight of polyethylene glycol, ultrasonically dispersing for 2.5 hours, sintering for 7 hours in a 550 ℃ vacuum furnace, cooling, and carrying out airflow crushing and screening classification to obtain the radiation-proof gradient composite material.
Performing FESEM observation on the core layer composite crystal prepared in the step S2, wherein the pattern (A) is the crystal morphology under the resolution of 1 μm, the pattern (B) is the crystal morphology under the resolution of 10 μm, and the pattern (C) and the pattern (D) are the crystal morphology under the resolution of 200 nm; as can be seen from the figure, the core layer composite crystal is layered and has a smooth surface;
characterizing the core layer composite crystal prepared in the step S2, wherein a spectrum (A) is an XRD diffraction pattern of the crystal, a spectrum (B) is a Raman spectrum scanning pattern of the crystal, and a spectrum (C) and a spectrum (D) are HRTEM patterns of the core layer composite crystal; as can be seen from the figure, the core layer composite crystal has MoO as the main component 3 。
Example 3
The preparation method of the radiation-proof gradient composite material comprises the following steps:
s1, BECQ powder preparation: weighing 30 parts of ferric nitrate, 35 parts of silver acetate, 35 parts of cerium acetate and 5 parts of polyvinyl alcohol according to a proportion, mixing, sintering at a high temperature, carrying out air flow crushing, and screening to obtain hollow spherical powder, adding 40 parts of samarium nitrate according to a proportion, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare BECQ powder with a core-shell structure; the chemical vapor deposition method comprises the following specific processes: introducing hydrogen into the reaction container at a flow rate of 120ml/min and argon at a flow rate of 180ml/min, carrying out reduction reaction at a temperature of 1000 ℃, and carrying out heat preservation reaction for 70min to obtain a metal samarium coating on the surface of the hollow spherical powder;
s2, preparation of core layer composite crystal: putting carbon powder in a molybdenum wire resistance furnace, introducing a mixed solution containing ethanol and boric acid into a working cavity of the molybdenum wire resistance furnace by a control device, wherein the mass fraction of the ethanol in the mixed solution of the ethanol and the boric acid is 25 percent, the mass fraction of the boric acid is 75 percent, introducing a certain amount of argon gas as a protective gas, introducing the flow of the argon gas is 150ml/min, finally starting a heating device to heat the molybdenum wire resistance furnace, the heating rate is 10 ℃/min, controlling the temperature at 1200 ℃, and reacting for 3 hours to obtain MoO 3 A core layer composite crystal;
s3, preparing the radiation-proof gradient composite material: mixing 50 parts by weight of BECQ powder prepared in the step S1, 40 parts by weight of core layer composite crystal and 35 parts by weight of polyethylene glycol, ultrasonically dispersing for 3 hours, sintering for 8 hours in a vacuum furnace at 600 ℃, cooling, and carrying out airflow crushing and screening grading to obtain the radiation-proof gradient composite material.
Comparative example 1
The whole preparation method is the same as that of example 2, except that no BECQ powder is added in the preparation process of the radiation-proof gradient composite material.
The preparation method of the radiation-proof gradient composite material comprises the following steps:
s2, preparation of core layer composite crystal: putting carbon powder in a molybdenum wire resistance furnace, introducing a mixed solution containing ethanol and boric acid into a working cavity of the molybdenum wire resistance furnace by a control device, wherein the mass fraction of the ethanol in the mixed solution of the ethanol and the boric acid is 25 percent, the mass fraction of the boric acid is 75 percent, introducing a certain amount of argon gas as a protective gas, introducing the flow of the argon gas is 150ml/min, finally starting a heating device to heat the molybdenum wire resistance furnace, the heating rate is 10 ℃/min, controlling the temperature at 1100 ℃, and reacting for 3 hours to obtain MoO 3 A core layer composite crystal;
s3, preparing the radiation-proof gradient composite material: and (2) mixing 42 parts by weight of BECQ powder prepared in the step S1, 35 parts by weight of core layer composite crystal and 28 parts by weight of polyethylene glycol, performing ultrasonic dispersion for 2.5 hours, sintering for 7 hours in a 550 ℃ vacuum furnace, cooling, performing air flow crushing, and performing screening classification to obtain the radiation-proof gradient composite material.
Comparative example 2
The whole preparation method is the same as that of example 2, except that the outer layer of the core layer composite crystal is not added in the preparation process of the radiation-proof gradient composite material.
Comparative example 3
A radiation protective material was prepared using the method of example 5 in application publication No. CN 111228142A.
Example 4 radiation Performance testing
The radiation performance test is performed on the radiation protection gradient composite materials prepared in the embodiments 1 to 3 and the comparative examples 1 to 2, specifically, the test instrument is a thermoluminescent dosimeter (RGD-3B/S), the measurement range is 0.01 μ Gy to 10Gy, the linear deviation is less than 1%, the light source stability is not more than 0.5% (continuous 10h), the maximum heating temperature is 400 ℃, the linear heating rate is 1 ℃/S to 40 ℃/S, the specific test standard is that the surface absorption amount is tested according to GBZ128 to 2002 and GBZ207 to 2008, meanwhile, lead with the weight corresponding to each radiation protection material is respectively adopted as the surface absorption amount for the test of the standard sample, and the specific test result is shown in table 1:
TABLE 1 test results table
Figure BDA0002947934720000101
As can be seen from the data in Table 1, in comparative example 1, because no BECQ powder is added, the radiation-proof gradient composite material prepared has lower radiation resistance, the surface absorption capacity (mGy) of the composite material is 60.12, and the radiation-proof gradient composite material reaches 10.16% of the corresponding surface absorption capacity (mGy) of the standard sample (lead); in the comparative example 2, the outer layer of the core layer composite crystal is not added, the radiation resistance performance of the prepared radiation-proof gradient composite material is lower than that of the composite material in the examples 1-3, the surface absorption amount (mGy) of the composite material is 92.05 and reaches 75.54% of the corresponding surface absorption amount (mGy) of a standard sample (lead), and the result shows that the radiation resistance performance is further enhanced by adding the outer layer of the core layer composite crystal on the surface of the hollow spherical powder; in the comparative example 3, the radiation protection material is prepared by adopting the method of the embodiment 5 in the application number CN111228142A, the radiation performance of the prepared radiation protection gradient composite material is lower than that of the embodiments 1-3, the surface absorption capacity (mGy) is 105, and reaches 78.26% of the corresponding surface absorption capacity (mGy) of a standard sample (lead), because the core of the radiation protection gradient composite material prepared in the comparative example 3 has more components than that of the invention, polyvinyl alcohol is adopted for coating the shell, the core has less components, and the metal samarium coating is coated by adopting a chemical deposition method for coating the shell, the result shows that the radiation resistance performance of the prepared radiation protection gradient composite material is obviously improved after the shell is coated by adopting the chemical deposition method; the surface absorption capacity (mGy) of the radiation-proof gradient composite material prepared in example 1 was 138.75, which was 95.45% of the corresponding surface absorption capacity (mGy) of the standard sample (lead); the surface absorption capacity (mGy) of the radiation-proof gradient composite material prepared in example 2 is 137.50, which reaches 96.63% of the corresponding surface absorption capacity (mGy) of the standard sample (lead); the surface absorption capacity (mGy) of the radiation-proof gradient composite material prepared in the embodiment 3 is 131.84, which reaches 93.12% of the corresponding surface absorption capacity (mGy) of a standard sample (lead), and the result shows that the radiation-proof gradient composite material has better radiation resistance and has a certain application prospect in the field of materials.
Example 5 application of radiation protective gradient composite material in preparing foam material
The radiation-proof gradient composite material prepared in the embodiment 2 is added into a foam material, the foam material is prepared by adopting the prior art, and details are not repeated herein. And (3) taking the foam material without the radiation-proof gradient composite material as a blank control, and carrying out a radiation performance test:
the result shows that the prepared foam material has almost no radiation resistance performance without adding a radiation-proof gradient composite material; the radiation-proof gradient composite material is added, the surface absorption capacity (mGy) of the prepared foam material is 137.50, and reaches 96.63% of the corresponding surface absorption capacity (mGy) of a standard sample (lead), so the radiation-proof gradient composite material has a good application prospect in the field of preparing the foam material.
The above embodiments are merely for illustrating the technical solutions of the present invention and not for limiting the present invention, and the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that changes, modifications, additions or substitutions within the spirit and scope of the present invention may be made by those skilled in the art without departing from the spirit of the present invention, and shall also fall within the scope of the claims of the present invention.

Claims (8)

1. The preparation method of the radiation-proof gradient composite material is characterized by comprising the following steps of:
s1, BECQ powder preparation: weighing an iron source ion precursor, a silver source ion precursor, a rare earth cerium source ion precursor and a dispersing agent according to a ratio, mixing, performing high-temperature sintering, airflow crushing and screening to obtain hollow spherical powder, adding a samarium source ion precursor according to a ratio, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare the BECQ powder with a core-shell structure;
s2, preparation of core layer composite crystal: putting carbon powder in a molybdenum wire resistance furnace, introducing a mixed solution containing ethanol and boric acid into a working cavity of the molybdenum wire resistance furnace through a control device, introducing a certain amount of argon as a protective gas, starting a heating device to heat the molybdenum wire resistance furnace, controlling the temperature to be 1000-1200 ℃, and reacting for a period of time to obtain MoO 3 A core layer composite crystal;
s3, preparing the radiation-proof gradient composite material: mixing 35-50 parts by weight of BECQ powder prepared in the step S1, 30-40 parts by weight of core layer composite crystal and 20-35 parts by weight of polyethylene glycol, ultrasonically dispersing for 2-3 hours, sintering in a vacuum furnace at 500-600 ℃ for 6-8 hours, cooling, and carrying out airflow crushing and screening grading to obtain the radiation-proof gradient composite material.
2. The method of claim 1, wherein in step S1, the BECQ core comprises the following components in parts by weight: 15-30 parts of iron source ion precursor, 25-35 parts of silver source ion precursor, 20-35 parts of rare earth cerium source ion precursor and 2-5 parts of dispersing agent, wherein the BECQ shell comprises 25-40 parts of samarium source ion precursor.
3. The method for preparing a radiation-proof gradient composite material according to claim 2, wherein the iron source ion precursor is one of ferric nitrate and ferric sulfate, the silver source ion precursor is one of silver nitrate and silver acetate, the rare earth cerium source ion precursor is one of cerium acetate and cerium nitrate, the dispersant is polyvinyl alcohol, and the samarium source ion precursor is samarium nitrate.
4. The method for preparing a radiation-proof gradient composite material according to claim 1, wherein the step S1 is a specific method for coating the hollow sphere-shaped powder by using a chemical vapor deposition method, which comprises the following steps: firstly, adding the samarium source ion precursor into a hollow spherical powder reaction container, then introducing a certain amount of hydrogen into the reaction container, introducing the hydrogen at a flow rate of 120ml/min, carrying out reduction reaction at a temperature of 900-1000 ℃, simultaneously introducing a certain amount of argon as a protective gas at a flow rate of 180ml/min, and obtaining a metal samarium coating shell on the surface of the hollow spherical powder after 70min of heat preservation reaction.
5. The method for preparing a radiation-proof gradient composite material according to claim 1, wherein in the step S2, the mixed solution of ethanol and boric acid contains 25% by mass of ethanol and 75% by mass of boric acid, the flow rate of argon gas is 150ml/min, the heating rate is 10 ℃/min, and the reaction is carried out for 3 hours.
6. The method for preparing a radiation-proof gradient composite material as claimed in claim 1, wherein in step S3, the polyethylene glycol is PEG-600.
7. The radiation protective gradient composite material obtained by the method for preparing a radiation protective gradient composite material according to any one of claims 1 to 6, wherein the radiation protective gradient composite material comprises an inner layer (1) of BECQ powder and an outer layer (2) of core layer composite crystal.
8. Use of a radiation protection gradient composite material obtained by the method of preparing a radiation protection gradient composite material according to any one of claims 1 to 6 for preparing a foam material.
CN202110199269.7A 2021-02-23 2021-02-23 Anti-radiation gradient composite material and preparation method and application thereof Active CN112895621B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110199269.7A CN112895621B (en) 2021-02-23 2021-02-23 Anti-radiation gradient composite material and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110199269.7A CN112895621B (en) 2021-02-23 2021-02-23 Anti-radiation gradient composite material and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112895621A CN112895621A (en) 2021-06-04
CN112895621B true CN112895621B (en) 2022-08-05

Family

ID=76124502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110199269.7A Active CN112895621B (en) 2021-02-23 2021-02-23 Anti-radiation gradient composite material and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112895621B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113321877B (en) * 2021-06-15 2023-04-07 天津天颐科苑科技有限公司 Recyclable flexible radiation-proof sheet and preparation method thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1019373A (en) * 1962-08-10 1966-02-02 Atomic Energy Authority Uk A new glass containing radioactive waste oxides
JP5730670B2 (en) * 2011-05-27 2015-06-10 株式会社Adeka Method for producing thin film containing molybdenum oxide, and raw material for forming thin film containing molybdenum oxide
US9765271B2 (en) * 2012-06-27 2017-09-19 James J. Myrick Nanoparticles, compositions, manufacture and applications
CN110117457A (en) * 2019-05-28 2019-08-13 河南嘉和节能科技有限公司 A kind of high temperature resistant anti-infrared attenuation energy-saving coatings
CN111228142A (en) * 2020-03-23 2020-06-05 武汉市莎卡娜尔生物技术有限公司 Radiation protection material, preparation method thereof and skin care product
CN111572133A (en) * 2020-05-27 2020-08-25 成都盛帮密封件股份有限公司 Flexible material with nuclear radiation protection and electromagnetic shielding functions, and preparation method and application thereof
CN112011180A (en) * 2020-08-28 2020-12-01 武汉市莎卡娜尔科技有限公司 Wave-absorbing radiation-proof plastic and preparation method thereof

Also Published As

Publication number Publication date
CN112895621A (en) 2021-06-04

Similar Documents

Publication Publication Date Title
Yan et al. An ultra-small NiFe 2 O 4 hollow particle/graphene hybrid: fabrication and electromagnetic wave absorption property
Yang et al. Dramatically enhanced electromagnetic wave absorption of hierarchical CNT/Co/C fiber derived from cotton and metal-organic-framework
Yan et al. Enhanced electromagnetic wave absorption induced by void spaces in hollow nanoparticles
Wang et al. Activating microwave absorption via noncovalent interactions at the interface based on metal-free graphene nanosheets
Kumar et al. Nickel nanoparticles embedded in carbon foam for improving electromagnetic shielding effectiveness
CN101179921B (en) Method for preparing electromagnetic shielding light graphite based nanometer magnetic metal composite material
Singh et al. Raman and Fourier-transform infrared spectroscopic study of nanosized zinc ferrite irradiated with 200 MeV Ag15+ beam
CN104099062B (en) Compounded wave-absorbing material of grapheme/four-pin zinc oxide whisker and preparation method thereof
CN112895621B (en) Anti-radiation gradient composite material and preparation method and application thereof
Sun et al. Biomass-derived carbon decorated with Ni0. 5Co0. 5Fe2O4 particles towards excellent microwave absorption performance
Zhu et al. Synthesis and electromagnetic wave absorption performance of NiCo 2 O 4 nanomaterials with different nanostructures
Zhang et al. Enhanced microwave absorption property of ferroferric Oxide: The role of magnetoelectric resonance
Kang et al. Porous core-shell zeolitic imidazolate framework-derived Co/NPC@ ZnO-decorated reduced graphene oxide for lightweight and broadband electromagnetic wave absorber
Su et al. Fe/Fe3O4/biomass carbon derived from agaric to achieve high-performance microwave absorption
CN111228142A (en) Radiation protection material, preparation method thereof and skin care product
Meng et al. A facile coprecipitation method to synthesize FexOy/Fe decorated graphite sheets with enhanced microwave absorption properties
He et al. Multispectral electromagnetic shielding using ultra-thin metal-metal oxide decorated hybrid nanofiber membranes
Liang et al. A novel synthesis of Porous Fe4N/carbon hollow microspheres for thin and efficient electromagnetic wave absorbers
Wu et al. Polymer‐derived Co2Si@ SiC/C/SiOC/SiO2/Co3O4 nanoparticles: microstructural evolution and enhanced EM absorbing properties
Gharissah et al. Composites cement/BaSO4/Fe3O4/CuO for improving X-ray absorption characteristics and structural properties
Zhou et al. Interstitial boron-doped FeCoNiCr high entropy alloys with excellent electromagnetic-wave absorption and resistance to harsh environments
Wang et al. Preparation and electromagnetic-wave-absorption properties of a nitrogen-doped carbon–supported iron (II, III) oxide composite
Rehman et al. Hierarchical‐Bioinspired MOFs Enhanced Electromagnetic Wave Absorption
Sun et al. 3D hierarchical porous structure formed by CS/GP/Ni0. 5Co0. 5Fe2O4 for high-efficiency microwave absorption
Wei et al. Synergistic effect of polyindole decoration on bismuth neodymium ferrite powder for achieving wideband microwave absorber

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant