CN113012838B

CN113012838B - Anti-radiation composite colloidal particle and preparation method and application thereof

Info

Publication number: CN113012838B
Application number: CN202110199229.2A
Authority: CN
Inventors: 何浏; 任婕
Original assignee: Wuhan Shakanar Technology Co ltd
Current assignee: Wuhan Shakanar Technology Co ltd
Priority date: 2021-02-23
Filing date: 2021-02-23
Publication date: 2023-05-05
Anticipated expiration: 2041-02-23
Also published as: CN113012838A

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a radiation-proof composite colloidal particle, and a preparation method and application thereof. The radiation-resistant composite colloidal particle comprises the following components in parts by weight: 10 to 30 parts of BECQ powder, 70 to 90 parts of polymer, 0.5 to 0.9 part of antioxidant, 0.3 to 0.8 part of ultraviolet absorber and 0.3 to 0.5 part of antibacterial agent. In the invention, the BECQ powder is a multi-element micron particle and has a core-shell structure, can effectively shield high-energy radiation rays, can enable incident energy to generate eddy current loss on one hand, and meanwhile, a nickel source ion precursor on the surface of the BECQ powder can have a certain shielding effect on the rays; in addition, the composite colloidal particle provided by the invention also contains an antioxidant, an ultraviolet absorber and an antibacterial agent, so that the anti-radiation composite colloidal particle has certain anti-radiation performance and certain anti-ultraviolet, antioxidant and antibacterial capabilities, and has a certain application prospect in the field of materials.

Description

Anti-radiation composite colloidal particle 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 composite colloidal particle, and a preparation method and application thereof.

Background

With the rapid development of modern science and technology, various high-energy rays (X-rays, gamma-rays) are increasingly used in the fields of military, communication, medicine, industry and agriculture, and the like, and in daily life. But brings convenience and enjoyment to people, and various high-energy rays bring some harm to people to a certain extent. Current research shows that the effect of radiation on the human body is mainly in several aspects: electromagnetic radiation is the main causative agent of cardiovascular disease, diabetes, and cancer mutations; direct impact injury is caused to the reproductive system, the nervous system and the immune system of a human body; electromagnetic radiation is a causative factor for abortion, infertility, teratocarcinoma and other diseases in pregnant women; excessive electromagnetic radiation directly affects children tissue development, bone development, vision deterioration, liver hematopoietic function deterioration, and retinal detachment caused by serious cases; electromagnetic radiation can cause endocrine disorders. Therefore, how to reduce various radiation intensities, prevent radiation pollution, effectively protect the environment and protect the health of human bodies becomes a research hotspot of a plurality of scholars.

The radiation protection material is a material capable of absorbing or dissipating radiation energy and protecting human bodies or instruments, and because radiation sources causing human body injury are various (including ionizing radiation and non-ionizing radiation), energy levels of radiation generated by the radiation sources are different, and materials resisting the radiation are different, so that various made radiation protection products have various characteristics, at present, the main radiation protection materials comprise radiation protection lead glass, lead plates, protective doors, various protective coatings and the like, and the radiation protection materials comprise transparent materials and opaque materials according to different use occasions and can be divided into radiation clothes for resisting ultraviolet rays, microwaves, X rays and neutrons according to different shielding rays.

X-rays are photon radiation, essentially electromagnetic waves, with a strong penetrability, which are commonly used in medical devices for examining the viscera of the human body for certain diseases or for quality detection of industrial products. The related staff can hurt the gonads, mammary glands, red bone marrow and the like of human bodies when contacting the rays for a long time, and can cause diseases such as leukemia, bone tumor and the like if the dosage exceeds a certain dosage, thereby bringing serious threat to life. The traditional medical shielding material is lead, the atomic number of the lead is 82, and the lead has good energy absorption property and is an ideal material for shielding high-energy ionizing radiation. However, a particle absorption capacity weak region (i.e., a "weak absorption region" of lead) exists for ionizing radiation having an energy of between 40keV and 88.0keV, and therefore the defect is obvious in the radiation-proof material made of lead as the only absorbing substance. In addition, the lead oxide in the protective products of products such as lead-containing glass, organic glass, rubber and the like is extremely tired and even damaged on the back and waist muscles of medical radiologists due to the heaviness, and the lead oxide in the protective products has certain toxicity and can pollute the environment to a certain extent, so the development of lead-free or lead-free radiation-proof materials is extremely important.

Disclosure of Invention

Aiming at the problems in the prior art, the invention aims to provide a radiation-proof composite colloidal particle, and a preparation method and application thereof. Solves the problems that lead oxide in the traditional lead-containing radiation-proof material has certain toxicity and can pollute the environment to a certain extent.

An object of the present invention is to provide a radiation protection composite colloidal particle.

The radiation-proof composite colloidal particle comprises the following components in parts by weight: 10 to 30 parts of BECQ powder, 70 to 90 parts of polymer, 0.5 to 0.9 part of antioxidant, 0.3 to 0.8 part of ultraviolet absorber and 0.3 to 0.5 part of antibacterial agent.

Preferably, the polymer is one or more of polypropylene, polyamide and polytetrafluoroethylene.

Preferably, the antioxidant is one or more of IF168, IN3114 and INB 215.

Preferably, the ultraviolet absorber is CHIMASSORB 2020BOX and the antimicrobial agent is IRGAGUARD B1000.

Preferably, the BECQ powder has a core-shell structure in parts by weight, and the BECQ inner core comprises the following components in parts by weight: 20-35 parts of titanium source ion precursor, 40-55 parts of zinc source ion precursor, 20-35 parts of rare earth cerium source ion precursor and 3-7 parts of dispersing agent, wherein the BECQ shell component is 30-50 parts of nickel source ion precursor.

More preferably, the titanium source ion precursor is butyl titanate, the zinc source ion precursor is one of zinc nitrate and zinc acetate, the rare earth cerium source ion precursor is one of cerium sulfate and cerium nitrate, the dispersing agent is polyvinyl alcohol, and the nickel source ion precursor is nickel chloride hexahydrate.

According to the invention, the inventor finds that the titanium source ion precursor, the zinc source ion precursor, the rare earth cerium source ion precursor and the dispersing agent are weighed according to the proportion through a large number of experimental optimization, and are mixed, and through high-temperature sintering, jet milling and screening, hollow spherical powder is obtained, the hollow spherical powder has a hollow structure and can effectively shield high-energy radiation rays, and further, the nickel source ion precursor is added according to the proportion and is coated by using a chemical vapor deposition method, so that the BECQ powder with a core-shell structure is prepared, on the one hand, the incident energy of the BECQ powder can generate vortex loss, and meanwhile, the nickel source ion precursor outer shell on the surface of the BECQ powder can have a certain shielding effect on the radiation rays; the ultraviolet absorber is added to the composite colloidal particles on the basis of the BECQ powder, the ultraviolet absorption capacity is further enhanced, and the antioxidant and the antibacterial agent are added to further improve the performances of the composite colloidal particles in terms of oxidization resistance, antibacterial property and the like. Therefore, the composite colloidal particle has radiation resistance, certain ultraviolet resistance, oxidation resistance, antibacterial capacity and other capacities, and has a certain application prospect in the field of materials.

The invention further aims at providing a preparation method of the radiation-proof composite colloidal particle.

The preparation method comprises the following steps:

s1, BECQ powder preparation: the preparation method of the BECQ powder comprises the steps of weighing a titanium source ion precursor, a zinc source ion precursor, a rare earth cerium source ion precursor and a dispersing agent according to the proportion, mixing, performing high-temperature sintering, jet milling and screening to obtain hollow spherical powder, adding a nickel source ion precursor according to the proportion, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare the BECQ powder with a core-shell structure;

s2: uniformly mixing 10-30 parts by weight of BECQ powder prepared in the step S1, 70-90 parts by weight of polymer, 0.5-0.9 part by weight of antioxidant, 0.3-0.8 part by weight of ultraviolet absorbent and 0.3-0.5 part by weight of antibacterial agent to obtain a mixture;

s3: mixing, extruding, wiredrawing and cutting the mixture with the mass fraction of 60% and the polymer with the mass fraction of 40% which are prepared in the step S2 into composite colloidal particles at 155 ℃, wherein the polymer is one or more of polypropylene, polyamide and polytetrafluoroethylene.

Preferably, in the step S1, the specific method for coating the hollow sphere powder by using a chemical vapor deposition method is as follows: firstly, dehydrating and drying the nickel chloride hexahydrate, adding the nickel chloride hexahydrate into a hollow spherical powder reaction container, then introducing a certain amount of hydrogen into the reaction container, carrying out reduction reaction at a certain temperature, simultaneously introducing a certain amount of argon to be used as a protective gas, and finally obtaining a metal nickel coating shell on the surface of the hollow spherical powder after a period of heat preservation reaction.

More preferably, the flow rate of the hydrogen gas is 120ml/min, the flow rate of the argon gas is 180ml/min, the temperature of the reduction reaction is 900-1000 ℃, and after the heat preservation reaction for 70min, the metallic nickel coating is finally obtained on the surface of the hollow spherical powder.

The invention finally aims to provide an application of the radiation-proof composite colloidal particles in preparing melt-blown non-woven fabrics.

Compared with the prior art, the invention has the following advantages:

1) In the invention, the BECQ powder is a multi-element micron particle and has a core-shell structure, can effectively shield high-energy radiation rays, can enable incident energy to generate eddy current loss on one hand, and meanwhile, a nickel source ion precursor on the surface of the BECQ powder can have a certain shielding effect on the rays;

2) The composite colloidal particle is characterized in that an ultraviolet absorber is added on the basis of BECQ powder, the ultraviolet absorption capacity is further enhanced, and an antioxidant and an antibacterial agent are added, so that the performances of the composite colloidal particle in the aspects of oxidization resistance, antibacterial property and the like are further improved. Therefore, the composite colloidal particle has radiation resistance, certain ultraviolet resistance, oxidation resistance, antibacterial capacity and other capacities, and has certain application situations in the field of materials.

Drawings

FIG. 1 is a flow chart of a preparation process of the composite colloidal particle;

FIG. 2 is a graph of ionization shielding performance test at 50kV for X-ray energy;

FIG. 3 is a graph of ionization shielding performance test at 60kV for X-ray energy.

Detailed Description

In order to enable those skilled in the art to better understand the technical solutions of the present invention, the following description of the technical solutions of the embodiments of the present invention will be made clearly and completely, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to fall within the scope of the present invention.

Conventional chemicals and instrumentation used in the present invention are commercially available unless otherwise specified.

Example 1

The preparation method of the composite colloidal particle comprises the following steps:

s1: weighing 20 parts of butyl titanate, 40 parts of zinc nitrate, 35 parts of cerium sulfate and 3 parts of polyvinyl alcohol according to the weight parts, mixing, performing high-temperature sintering, jet milling and screening to obtain hollow spherical powder, adding 30 parts of nickel chloride hexahydrate according to the weight parts, 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: and (3) introducing hydrogen into the reaction container at a flow rate of 120ml/min, introducing argon at a flow rate of 180ml/min, reducing at a temperature of 900 ℃, and performing heat preservation reaction for 70min to finally obtain a metal nickel coating on the surface of the hollow spherical powder.

S2: uniformly mixing 10 parts by weight of BECQ powder prepared in the step S1, 90 parts by weight of polypropylene, 0.5 part by weight of IF, 0.8 part by weight of CHIMASSORB 2020BOX and 0.3 part by weight of IRGAGUARD B to obtain a mixture;

s3: mixing, extruding, wiredrawing and dividing the mixture with the mass fraction of 60% and the polymer with the mass fraction of 40% which are prepared in the step S2 into composite colloidal particles at 155 ℃, wherein the polymer is a mixture of polypropylene and polyamide.

Example 2

s1: weighing 28 parts of butyl titanate, 50 parts of zinc acetate, 28 parts of cerium nitrate and 5 parts of polyvinyl alcohol according to the weight parts, mixing, performing high-temperature sintering, jet milling and screening to obtain hollow spherical powder, adding 40 parts of nickel chloride hexahydrate according to the weight parts, 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: and (3) introducing hydrogen into the reaction container at a flow rate of 120ml/min, introducing argon at a flow rate of 180ml/min, reducing at 950 ℃ for 70min, and obtaining a metallic nickel coating on the surface of the hollow spherical powder after heat preservation reaction.

S2: uniformly mixing 20 parts by weight of BECQ powder prepared IN the step S1, polypropylene, polyamide, polytetrafluoroethylene 80 parts, IF168, IN3114, INB215 0.7 parts, CHIMASSORB 2020BOX 0.6 parts and IRGAGUARD B1000.4 parts to obtain a mixture;

s3: mixing, extruding, wiredrawing and cutting the mixture with the mass fraction of 60% and the polymer with the mass fraction of 40% which are prepared in the step S2 into composite colloidal particles at 155 ℃, wherein the polymer is a mixture of polypropylene, polyamide and polytetrafluoroethylene.

Example 3

s1: according to weight portions, 35 portions of butyl titanate, 55 portions of zinc acetate, 20 portions of cerium nitrate and 7 portions of polyvinyl alcohol are weighed according to the proportion, and are mixed, high-temperature sintering, jet milling and screening are carried out to obtain hollow spherical powder, then 50 portions of nickel chloride hexahydrate are added according to the proportion, and a chemical vapor deposition method is used for coating the hollow spherical powder, so that BECQ powder with a core-shell structure is prepared; the chemical vapor deposition method comprises the following specific processes: and (3) introducing hydrogen into the reaction container at a flow rate of 120ml/min, introducing argon at a flow rate of 180ml/min, reducing at a temperature of 1000 ℃, and performing heat preservation reaction for 70min to finally obtain a metal nickel coating on the surface of the hollow spherical powder.

S2: uniformly mixing 30 parts by weight of BECQ powder prepared in the step S1, 70 parts by weight of polytetrafluoroethylene, 0.9 part by weight of INB215, 0.3 part by weight of CHIMASSORB 2020BOX and 0.5 part by weight of IRGAGUARD B1000 to obtain a mixture;

s3: mixing, extruding, wiredrawing and cutting the mixture with the mass fraction of 60% and the polymer with the mass fraction of 40% which are prepared in the step S2 into composite colloidal particles at 155 ℃, wherein the polymer is a mixture of polypropylene and polytetrafluoroethylene.

Comparative example 1

The whole preparation method is the same as in example 2, except that no BECQ powder is added during the preparation of the composite colloidal particles.

s2: uniformly mixing 100 parts of polymer, 0.7 part of antioxidant, 0.6 part of ultraviolet absorber and 0.4 part of antibacterial agent in parts by weight to obtain a mixture;

Comparative example 2

The whole preparation method is the same as in example 2, except that the step of coating the hollow sphere powder using the chemical deposition method is absent in the preparation of the BECQ powder.

Comparative example 3

The radiation protective material was prepared by the method of example 5 in application publication No. CN111228142 a.

Example 4 ionizing radiation protection efficacy verification

The radiation protective composite colloidal particles obtained in example 2 were used for the measurement of X-ray shielding properties, specifically by a high frequency digital flat panel camera system definition 8000 (general electric medical systems Co., ltd.). The measurement conditions were: (1) The measurement has completed the screening performance of the powder material compared with a lead equivalent (Beijing Kelida medical equipment development Co., ltd.) of a radiation protective garment 0.35 mm thick; (2) Exposure times ranging from 40 to 140 kilovolts peak and about 10mAs at X-ray energy levels were measured.

Specific test results are shown in fig. 2 and 3, the radiological imaging test shows that the brighter the image is, the stronger the shielding effect is, if no shielding effect is provided, no image appears in the image, the lower part of the image is a square lead plate, and the closer the color is to the lead plate, the stronger the radiation shielding performance is shown; when the X-ray intensity is 50kV and 60kV, the compound colloidal particle can be observed to be white bright spots, the color of the compound colloidal particle is similar to that of a reference object of a lower reference lead plate, and the image test result shows that: 1) The composite colloidal particles have obvious shielding effect under the intensity of 50kV and 60 kV; 2) From the radiological image results, it was shown that under this intensity condition, the shielding performance of the composite colloidal particles was similar to that of a 1mm thick lead plate.

Example 5 radiation Performance test

The radiation performance test was performed by taking the radiation protection composite colloidal particles prepared in examples 1 to 3 and comparative examples 1 to 2, specifically, the test instrument was a thermoluminescent dosimeter (RGD-3B/S), the measurement range was 0.01. Mu. Gy-10Gy, the linear deviation was less than 1%, the light source stability was not more than 0.5% (continuous 10 hours), the maximum heating temperature was 400 ℃, the linear heating rate was 1 ℃/S-40 ℃/S, the specific test standard was according to GBZ-2002 and GBZ-207-2008, and the surface absorption was tested by using lead corresponding to the weight of each of the radiation protection materials as a test surface absorption for a standard sample, and the specific test results are shown in Table 1:

table 1 test results table

As can be seen from the data in table 1, the radiation resistant composite colloidal particles prepared in comparative example 1 had almost no radiation resistant property due to the absence of added BECQ powder, and had a surface absorption amount (mGy) of 0.15; the step of coating the hollow sphere powder by using a chemical deposition method is absent in comparative example 2, the radiation-resistant performance of the prepared radiation-resistant composite colloidal particles is lower than that of examples 1-3, the surface absorption capacity (mGy) of the particle is 93.03, and 76.54% of the corresponding surface absorption capacity (mGy) of a standard sample (lead) is achieved, and the result shows that the radiation-resistant performance of BECQ powder with a core-shell structure formed after the surface of the hollow sphere powder is coated with nickel by using the chemical deposition method is further enhanced; in comparative example 3, the radiation protection material is prepared by adopting the method of example 5 in application number publication No. CN111228142A, the radiation resistance of the prepared radiation resistant composite colloidal particles is lower than that of examples 1-3, the surface absorption capacity (mGy) of the radiation resistant composite colloidal particles is 105 and reaches 78.26% of the surface absorption capacity (mGy) of the corresponding reference sample (lead), and as the core component of the radiation resistant composite colloidal particles prepared in comparative example 3 is more than that of the radiation resistant composite colloidal particles prepared in the invention, the coating of the shell adopts polyvinyl alcohol, the core component is less, the coating of the shell adopts a chemical deposition method to coat a metal nickel coating, and the result shows that the radiation resistance of the prepared radiation resistant composite colloidal particles is obviously improved after the coating of the shell is carried out by the chemical deposition method of the invention; the radiation complex colloidal particle prepared in example 1 had a surface absorption (mGy) of 128.57, reaching a corresponding 88.45% of the surface absorption (mGy) of the standard sample (lead); the radiation complex colloidal particle prepared in example 2 had a surface absorption capacity (mGy) of 127.53, reaching 89.63% of the corresponding surface absorption capacity (mGy) of the standard sample (lead); the surface absorption capacity (mGy) of the radiation composite colloidal particle prepared in the embodiment 3 is 123.34, which reaches 87.12% of the corresponding surface absorption capacity (mGy) of the standard sample (lead), and the result shows that the composite colloidal particle has better radiation resistance and has a certain application prospect in the field of materials.

Example 6 application of radiation protective composite colloidal particles in preparation of melt blown nonwoven fabrics

Mixing and feeding the anti-radiation composite colloidal particles with the mass fraction of 75% and the polymer with the mass fraction of 25% prepared in the example 2, carrying out melt extrusion, forming fibers, cooling the fibers, forming a net, and reinforcing the net into cloth to prepare a melt-blown non-woven fabric; taking the non-radiation-resistant composite colloidal particles as blank control, and carrying out radiation performance test:

as a result, it was found that the prepared melt-blown nonwoven fabric hardly had the radiation resistance without adding the radiation-resistant composite colloidal particles; the surface absorption capacity (mGy) of the prepared melt-blown non-woven fabric is 95.65 by adding the radiation-proof composite colloidal particles, and the corresponding 67.22% of the surface absorption capacity (mGy) of the standard sample (lead) is achieved, so that the radiation-proof composite colloidal particles have good application prospects in the field of preparing the melt-blown non-woven fabric.

The above examples are provided for illustrating the technical scheme of the present invention and not for limiting the same, and the present invention has been described in detail with reference to the preferred embodiments, and it should be understood that those skilled in the art can make variations, modifications, additions or substitutions within the spirit and scope of the present invention without departing from the scope of the present invention as defined in the appended claims.

Claims

1. The preparation method of the radiation-proof composite colloidal particle is characterized by comprising the following steps of:

s1, BECQ powder preparation: weighing a titanium source ion precursor, a zinc source ion precursor, a rare earth cerium source ion precursor and a dispersing agent, mixing, performing high-temperature sintering, jet milling and screening to obtain hollow spherical powder, adding a nickel source ion precursor, and coating the hollow spherical powder by using a chemical vapor deposition method to prepare BECQ powder with a core-shell structure; wherein: 20-35 parts of titanium source ion precursor, 40-55 parts of zinc source ion precursor, 20-35 parts of rare earth cerium source ion precursor, 3-7 parts of dispersing agent and 30-50 parts of nickel source ion precursor;

2. The method for preparing the anti-radiation composite colloidal particle according to claim 1, wherein the titanium source ion precursor is butyl titanate, the zinc source ion precursor is one of zinc nitrate and zinc acetate, the rare earth cerium source ion precursor is one of cerium sulfate and cerium nitrate, the dispersing agent is polyvinyl alcohol, and the nickel source ion precursor is nickel chloride hexahydrate.

3. The preparation method of the radiation-proof composite colloidal particle as defined in claim 2, wherein in the step S1, the specific method for coating the hollow sphere powder by using a chemical vapor deposition method is as follows: firstly, dehydrating and drying the nickel chloride hexahydrate, adding the nickel chloride hexahydrate into a hollow spherical powder reaction container, then introducing hydrogen into the reaction container, heating to perform reduction reaction, introducing argon to serve as shielding gas, and finally obtaining a metal nickel coating shell on the surface of the hollow spherical powder after thermal insulation reaction.

4. The method for preparing the radiation-proof composite colloidal particle according to claim 3, wherein the flow rate of the hydrogen gas introduced into the reaction vessel is 120ml/min, the flow rate of the argon gas introduced into the reaction vessel is 180ml/min, the temperature of the reduction reaction is 900-1000 ℃, and after the heat preservation reaction is carried out for 70min, the metal nickel coating shell is finally obtained on the surface of the hollow spherical powder.

5. The method for preparing the radiation-proof composite colloidal particle according to claim 1, wherein the antioxidant is one or more of 168, 3114 and B215.

6. Use of the radiation protective composite colloidal particles produced by the method for producing a radiation protective composite colloidal particle according to any one of claims 1 to 5 for producing a melt-blown nonwoven fabric.