CN114921097A - Nontoxic radiation-proof organic silicon composite material and preparation method thereof - Google Patents
Nontoxic radiation-proof organic silicon composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of ray shielding materials, in particular to a non-toxic radiation-proof organic silicon composite material and a preparation method thereof. The non-toxic radiation-proof organic silicon composite material comprises a base material and radiation-proof filling particles dispersed on the base material; the base material is rubber; the radiation-proof filling particles are tungsten powder; the weight ratio of the matrix material to the radiation-proof filling particles is 1 (5-18); the radiation-proof filling particles comprise the following components in parts by weight: 70-80 parts of first particles, 10-15 parts of second particles, 5-10 parts of third particles and 0-5 parts of fourth particles, wherein the Fisher's particle size of each particle is (15-20) mu m, (5-10) mu m, (2-3) mu m and (0.1-1) mu m, and the tap density of each particle is more than 12.5g/cm 3 More than 10.5g/cm 3 Greater than 9.5g/cm 3 More than 7.5g/cm 3 . The non-toxic radiation-proof organic silicon composite material has the advantages of non-toxicity and environmental protection, has high radiation shielding performance and good mechanical performance.
Description
Technical Field
The invention relates to the technical field of ray shielding materials, in particular to a non-toxic radiation-proof organic silicon composite material and a preparation method thereof.
Background
With the increasing development of various basic researches and technologies around nuclear energy and ray application in the fields of nuclear power energy, medical detection, military wars, aerospace, civil security and the like, ray protection is increasingly important. Therefore, a nuclear ray shielding material capable of effectively reducing the damage of accidental radiation also becomes one of research hotspots with social value and economic value.
The traditional nuclear ray shielding material is mainly metal lead and a polymer composite material thereof, has good energy absorption characteristic, has good shielding effect on low-energy and high-energy X rays and gamma rays, and is low in cost and easy to process. However, lead has low melting point and biological toxicity, lead vapor is formed at high temperature, and lead-containing waste gas, waste water, waste residue and the like pollute the atmosphere, water sources and crops, thereby seriously endangering human health.
According to the european union "instructions on limiting the use of certain harmful components in electronic and electrical equipment (RoHS instructions)," instructions for scrapping electronic and electrical equipment (WEEE instructions), "registration, evaluation, authorization and restriction of chemicals" (REACH regulations), "lead is listed as one of the harmful substances of limited use and high concern. With the continuous strengthening of ecological civilization construction and environmental management measures in China, the state will continuously and forcibly close processing factories without lead subsequent processing capacity, so that lead-free shielding materials will have great requirements, and researches on the application of other materials to the field of ray shielding instead of lead are imperative.
Tungsten has an atomic number of 74 and a density of 19.35g/cm 3 The tungsten density is the density of lead (11.34 g/cm) 3 ) 170.6%, it is known to those skilled in the art that there is a close relationship between radiation protection and material density, with greater density giving better shielding performance. The shielding tungsten composite material is larger than the lead composite material under the same adding amount (namely loading amount), and the tungsten alloy has no harm to people or environment in long-term use. Tungsten has good ray shielding performance and does not generate secondary electron radiation, and is an ideal choice for being used as a nuclear radiation shielding material.
The nuclear ray shielding material is required to be manufactured into various shapes of products (such as a sleeve structure, a laminate structure, etc.) when applied at the back end, and the products of the nuclear ray shielding material are required to maintain certain flexibility for use.
However, tungsten is a high-melting-point refractory metal, and has poor toughness and plasticity in a sintering state and difficult forming processing, and meanwhile, tungsten powder also has the defects of rough surface, low apparent density and the like.
Specifically, the content of the tungsten powder affects the processing and finished product performance of the prepared nuclear ray shielding material, and the mechanical properties (such as fluidity and the like) of the nuclear ray shielding material in the preparation process are also affected by the content of the added tungsten powder; however, due to the characteristics of tungsten, if the addition ratio of tungsten powder is simply increased, the mechanical properties (stretch bending property, flexibility and other processability) of the prepared nuclear ray shielding material are insufficient, and the problems of poor processability, poor forming finished product and the like of the material can occur, so that the prepared nuclear ray shielding material is limited in application, and therefore, the loading amount of tungsten powder on the composite material substrate is small, and the prepared material has poor radiation resistance.
In conclusion, how to obtain a radiation shielding material filled with tungsten powder, which has the advantages of no toxicity, environmental protection, high radiation resistance, and good mechanical properties and processing formability is a problem to be solved in the field.
The Chinese patent application with the application number of CN200810147941.2 and the publication date of 2009, 05 and 13 discloses a flexible composite radiation shielding material, which is prepared by mixing a base material and a shielding substance according to a ratio, and then carrying out mixing, crushing, granulating and extruding processes. The base material is thermoplastic elastomer (TPE), and the content of the base material is 15-95% of the total weight; the shielding substance is boron compound, lead, tungsten and their compounds; the content of boron compound is 0-75% of the total weight; the content of lead, tungsten and their compounds is 0-85% of total weight. In the scheme of the Chinese patent application, metal lead is still adopted, and the prepared material cannot meet the requirements of no toxicity, environmental protection and the like.
Disclosure of Invention
To solve the problems mentioned in the background art: the metal lead and the polymer composite material thereof have the problem that the toxicity can cause harm to people and environment; the radiation shielding material prepared by adopting the tungsten powder as the filler has the problems of difficult combination of good mechanical property and high radiation resistance and serious influence on the application.
The invention provides a nontoxic radiation-proof organic silicon composite material, which comprises a base material and radiation-proof filling particles dispersed on the base material; the base material is rubber; the radiation-proof filling particles are tungsten powder; the weight ratio of the matrix material to the radiation-proof filling particles is 1 (5-18);
the radiation-proof filling particles comprise the following components in parts by weight: 70-80 parts of first particles, the Fisher size of the first particles is (15-20) mu m, and the tap density is more than 12.5g/cm 3 (ii) a 10-15 parts of second particles, the Fisher size of which is (5-10) mu m, and the tap density of which is more than 10.5g/cm 3 (ii) a 5-10 parts of third particles, the Fisher size of the third particles is (2-3) mu m, and the tap density is more than 9.5g/cm 3 (ii) a 0-5 parts of fourth particles, the Fisher size of the fourth particles is (0.1-1) mu m, and the tap density is more than 7.5g/cm 3 。
Firstly, tungsten powder is used as radiation-proof filling particles to replace the traditional lead powder, the density of the tungsten powder exceeds that of lead, and the tungsten powder is almost free of biotoxicity, does not pollute the environment, and has the advantages of no toxicity, environmental protection and the like;
secondly, there is a technical obstacle in the process of adding tungsten powder as radiation-proof filling particles:
on one hand, tungsten is a high-melting-point refractory metal and has the defects of poor toughness and plasticity in a sintering state, difficult forming and processing and the like, meanwhile, tungsten powder also has the defects of rough surface, low apparent density and the like, and in the traditional scheme of directly adding tungsten powder with single-specification granularity or general large-range tungsten powder filler components, the loading capacity of the tungsten powder on a composite material substrate is small, the compactness is poor, and the prepared material has poor radiation resistance.
Specifically, on one hand, the adding proportion of tungsten powder can be increased in order to obtain better radiation protection performance, but the content of tungsten powder also affects the processing and finished product performance of the prepared nuclear ray shielding material, and due to the characteristics of tungsten, if the adding proportion of tungsten powder is simply increased, the mechanical performance (tensile flexibility, flexibility and other processability) of the prepared nuclear ray shielding material is difficult to meet the requirements, and the processing and forming performance is poor (for example, the tungsten powder falls off, a material product is difficult to stably form and is easy to form slag and the like), so that the prepared nuclear ray shielding material is subjected to various limitations in application, and the loading amount of the tungsten powder in a base material is limited;
on the other hand, it is known in the art that the particle size of the tungsten powder filler affects the processing and finished product properties of the prepared composite material of the nuclear ray shielding material; the inventor finds out through exploration experiments that: in the traditional scheme of directly adding tungsten powder with single specification granularity or general large-range tungsten powder filler components, the influence of specification and size matching of the tungsten powder on the shielding performance is ignored; if the granularity of the tungsten powder filler is too small, the specific surface area is large, agglomeration is easy to generate, so that the tungsten powder is difficult to disperse, the processing performance is different, the dispersion is uneven, the loading capacity of the tungsten powder is small, and the radiation protection performance is poor and uneven; the tungsten powder has too large particle size, the mechanical properties (i.e. mechanical properties such as stretchability and flexibility) of the prepared material are poor, the product application is limited, and gaps exist among the large-particle tungsten powder, which leads to low compactness of the prepared material and poor radiation protection performance of the material.
The invention adopts tungsten powder with specific specification size and tap density to compound according to a certain proportion, and is assisted with specific rubber matrix material to prepare the nontoxic radiation-proof organic silicon composite material, which can effectively overcome the defects:
the tungsten powder adopted by the radiation-proof filling particles is not a single specification or a general large-range tungsten powder filler combination (for example, a multi-medium type stone tungsten powder combination and a free combination of tungsten powder in a large specification range are adopted), but several tungsten powders with specific specifications and sizes (the particle size and the tap density characteristics of the tungsten powders are specifically limited) are compounded according to a certain proportion, so that the radiation-proof filling particles which are well matched and high in density and are homogeneously compounded are obtained, the tungsten powder compounding formulas with different specifications and sizes can reach the optimal stacking degree under the condition of the same addition amount, gaps among the tungsten powders are small under the high stacking degree, and the optimal radiation-proof effect is realized.
The key technology for filling the tungsten powder is to adjust the specification sizes and the proportions of particles with different particle sizes in the tungsten powder, and subdivide the tungsten powder into the tungsten powder (namely, a first particle, a second particle, a third particle and a fourth particle) with a plurality of specific particle sizes and tap densities; in the nontoxic radiation-proof organic silicon composite material prepared by the invention, a matrix material (namely rubber) forms a network around the radiation-proof filling particles, and tungsten powder is dispersed and filled on the matrix material; the tungsten powder with specific particle size and specific tap density is matched with the tungsten powder with specific particle size and specific tap density, so that the tungsten powder with large and small particles can be optimally matched, and a required filling state is obtained through the synergistic effect of the tungsten powder with small tungsten powder addition, so that the prepared material has high radiation resistance;
in conclusion, the invention compounds several tungsten powders with specific specification sizes and tap densities according to a certain proportion, can customize radiation-proof filling particles with different densities, is assisted by a specific rubber matrix material, realizes the preparation of a material with high radiation-proof performance under the condition of less tungsten powder addition amount through the synergistic effect of the tungsten powder and the matrix material according to the specific proportion, and simultaneously the prepared nontoxic radiation-proof organosilicon composite material has good mechanical performance.
In addition, the function of limiting the tap density of the powder is to improve the mixing uniformity of the powder, a rubber matrix is filled with large particles at first, then small particles are added to fill gaps among the large particles, and after all the gaps of the large particles are gradually filled with the small particles, the added small particles can separate the large particles, so that the porosity of a system is improved; by limiting the tap density of the tungsten powder, the minimum system porosity can be achieved according to the existing proportion of the radiation-proof filling particles, so that a better radiation-proof effect is realized, and the mechanical property reduction degree of a matrix is reduced.
The non-toxic radiation-proof organic silicon composite material provided by the invention has the advantages of non-toxicity and environmental protection, and has high radiation-proof performance under the condition of less tungsten powder addition; meanwhile, the base material rubber can keep the elasticity and the ductility of the base material rubber and keep the flexibility of the base material, the non-toxic radiation-proof organic silicon composite material has good mechanical property, the application extension of a formed product of the material in various application places is facilitated (for example, the material is made into a flexible pipe sleeve which can be stretched and bent, a plate and other protective products), the processability is good, and the apparent property of a formed finished product is good.
It should be noted that "large particles" and "small particles" described herein do not refer to "first particles" and "fourth particles" simply, and the large particles and the small particles are relative concepts herein, and according to different particle sizes and sizes of gaps between the particles, the first particles, the second particles, the third particles, and the fourth particles are correspondingly filled between the gaps with different sizes, and the filling manner is diversified, so that the best collocation effect can be achieved by matching the tungsten powders with various specifications and sizes.
In one embodiment, the composition comprises the following components in parts by weight: 100 parts of base material, 500-1800 parts of anti-radiation filling particles, 0.5-1.5 parts of vulcanizing agent, 0-10 parts of filler, 0-5 parts of processing oil, 0.05-5 parts of processing aid and 2-10 parts of coupling agent.
In one embodiment, the rubber is silicone rubber.
In one embodiment, the rubber is one or more of methyl vinyl mixed silica gel and phenyl mixed silica gel.
In one embodiment, the hardness of the rubber is Shore A30-65.
In one embodiment, the filler is a boron compound; the filler is one or a combination of more of hexagonal boron nitride and cubic boron nitride.
In one embodiment, the vulcanizing agent is one or more of a bis 2,4 vulcanizing agent, a bis 2,5 vulcanizing agent, and a platinum vulcanizing agent.
In one embodiment, the processing oil is a dimethylhydroxysilicone oil; the processing aid is an internal release agent.
In one embodiment, the matrix material, the radiation-proof filler particles, the vulcanizing agent, the filler, the processing oil and the processing aid are lead-free.
The invention also provides a preparation method of the nontoxic radiation-proof organic silicon composite material, which comprises the following steps:
s10, mixing powder: weighing the first particles, the second particles, the third particles and the fourth particles according to a certain weight, and mixing to obtain uniformly mixed radiation-proof filling particles;
s20, mixing rubber: weighing the base material, the processing aid, the radiation-proof filling particles, the filler, the processing oil, the coupling agent and the vulcanizing agent according to a certain weight, and banburying in a banbury mixer to obtain a banburying product;
s30, vulcanization: and vulcanizing the banburying product prepared by the step S20, and cooling after vulcanization to prepare the non-toxic radiation-proof organic silicon composite material.
Based on the above, compared with the prior art, the non-toxic radiation-proof organic silicon composite material provided by the invention has the following beneficial effects:
the tungsten powder is adopted to replace the traditional lead powder, the density of the tungsten powder exceeds that of lead, the tungsten powder is almost free of biotoxicity, the environment cannot be polluted, and the tungsten powder has the advantages of no toxicity, environmental protection and the like;
according to the invention, tungsten powder with specific granularity and tap density is compounded according to a certain proportion to obtain a homogeneous compound filler with good matching and high density; by matching the compound tungsten powder with a rubber matrix material, the prepared material has high radiation shielding performance;
the invention has the advantages of no toxicity, environmental protection, high radiation shielding performance and good mechanical performance.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure and/or components particularly pointed out in the written description and claims hereof.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the embodiments of the present invention with reference to the technical solutions thereof, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments; the technical features designed in the different embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be noted that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and are not to be construed as limiting the present invention; it will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention provides a preparation method of a nontoxic radiation-proof organic silicon composite material, which comprises the following steps:
(1) mixing powder: weighing the first particles, the second particles, the third particles and the fourth particles according to a certain weight, and mixing to obtain uniformly mixed radiation-proof filling particles; preferably, the first particles, the second particles, the third particles and the fourth particles are mixed in a V-shaped powder mixer for 6-10 hours.
(2) Rubber mixing: weighing the base material, the processing aid, the radiation-proof filling particles, the filler, the processing oil, the coupling agent and the vulcanizing agent according to a certain weight, and banburying in a banbury mixer to obtain a banburying product;
preferably, the rubber mixing process comprises the following steps: after the temperature of the internal mixer is set to be 30-60 ℃, firstly adding rubber for banburying for 3-5 min, then adding a processing aid for continuously banburying for 5-10 min, continuously adding radiation-proof filling particles and a filler for banburying for 5-10 min (the middle of the filler is cleaned timely according to actual needs), then adding a coupling agent and processing oil for continuously banburying for 5-10 min until the mixture is uniform, then discharging the material and placing the material at normal temperature for more than 4 h; and finally, setting the temperature of an internal mixer to be 30-60 ℃, adding the uniformly mixed materials for internal mixing for 3-10 min, adding a vulcanizing agent for continuous internal mixing for about 5-10 min, discharging the uniformly mixed materials, and standing for more than 4 hours to obtain an internal mixing product
(3) And (3) vulcanization: and (3) vulcanizing the banburying product prepared in the step (2), and cooling after vulcanization to obtain the non-toxic radiation-proof organosilicon composite material. Preferably, the banburying product is placed in a mold for vulcanization, the primary vulcanization temperature is set to be 150-180 ℃, the primary vulcanization time is 10-30 min, the secondary vulcanization temperature is 180-210 ℃, and the vulcanization time is 2-16 h.
The invention provides a formula of a nontoxic radiation-proof organic silicon composite material, which comprises the following components: 100 parts of a base material, 500-1800 parts of anti-radiation filling particles, 0.5-1.5 parts of a vulcanizing agent, 0-10 parts of a filler, 0-5 parts of processing oil, 0.05-5 parts of a processing aid and 2-10 parts of a coupling agent;
wherein the base material is silicon rubber; the radiation-proof filling particles are tungsten powder, the radiation-proof filling particles comprise 70-80 parts of first particles, the Fisher particle size of the first particles is (15-20) mu m, and the tap density of the first particles is more than 12.5g/cm 3 (ii) a 10-15 parts of second particles, the Fisher size of which is (5-10) mu m, and the tap density of which is more than 10.5g/cm 3 (ii) a 5-10 parts of third particles, the Fisher size of the third particles is (2-3) mu m, and the tap density is more than 9.5g/cm 3 (ii) a 0-5 parts of fourth particles, the Fisher size of the fourth particles is (0.1-1) mu m, and the tap density is more than 7.5g/cm 3 . According to the nontoxic radiation-proof organic silicon composite material provided by the invention, the radiation-proof filling particles are dispersed in the matrix material, and the matrix material forms a network around the radiation-proof filling particles.
It should be noted that:
the radiation protective filler particles referred to herein are of a size that is the "size" of the particles rather than their "particle diameter" (as diameter implies a sphere). The sizes of the radiation-proof filling particles are in the level of microscopic particles, the sizes of the microscopic particles are not determined by a standard screening technology used for macroscopic abrasive particles any more, and instead, the particle size values of the radiation-proof filling particles are expressed by the 'Fisher' particle size; the term "Fisher size" as used herein refers to a known particle size expression and refers to a powder particle size value, and the basic method of testing is the steady flow air permeation method, i.e., the specific surface area and average particle size are measured at constant air flow rate and pressure. The fisher method is a relative measurement method which cannot accurately determine the true particle size of the powder and is only used to control the process and the quality of the product;
as used herein, "tap density" refers to the mass per unit volume of a powder in a container measured after tapping under specified conditions. Tap density or bulk density (known in some industries as apparent density) is defined as the mass of a sample divided by its volume, which includes the sample itself and the sample pores and their sample interstitial volumes. The method is a powder performance representation mode widely applied and accepted in the prior art, and is not described again here;
the "shore hardness" is a standard of hardness of materials, and is mainly divided into three types, namely type A, type C and type D, and the "shore hardness A" is type A; it can be known that the A-type Shore hardness test method is an existing widely applied and approved rubber hardness measurement means, and is not described here;
the expression "to" is used herein to indicate a range of values, and the expression of the range includes two endpoints.
The invention also provides the following examples and comparative examples:
the formulations (unit: parts by weight) of the examples and comparative examples provided by the present invention are shown in the following table 1:
TABLE 1
The types of raw materials of the components in the examples and the comparative examples in the table 1 are selected consistently, and the components are specifically as follows:
the base material is silicon rubber, specifically phenyl mixed silica gel JY-771/30U, and the hardness of the base material is Shore 30A; the vulcanizing agent is a bis 2,5 vulcanizing agent; the filler is boron nitride, specifically hexagonal boron nitride; the processing oil is dimethyl hydroxyl silicone oil; the processing aid is an internal release agent, specifically an internal release agent FC-606; the coupling agent is silane coupling agent Si-69;
the specific formulations of the first mixed tungsten powder, the second mixed tungsten powder, the third mixed tungsten powder and the fourth mixed tungsten powder in table 1 are as follows:
the first mixed tungsten powder comprises the following components in percentage by weight:
70% of first granules having a Fisher size of 15 μm and a tap density of 13.13g/cm 3 ；
15% of second granules having a Fisher size of 9 μm and a tap density of 11.46g/cm 3 ；
10% of the third particles of the second type,fisher particle size of 2 μm and tap density of 9.57g/cm 3 ；
5% of fourth granules having a Fisher size of 1 μm and a tap density of 7.95g/cm 3 ；
Second mixed tungsten powder:
80% of first particles, 18 μm Fisher-size, tap density 13.42g/cm 3 ；
10% of second granules having a Fisher size of 5 μm and a tap density of 10.57g/cm 3 ；
10% of third granules having a Fisher size of 2 μm and a tap density of 9.57g/cm 3 ；
Third mixed tungsten powder:
70% of first particles, 15 μm Fisher-Tropsch size, tap density 13.13g/cm 3 ；
15% of second granules having a Fisher size of 5 μm and a tap density of 10.57g/cm 3 ；
10% of third granules having a Fisher size of 3 μm and a tap density of 10.3g/cm 3 ；
5% of fourth granules with a Fisher size of 0.2 μm and a tap density of 7.57g/cm 3 ；
Fourth mixed tungsten powder:
80% of first particles, 18 μm Fisher-size, tap density 13.42g/cm 3 ；
10% of second granules having a Fisher size of 9 μm and a tap density of 11.46g/cm 3 ；
10% of third granules having a Fisher size of 3 μm and a tap density of 10.3g/cm 3 ；
According to the formula shown in the table 1, the nontoxic radiation-proof organosilicon composite material is prepared by the following preparation method according to the raw material components in the examples and the comparative examples, and the preparation steps are as follows:
(1) mixing powder: weighing the first particles, the second particles, the third particles and the fourth particles according to a certain weight, and mixing the first particles, the second particles, the third particles and the fourth particles in a V-shaped powder mixer for 8 hours.
(2) Rubber mixing: after the temperature of an internal mixer is set to be 30 ℃, firstly adding rubber for internal mixing for 5min, then adding a processing aid for continuous internal mixing for 5min, continuously adding radiation-proof filling particles and fillers for internal mixing for 10min (the middle is used for cleaning the fillers timely according to actual needs), then adding a coupling agent and processing oil for continuous internal mixing for 10min until the materials are uniformly mixed, then discharging the materials and placing the materials at normal temperature for more than 4 h;
finally, setting the temperature of an internal mixer to be 30 ℃, adding the uniformly mixed materials for internal mixing for 5min, adding a vulcanizing agent for continuous internal mixing for about 5min, discharging the uniformly mixed materials, and standing for more than 4 hours to obtain an internal mixing product
(3) And (3) vulcanization: vulcanizing the banburying product prepared in the step (2), wherein the vulcanizing process comprises the following steps: placing the banburying product in a mold for vulcanization, wherein the primary vulcanization temperature is set to be 170 ℃, the primary vulcanization time is 20min, the secondary vulcanization temperature is 200 ℃, and the vulcanization time is 4 h; and cooling after vulcanization to obtain the non-toxic radiation-proof organic silicon composite material.
The nontoxic radiation-proof organosilicon composite materials prepared in the examples and the comparative examples are tested for relevant indexes, and the test results are shown in the following table 2
TABLE 2
Wherein the test standard of the tensile strength is as follows: measuring the tensile stress strain performance of GB/T528-2009 vulcanized rubber or thermoplastic rubber; the density test standard is: measuring the density of GB/T533-2008 vulcanized rubber or thermoplastic rubber; lead equivalent test standard: YY0292.1-1997 part 1 of a medical diagnostic X-ray radiation protection device: and (4) measuring the attenuation performance of the material.
The test results of the comparative example show that:
the nontoxic radiation-proof organic silicon composite material prepared in the embodiment has high radiation shielding performance, good mechanical performance, good tensile performance, good flexibility, and favorable application expansion of a formed product in various application places, the processability of the material in the embodiment is good, the fusion of tungsten powder and a base material is good, a formed finished product (such as a sample plate sample strip in a radiation shielding test and a tensile test) has good performance, the surface of the finished product is smooth, and the phenomena of powder falling, slag crushing after stress and the like do not occur.
Compared with example 1, the tensile property of comparative example 1 is poor, the radiation shielding property is poor, and the density is low; in addition, the processability is poor, the fusion property of tungsten powder and a matrix material is poor, and the banburying is difficult; in addition, the surface of the tungsten powder is easy to fall off, and the loss of the tungsten powder easily causes the deterioration of the radiation shielding performance.
The radiation shielding performance of comparative example 2 is reduced compared to example 1; the tensile property of the composite material is poor, and the application of the prepared nontoxic radiation-proof organic silicon composite material at the back end is limited.
Compared with example 1, the radiation shielding performance of comparative example 3 is only reduced, but the tensile property is obviously poor, the surface of the finished product is relatively rough and not smooth, and the application of the prepared nontoxic radiation protection organic silicon composite material at the back end is limited.
In conclusion, the invention has the advantages of no toxicity, environmental protection, high radiation shielding performance, good mechanical performance, good processability and good performance of a formed finished product.
It should be noted that:
in addition to the practical choices presented in the above specific embodiments, the weight ratio of the matrix material to the radiation-proof filling particles can be in the range of 1 (5-18), including but not limited to the embodiments described above; wherein, by weight, the radiation-proof filling particles comprise: 70-80 parts of first particles, the Fisher size of the first particles is (15-20) mu m, and the tap density is more than 12.5g/cm 3 (ii) a 10-15 parts of second particles, the Fisher size of which is (5-10) mu m, and the tap density of which is more than 10.5g/cm 3 (ii) a 5-10 parts of third particles, the Fisher particle size of the third particles is (2-3) mu m, and the tap density is more than 9.5g/cm 3 (ii) a 0-5 parts of fourth particles, the Fisher size of the fourth particles is (0.1-1) mu m, and the tap density is more than 7.5g/cm 3 Including but not limited toIn the embodiments described above;
in addition to the practical choices presented in the above specific examples, the nontoxic radiation protection organosilicon composite material preferably comprises the following components in parts by weight: 100 parts of a base material, 500-1800 parts of radiation-proof filling particles, 0.5-1.5 parts of a vulcanizing agent, 0-10 parts of a filler, 0-5 parts of processing oil, 0.05-5 parts of a processing aid and 2-10 parts of a coupling agent; under the concept of the invention, the distribution ratio of each component can be adjusted adaptively within the preferable ratio range, including but not limited to the scheme of the above embodiment;
in addition to the actual choices embodied in the above specific embodiments, preferably, the rubber may be a silicone rubber, which is an existing material, specifically, one or a combination of more of methyl vinyl mixed silica gel and phenyl mixed silica gel may be selected, and the hardness of the silicone rubber may be within the range of shore a 30-65, including but not limited to the actual choices embodied in the above embodiments;
in addition to the practical choices embodied in the above specific embodiments, preferably, the filler may be selected from boron compounds, and particularly, one or more combinations of hexagonal boron nitride and cubic boron nitride may be preferred, including but not limited to the practical choices embodied in the above embodiments; besides the scheme of optimizing the boron compound, the filler can also be white carbon black, boron carbide and other fillers commonly used in the field, and the type of the filler can be adaptively selected under the concept of the invention;
in addition to the practical choices embodied in the above specific examples, preferably, the vulcanizing agent may be selected from one or more combinations of bis 2,4 vulcanizing agent, bis 2,5 vulcanizing agent, platinum vulcanizing agent, including but not limited to the practical choices embodied in the above examples;
in addition to the practical choices presented in the above specific embodiments, preferably, the processing oil is an existing material, and specifically, dimethylhydroxysilicone oil may be selected; the processing aid is an existing internal release agent, for example, an optional internal release agent FC-606 can be implemented, including but not limited to the actual choices embodied in the above embodiments; the processing oil and the processing aid are common raw materials in the field, and under the concept of the invention, the types of the processing oil and the processing aid can be adaptively selected;
in addition to the practical choices embodied in the above specific embodiments, preferably, the coupling agent is an existing material, and specifically, a silane coupling agent, such as an existing commercially available silane coupling agent KH-550, silane coupling agent KH-560, silane coupling agent KH-570, and silane coupling agent Si-69, may be selected, including but not limited to the practical choices embodied in the above embodiments;
in summary, the specific parameters or some common reagents or raw materials in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention. In addition, the raw materials used may be those commercially available or prepared by methods conventional in the art, unless otherwise specified.
In addition, it will be appreciated by those skilled in the art that, notwithstanding the many problems inherent in the prior art, each embodiment or solution of the present invention may be improved in one or more respects, without necessarily simultaneously solving all the technical problems inherent in the prior art or in the background art. It will be understood by those skilled in the art that nothing in a claim should be taken as a limitation on that claim.
Although terms such as vulcanising agents, fillers etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any one or more of the appended limitations; the terms "first," "second," and the like in the description and in the claims, if any, of the embodiments of the invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A nontoxic radiation-proof organic silicon composite material comprises a base material and radiation-proof filling particles dispersed on the base material; the method is characterized in that: the base material is rubber; the radiation-proof filling particles are tungsten powder;
the weight ratio of the matrix material to the radiation-proof filling particles is 1 (5-18);
the radiation-proof filling particles comprise the following components in parts by weight:
70-80 parts of first particles, the Fisher size of which is (15-20) mu m, and the tap density of which is more than 12.5g/cm 3 ；
10-15 parts of second particles, the Fisher size of which is (5-10) mu m, and the tap density of which is more than 10.5g/cm 3 ；
5-10 parts of third particles, the Fisher size of the third particles is (2-3) mu m, and the tap density is more than 9.5g/cm 3 ；
0-5 parts of fourth particles, the Fisher size of the fourth particles is (0.1-1) mu m, and the tap density is more than 7.5g/cm 3 。
2. The non-toxic radiation protective silicone composite material according to claim 1, characterized in that: the paint comprises the following components in parts by weight:
100 parts of a base material, 500-1800 parts of radiation-proof filling particles, 0.5-1.5 parts of a vulcanizing agent, 0-10 parts of a filler, 0-5 parts of processing oil, 0.05-5 parts of a processing aid and 2-10 parts of a coupling agent.
3. The non-toxic radiation protective organosilicon composite material according to claim 1, characterized in that: the rubber is silicon rubber.
4. The non-toxic radiation protective silicone composite material according to claim 3, characterized in that: the rubber is one or a combination of a plurality of methyl vinyl mixing silica gel and phenyl mixing silica gel.
5. The non-toxic radiation protective organosilicon composite material according to claim 4, characterized in that: the hardness of the rubber is Shore A30-65.
6. The non-toxic radiation protection organosilicon composite material according to claim 2, characterized in that: the filler is a boron compound;
the filler is one or a combination of more of hexagonal boron nitride and cubic boron nitride.
7. The non-toxic radiation protective silicone composite material according to claim 2, characterized in that: the vulcanizing agent is one or a combination of a double 2,4 vulcanizing agent, a double 2,5 vulcanizing agent and a platinum vulcanizing agent.
8. The non-toxic radiation protection organosilicon composite material according to claim 2, characterized in that: the processing oil is dimethyl hydroxyl silicone oil;
the processing aid is an internal release agent.
9. The non-toxic radiation protective silicone composite material according to claim 2, characterized in that: the base material, the radiation-proof filling particles, the vulcanizing agent, the filler, the processing oil and the processing aid do not contain lead element.
10. A method for preparing a nontoxic radiation protective silicone composite material according to any one of claims 1 to 9, characterized in that: the method comprises the following steps:
s10, mixing powder: weighing the first particles, the second particles, the third particles and the fourth particles according to a certain weight, and mixing to obtain uniformly mixed radiation-proof filling particles;
s20, mixing rubber: weighing the base material, the processing aid, the radiation-proof filling particles, the filler, the processing oil, the coupling agent and the vulcanizing agent according to a certain weight, and banburying in a banbury mixer to obtain a banburying product;
s30, vulcanization: and vulcanizing the banburying product prepared by the step S20, and cooling after vulcanization to prepare the non-toxic radiation-proof organic silicon composite material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115181428A (en) * | 2022-08-25 | 2022-10-14 | 中广核工程有限公司 | Organic silicon composite material and preparation method and application thereof |
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