JPH0525079B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a radiation dosimeter element for accurately and conveniently measuring the absorbed dose due to ionizing radiation such as gamma rays, X-rays, electron beams, heavily charged particle beams, and neutron beams. It is related to. [Background Art] In recent years, large-scale facilities that handle radioactive materials, such as nuclear power plants and radioactive waste treatment facilities, and various irradiation facilities such as particle beams and gamma rays have become popular. These facilities are required to accurately and easily measure radiation doses over a wide dose range, not only under normal conditions, but also under environments such as high temperature and high humidity. As a solid-state radiation dosimeter aimed at high-level dose measurement between conventional 10Gy and 100kGy,
Known dosimeters include thermoluminescence dosimeters, lyoluminescence dosimeters, polymethyl methacrylate dosimeters, radial chromic die film dosimeters, and cobalt glass dosimeters. In all of these methods, after irradiating a solid-state element with radiation, the amount of light emitted from the solid-state element and the absorption of light at a specific wavelength are measured to determine the irradiation dose. However, these dosimeters have the following drawbacks. (1) Even under the same irradiation and environmental conditions, the dose response (i.e., the amount of light emitted and the amount of light absorbed) varies greatly (excluding glass dosimeters). (2) Shows the so-called fading phenomenon in which the dose response after irradiation changes over time (excluding thermoluminescence dosimeters and radial chromic di-film dosimeters). 3. Effective dose measurement range is narrow. (4) For radiochromic di-film dosimeters and liyoluminescence dosimeters, the dose response varies greatly depending on the environment at the time of irradiation, such as temperature and humidity. When amino acids are irradiated with radiation in a crystalline state, they produce unique radicals (free radicals) that are stable in proportion to the absorbed dose. (CEA-R-3913, France 1970). However, the amino acid crystal powder itself is
Since it is soluble in water, it is affected by water and high humidity in water or air. Furthermore, since the powder is fine and easily charged with static electricity, it is difficult to accurately weigh it and fill it into a measuring tester, making it extremely inconvenient to handle. For these reasons, amino acid crystal powder as it is lacks value as a practical dosimeter, and research has been conducted to develop a dosimeter that takes advantage of the characteristics of amino acid crystal powder. Among the research results to date, paraffin or powdered cellulose is used as a medium, and after dispersing amino acid crystal powder in this, compression molding is performed to create a pellet-like product, which is used as a dosimeter element. A method is proposed. (Int.J.
AppI.Radiat.Isot, 33, 1101 (1982), Radiat.
Protection, EUR7448−EN Vo12489 (1982)). However, molded products made using media such as paraffin or cellulose are fragile, and even after molding, weak force or vibration can cause them to deform or chip, making accurate dose measurements impossible. Further, since only compression molding (paraffin, cellulose) or casting method (paraffin) can be used as a molding method, the molded bodies obtained are limited to pellet-like shapes or short cylinder or prismatic shapes. Moreover, it is almost impossible to mass-produce molded bodies using the above method. In addition to the above, the following drawbacks are also listed. Paraffin has a melting point of approximately 70°C at its highest, so it cannot be used at high temperatures, for example when measuring the dose of a sample in a metal container that is irradiated at a high dose rate, as paraffin will melt. When cellulose is used, the cellulose itself generates peroxide radicals when irradiated, so the radicals generated in the amino acid crystals and the ESR signal overlap, making it difficult to determine the accurate radical concentration of the amino acid crystals alone. This leads to inaccurate dosimetry and
The measurable dose range is narrower than that for amino acids alone. In addition, in the case of cellulose, it is difficult to obtain a uniform composition because it is a mixture of powders, and there are large variations among individual molded bodies. To overcome the above drawbacks, alanine dosimeter elements using polymers such as ethylene propylene rubber, low-density polyethylene, and polystyrene have been proposed (Kojima, 3 others; Proceedings of the 46th Applied Physics Conference). 1985, Autumn), Kojima, and 3 others; Radiation Process Symposium Abstracts P9 (1985, 11, 18)). Furthermore, Japanese Patent Application Laid-Open No. 61-57878 proposes an alanine dosimeter element using synthetic rubber and natural rubber as media. Methods using polymers and rubber as media have the advantage that various molding methods can be used, mass production is possible, and unlike paraffin, they can be used at temperatures above 70°C. Furthermore, since a uniform composition can be easily obtained, its practicality as a dosimeter element has been dramatically increased. [Problems to be Solved by the Invention] As a result of studying the mass production of dosimeter elements using polymer as a medium, the following problems became clear.
In other words, as mentioned above, dosimeter elements using amino acids measure the dose by determining the radical concentration using ESR.
It is read from the spectrum, but by using a polymer as a medium, the baseline of the ESR spectrum is tilted and the spectrum is distorted, which makes it impossible to measure with high precision, and there is a large variation in measurement between dosimeter elements. A problem arose. Also,
Manufacturing problems also arose, such as the rubber or resin amino acid composition sticking to the molding equipment and molding mold. The present invention has been made based on the above,
The purpose of this invention is to provide a rubber or resin molded dosimeter element that can eliminate the baseline slope of the ESR spectrum and the distortion of the amino acid spectrum, and that is uniform and easy to mass-produce. [Means for Solving the Problems] The molded dosimeter element of the present invention is characterized by being formed by molding a resin composition made of rubber such as synthetic rubber or natural rubber containing amino acid crystal powder and a lubricant. That is. In addition, the molded dosimeter element of the present invention is a synthetic material in which the amount of free radicals generated in the resin by irradiation with ionizing radiation is 1/10 or less of the amount of radicals generated in the amino acid crystal by the same irradiation. It is characterized in that it is formed by molding a resin composition made of a resin containing amino acid crystal powder and a lubricant. Furthermore, in the molded dosimeter element of the present invention, the radicals generated in the resin by irradiation with ionizing radiation are unstable and attenuate within a short time at room temperature, reducing the amount of radicals generated in the amino acid crystal by equivalent irradiation. /Ten
It is characterized in that it is formed by molding a resin composition made of the following synthetic resin containing amino acid crystal powder and a lubricant. The synthetic rubber used in the present invention is preferably one in which almost no radicals exist after irradiation at a temperature around room temperature or higher, such as ethylene propylene (-diene) copolymer, ethylene-vinyl acetate copolymer, chloroprene rubber, Nitrile rubber, butyl rubber, synthetic isoprene rubber, styrene-butadiene copolymer, styrene-butadiene-acrylonitrile copolymer, butadiene rubber, acrylic rubber, urethane rubber, silicone rubber, chlorosulfonated polyethylene, polyisobutylene,
Examples include polyester rubber, epichlorohydrin rubber, tetrafluoroethylene-propylene alternating copolymer, and the like. The synthetic resin used in the present invention has a small amount of radicals generated in the resin upon irradiation, or the radicals generated in the resin decay within a short time of about 1 to 3 hours at room temperature of 15 to 25 degrees Celsius. It is necessary that the amount be 1/10 or less of the amino acid crystal radical. Furthermore, in order to mix and mold amino acid crystals and resin, it is desirable that the softening point and melting point of the resin be lower than the melting point of the amino acid crystals (293°C). From this, resins that generate a small amount of radicals due to irradiation include polystyrene, acrylonitrile-styrene resin, hard acrylonitrile-butadiene-styrene resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polycarbonate resin, etc. Examples of resins that rapidly attenuate include low-density polyethylene (which also produces a small amount of radicals), polypropylene, polyester resin, and nylon 12. The blending ratio of these rubbers or synthetic resins and amino acid crystal powder is not particularly stipulated, but the upper limit is:
The lower limit is determined by whether or not it contains an effective amount of amino acids as a dosimeter element, depending on the moldability and whether it maintains practical mechanical properties when handling the molded body. Rubber or synthetic resin 100 Amino acid crystal powder 10-1000 parts by weight
Parts by weight are suitably selected, preferably from 100 to 600 parts by weight. The amino acid crystal powder used in the present invention includes glycine, valine, and leucine, which are monoamino monocarboxylic acids, serine, which is an oxyamino acid, cysteine, which is an amino acid containing sulfur,
Those with relatively low molecular weight and high crystallinity such as cystine, monoaminodicarboxylic acid lysine, arginine, and aromatic ring-containing amino acids phenylalanine and anthranilic acid are effective. The lubricant may be mixed with the rubber or resin in advance, or may be added at the time of mixing the rubber or resin with the amino acid crystal powder. In the present invention, by adding a lubricant, it is possible to eliminate the slope of the baseline of the ESR spectrum and the distortion of the amino acid spectrum, and the effect unique to resin molded dosimeter elements is that the mixture of amino acids and rubber or resin becomes uniform. It was discovered that it could be played. It is assumed that such effects are achieved because the addition of the lubricant relieves the mechanical stress on the amino acid powder during kneading and molding. The mixing ratio of rubber or resin and lubricant is not particularly specified, but the upper limit is determined by whether the accuracy of the dosimeter element can be maintained, and the lower limit is determined by whether the slope of the baseline of the ESR spectrum can be eliminated. , 0.1 to 20 lubricant per 100 parts by weight of resin
It is appropriate to select from a range of parts by weight. Examples of lubricants include paraffin wax such as paraffin wax, hydrocarbon resin such as polyethylene wax, stearic acid, hydroxystearic acid, complex stearic acid, hydrogenated oil, palmitic acid, margaric acid, nonadecylic acid, aragic acid, and oleic acid. Acids, fatty acids such as erucic acid, stearamide, oxy-stearoamide, oleyl amide, erucyl amide, ricinol amide, behen amide, methylol amide, methylene bis stearamide, methylene bis stearo behenamide, ethylene bis stearamide, etc. Fatty acid amide type, n-butyl stearate, methyl hydroxystearate, fatty acid ester type such as polyhydric alcohol fatty acid ester, saturated fatty acid ester, ketone wax,
Fatty acid ketones such as symmetrical aliphatic ketones derived from lauric acid, fatty alcohols such as higher alcohols and higher alcohol esters, partial esters of fatty acids and polyhydric alcohols such as glycerin fatty acid esters, hydroxystearic acid triglycerides, and sorbitan fatty acid esters. cadmium stearate, zinc stearate, calcium behenate, calcium stearate, cadmium laurate, cadmium ricinoleate, cadmium naphthenate, cadmium diethylhexoate, barium stearate, barium laurate, barium ricinoleate, barium naphthenate, Barium 2-ethylhexoate, calcium stearate, calcium laurate, calcium ricinoleate, strontium stearate,
Examples include metal soaps such as zinc laurate, zinc ricinoleate, zinc 2-ethylhexoate, lead stearate, tin stearate, magnesium stearate, dibasic lead stearate, lead naphthenate, and aluminum stearate. [Examples of the Invention] Examples 1 to 5, Comparative Example 1 Dose system elements were produced according to the formulations shown in each example in Table 1. In this case, polystyrene (Asahi Kasei Corporation)
While kneading 100 parts by weight of Styron 666, manufactured by Wako Pure Chemical Industries, Ltd., with a mixing roll at 150°C, 250 parts by weight of glycine crystal powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and a predetermined amount of lubricant were added and kneaded to form a uniform kneaded composition. did. In addition,
In Comparative Example 1, a similar kneading composition was prepared without adding a lubricant. Next, the kneaded composition was extruded into a string shape at 150°C using a Brabender extruder, and further press-molded at 170°C into small pieces with a diameter of 3.0 mmφ and a length of 3 cm using a mold to produce a dosimeter element. . The evaluation results of the kneading properties with a mixing roll, the extrudability with a Brabender extruder, and the adhesion with a mold when manufacturing the dosimeter elements of each example are shown in the first part.
Shown in the bottom column of the table. By adding a lubricant, the roll kneading properties and extrudability were improved compared to the comparative example. In addition, as a result of examining the ESR spectra of the prepared dosimeter elements, in Examples 1 to 5, the curve A in Fig. 1 was
As shown in , the baseline was flat with almost no slope. On the other hand, in Comparative Example 1, the slope was extremely large as shown by curve B in FIG. When the peak-to-peak height in Comparative Example 1 is defined as H', the relative values of the peak-to-peak height in each Example were determined and were as shown in the lower column of Table 1. ESR measurement is at modulation frequency 100KHz, Mod.2G, Power
It was performed at 4 mW and room temperature. Next, the ESR spectrum after the dosimeter element of Example 4 was irradiated with 5×10 ² Gy of ⁶⁰ Co-γ rays at room temperature is as shown by the solid line in FIG. For comparison, the ESR spectrum of only the amino acid powder is shown in FIG. 2 by a chain line. Peak height h of the curve in Figure 2
is a value corresponding to the concentration of radicals generated by absorption of radiation, and the amount of radicals generated in materials other than amino acids (ethylene ethyl acrylate copolymer, lubricant) is extremely small. Also, the height per unit weight of the ESR peak of the dosimeter element of Example 4 (proportional to the concentration of generated radicals)
Figure 3 shows the relationship between the absorbed dose and the absorbed dose. The logarithm of the absorbed dose and the logarithm of the ESR peak height show a nearly linear relationship, indicating that it can be used as a dosimeter element. It has been confirmed that the dosimeter elements of other Examples have similar characteristics to those of Example 4. Examples 6 to 9, Comparative Example 2 Dosimeter elements were produced according to the formulations shown in each example in Table 2. In this case, Examples 1 to 5 except that low density polyethylene (UBEZ-265, manufactured by Ube Industries, Ltd.) was used and the kneading temperature on the mixing roll was 130°C.
A uniform kneaded composition was prepared in the same manner as in the above. In Comparative Example 2, a similar kneading composition was prepared without adding a lubricant. Next, the kneaded composition was molded in the same manner as in Examples 1 to 5 to produce a dosimeter element, and the evaluation results and peak The relative value of the peak-to-peak height (based on the peak-to-peak height of Comparative Example 2) is
Shown in the bottom column of the table. Examples 10 to 12, Comparative Example 3 Dosimeter elements were produced according to the formulations shown in each example in Table 3. In this case, 100 parts by weight of ethylene propylene rubber (manufactured by Japan Synthetic Rubber Co., Ltd., EP02P) was heated to 90°C.
While kneading with a mixing roll, predetermined amounts of aspartic acid crystal powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade) and a lubricant were added and kneaded to obtain a uniform kneaded composition. In Comparative Example 3, a similar kneading composition was prepared without adding a lubricant. Next, the kneaded composition was molded in the same manner as in Examples 1 to 5 to produce a dosimeter element, and the evaluation results of kneading properties with a mixing roll, tackiness with a mold, and the relative peak-to-peak height were obtained. The values (based on the peak-to-peak height of Comparative Example 3) are shown in the lower column of Table 3.

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[Table] [Effects of the invention] As explained above, according to the present invention, ESR
The slope of the baseline of the spectrum can be eliminated, and the roll kneading properties are improved, so rubber or resin and amino acids are mixed uniformly, and a uniform element can be manufactured, which improves measurement accuracy. become able to. In addition, since extrudability is improved and adhesion in the mold is prevented, manufacturing efficiency can be improved and mass production becomes possible.

[Brief explanation of the drawing]

Figure 1 is an explanatory diagram of the difference in the baseline of the ESR spectra of the example and comparative example. Figure 2 is an explanatory diagram of the ESR spectrum after radiation irradiation.
The figure is an explanatory diagram of the relationship between the peak height per unit weight of the ESR spectrum of a dosimeter element and the absorbed dose.

Claims (1)

[Scope of Claims] 1. A rubber molded dosimeter element, characterized in that it is formed by molding a resin composition made of rubber containing amino acid crystal powder and a lubricant. 2. Amino acid crystal powder and a lubricant are contained in a synthetic resin in which the amount of free radicals generated in the resin by irradiation with ionizing radiation is 1/10 or less of the amount of radicals generated in amino acid crystals by the same irradiation. A resin molded dosimeter element, characterized in that it is formed by molding a resin composition. 3. Amino acids are added to synthetic resins in which the radicals generated in the resin by irradiation with ionizing radiation are unstable and decay within a short time at room temperature, resulting in less than 1/10 of the amount of radicals generated in amino acid crystals by equivalent irradiation. A resin molded dosimeter element, characterized in that it is formed by molding a resin composition containing crystal powder and a lubricant.