Polymer film material for quantitative detection of electron beam dose and preparation method thereof

Abstract

The invention discloses a polymer film material for electron beam dose quantitative detection and a preparation method thereof, the polymer film material comprises a functional molecule and a film matrix material, the functional molecule is selected from one of 2, 2 '-dipyridyl, 4, 4'-bipiperidine and 4, 4 '-dipyridyl, and the film matrix material is cellulose triacetate. The functional molecule polymer film material is used as a dosimeter for quantitatively detecting the dose of electron beam irradiation, the measurement principle is that the absorbance of the functional molecule polymer film material is increased along with the increase of the dose of electron beam irradiation, and the absorbance can be measured by using an ultraviolet-visible spectrophotometer; and then the electron beam irradiation dose is calculated according to the absorbance. Compared with a conventional commercial radiation film dosimeter, the functional molecule polymer film material prepared by the invention has the advantages of simple synthesis method, low cost and the like, the linear dose detection range of the functional molecule polymer film material is as wide as 0.1-120 KGy, and the functional molecule polymer film material is an electron beam dose quantitative detection material with excellent performance.

Description

Technical Field

[0001] The invention relates to the technical field of radiation dose detection, in particular to a polymer film material for quantitative electron beam dose detection and a preparation method thereof. Background Art

[0002] Ionizing radiation has a wide range of applications in medical diagnosis and treatment, material testing, industrial flaw detection, scientific research, and the nuclear industry. Accurate detection of radiation doses is an important prerequisite for the safe use of ionizing radiation. Current radiation detection methods can be divided into direct detection and indirect detection. Direct detectors mainly include gas ionization chambers, scintillator detectors, and semiconductor detectors. The principle is to use the release of photons and electrical effects when electron-hole pairs induced by radiation recombine, which can quickly and in real time detect the radiation received. Indirect detectors include liquid dosimeters and solid dosimeters. Among them, solid dosimeters are dosimeters that quantify the amount of radiation by using the proportionality between the radiation dose and its aftereffects in the material. Compared with real-time radiation detection equipment such as direct detectors, solid dosimeters have the characteristics of small size, portability, continuous monitoring, separation of test and reading signals, and a wide dose measurement range. They are more applicable in the detection of radiation doses, especially personal doses and environmental doses.

[0003] At present, solid radiation dosimeters mainly achieve the purpose of radiation detection by detecting the changes in the luminescence properties of materials after irradiation, including thermoluminescence, photoluminescence, and radiation photoluminescence. Among them, thermoluminescence dosimeters and photoluminescence dosimeters use thermal excitation or light excitation to induce fluorescence by the recombination of electron-hole pairs generated by radiation. They are one-time readings and have the disadvantage of poor stability. Although radiation photoluminescence dosimeters have the ability to read and count multiple times, their radiation blocking ability, low-dose detection sensitivity, detection threshold and other performance are generally not ideal. In addition, when reading the irradiation dose through luminescence testing technology, there is a problem of dose accumulation signal loss during the signal conversion process.

[0004] Compared with the detection method of reading the radiation dose through luminescence testing technology, quantitative detection of radiation dose by testing the change in absorbance of the material after irradiation reduces the loss of the dose accumulation signal of the material during the signal conversion process. The material stores the radiation dose information for a longer time, the material performance is more stable, the test cost is lower, and the operation is simpler. It is an ideal method for quantitative detection of radiation dose. Summary of the invention

[0005] The purpose of the present invention is to provide a polymer film material for quantitative detection of electron beam dose and a preparation method thereof, so as to solve the problem that when the luminescence test technology is used to read the irradiation dose, there is a loss of dose accumulation signal during the signal conversion process. The present invention performs quantitative detection of irradiation dose by testing the change in absorbance of the material after irradiation, which reduces the loss of dose accumulation signal of the material during the signal conversion process, the material stores radiation dose information for a longer time, the performance of the material is more stable, the test cost is lower, and the operation is simpler.

[0006] To achieve the above objectives, the first aspect of the present invention provides a polymer film material for quantitative detection of electron beam dose, the polymer film material comprising a functional molecule and a film matrix material, wherein the functional molecule is selected from one of 2,2'-bipyridine, 4,4'-bipiperidine and 4,4'-bipyridine, and the film matrix material is cellulose triacetate.

[0007] A second aspect of the present invention provides a method for preparing a polymer film material for quantitative detection of electron beam dose, comprising the following steps: (1) Mix dichloromethane and anhydrous ethanol to obtain solution I; (2) Add the functional molecule to solution I and perform sonication until the functional molecule is completely dissolved to obtain solution II; (3) Add cellulose triacetate to solution II and allow to dissolve at room temperature to obtain casting solution III; (4) Pour the casting solution III onto a glass plate and apply it by scraping. After standing and curing at room temperature, a polymer film material is obtained.

[0008] Preferably, the mass ratio of the functional molecule, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:35-45:70-80:450-500.

[0009] Preferably, the mass ratio of the functional molecule, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:40:75:460.

[0010] Preferably, in step (2), the ultrasonic dissolution time is 5 to 10 minutes.

[0011] Preferably, in step (3), the dissolution time at room temperature is 6 to 8 hours.

[0012] Preferably, in step (4), the coating thickness is 50-150 μm.

[0013] Preferably, in step (4), the coating speed is 40-50 cm / min.

[0014] Preferably, in step (4), the curing time at room temperature is 15 to 30 minutes.

[0015] Therefore, the present invention adopts the above-mentioned polymer film material for quantitative detection of electron beam dose and the preparation method thereof, which has the following beneficial effects: (1) The present invention uses 2,2'-bipyridine, 4,4'-bipiperidine and 4,4'-bipyridine as functional molecules and cellulose triacetate as the film matrix material, which has low cost, mild preparation conditions, simple preparation process, and high yield of functional molecule polymer film materials, which is conducive to commercialization.

[0016] (2) The linear dose detection range of the functional molecular polymer film material prepared by the present invention is as wide as 0.1~120KGy, which basically meets the general radiation dose detection needs and has a wide range of applications.

[0017] (3) The absorbance of the functional molecular polymer film material prepared by the present invention increases with the increase of the electron beam irradiation dose. The electron beam irradiation dose is calculated based on the absorbance of the functional molecular polymer film material. The functional molecular polymer film material of the present invention is used to detect the radiation dose. The operation is simple and the detection time is short. The detection personnel do not need to perform detection at the radiation source, which effectively avoids the harm of high-dose radiation to the detection personnel.

[0018] (4) The sensitivity of the functional molecular polymer film material of the present invention to electron beam irradiation dose detection can be adjusted by changing the mass of the added functional molecules, and in the wide range of the added functional molecule mass of 50~200 mg, the linear relationship of the functional molecular polymer film material in the detection range is maintained well.

[0019] (5) The functional molecular polymer film material prepared by the present invention has good stability.

[0020] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 A physical picture of the functional molecular polymer film material prepared by the present invention; Figure 2 The UV-visible absorption spectra of Example 1 of the functional molecular polymer film material prepared by the present invention after irradiation with different β-ray irradiation doses; Figure 3 The UV-visible absorption spectra of Example 2 of the functional molecular polymer film material prepared by the present invention after irradiation with different β-ray irradiation doses; Figure 4 The UV-visible absorption spectra of Example 3 of the functional molecular polymer film material prepared by the present invention after irradiation with different β-ray irradiation doses; Figure 5The relationship between the absorbance at 310 nm and the radiation dose of Examples 1-3 of the functional molecular polymer film material prepared by the present invention; Figure 6 The relationship between the absorbance at 310 nm and the radiation dose of Example 3-5 of the functional molecular polymer film material prepared by the present invention; Figure 7 This is a graph showing the relationship between the absorbance at 310 nm and the radiation dose of the functional molecular polymer film materials Example 3 and Example 5 prepared in the present invention after being placed in air for 130 days. DETAILED DESCRIPTION

[0022] The present invention will be further described below. It should be noted that this embodiment is based on the technical solution and provides a detailed implementation method and a specific operation process, but the present invention is not limited to this embodiment.

[0023] Example 1 This embodiment provides a method for preparing a functional molecular polymer film material for quantitative detection of electron beam dose, comprising the following steps: 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution were mixed evenly to obtain solution I. 50 mg of 2,2'-bipyridine was added to solution I and ultrasonicated for 5 min to completely dissolve it to obtain solution II. 3.75 g of cellulose triacetate was added to solution II and allowed to stand at room temperature for 6 h to dissolve to obtain casting solution III. Casting solution III was slowly poured onto a clean glass plate of an automatic scraper for scraping. The thickness of the scraped film was 50 µm and the scraping speed was 45 cm / min. After coating, the film was allowed to stand at room temperature for 20 min to solidify to obtain the functional molecular polymer film material.

[0024] Example 2 The difference between this embodiment and embodiment 1 is that the types of functional molecules are different. The functional molecule used in this embodiment is 4,4'-bipiperidine.

[0025] This embodiment provides a method for preparing a functional molecular polymer film material for quantitative detection of electron beam dose, comprising the following steps: 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution were mixed evenly to obtain solution I. 50 mg of 4,4'-bipiperidine was added to solution I and ultrasonicated for 5 min to completely dissolve it to obtain solution II. 3.75 g of cellulose triacetate was added to solution II and allowed to stand at room temperature for 6 h to dissolve to obtain casting solution III. Casting solution III was slowly poured onto a clean glass plate of an automatic scraper for scraping. The thickness of the scraped film was 50 µm and the scraping speed was 45 cm / min. After coating, the film was allowed to stand at room temperature for 20 min to solidify to obtain the functional molecular polymer film material.

[0026] Example 3 The difference between this embodiment and embodiment 1 is that the types of functional molecules are different. The functional molecule used in this embodiment is 4,4'-bipyridine.

[0027] This embodiment provides a method for preparing a functional molecular polymer film material for quantitative detection of electron beam dose, comprising the following steps: 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution were mixed evenly to obtain solution I. 50 mg of 4,4'-bipyridine was added to solution I and ultrasonicated for 5 min to completely dissolve it to obtain solution II. 3.75 g of cellulose triacetate was added to solution II and allowed to stand at room temperature for 6 h to dissolve to obtain casting solution III. Casting solution III was slowly poured onto a clean glass plate of an automatic scraper for scraping. The thickness of the scraped film was 50 µm and the scraping speed was 45 cm / min. After coating, the film was allowed to stand at room temperature for 20 min to solidify to obtain the functional molecular polymer film material.

[0028] Example 4 The difference between this embodiment and embodiment 3 is that the amount of the functional molecule added is different. The amount of the functional molecule added in this embodiment is 150 mg.

[0029] This embodiment provides a method for preparing a functional molecular polymer film material for quantitative detection of electron beam dose, comprising the following steps: 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution were mixed evenly to obtain solution I. 150 mg of 4,4'-bipyridine was added to solution I and ultrasonicated for 5 min to completely dissolve it to obtain solution II. 3.75 g of cellulose triacetate was added to solution II and allowed to stand at room temperature for 6 h to dissolve to obtain casting solution III. Casting solution III was slowly poured onto a clean glass plate of an automatic scraper for scraping. The thickness of the scraped film was 50 µm and the scraping speed was 45 cm / min. After coating, the film was allowed to stand at room temperature for 20 min to solidify to obtain the functional molecular polymer film material.

[0030] Example 5 The difference between this embodiment and embodiment 3 is that the added amount of the functional molecule is different. The added amount of the functional molecule in this embodiment is 200 mg.

[0031] This embodiment provides a method for preparing a functional molecular polymer film material for quantitative detection of electron beam dose, comprising the following steps: 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution were mixed evenly to obtain solution I. 200 mg of 4,4'-bipyridine was added to solution I and ultrasonicated for 5 min to completely dissolve it to obtain solution II. 3.75 g of cellulose triacetate was added to solution II and allowed to stand at room temperature for 6 h to dissolve to obtain casting solution III. Casting solution III was slowly poured onto a clean glass plate of an automatic scraper for scraping. The thickness of the scraped film was 50 µm and the scraping speed was 45 cm / min. After coating, the film was allowed to stand at room temperature for 20 min to solidify to obtain the functional molecular polymer film material.

[0032] Test example (1) Figure 1 This is a physical picture of the functional molecular polymer film material prepared in Example 3. Figure 1 It can be seen that the functional molecular polymer film material of the present invention is colorless and transparent, has uniform thickness, can be cut arbitrarily, has good flexibility, and is suitable for a variety of practical application scenarios.

[0033] (2) Figure 2-4 The UV-visible absorption spectra of the functional molecular polymer film materials prepared in Examples 1-3 after irradiation at different irradiation doses. It can be seen from the figure that as the irradiation dose increases, the absorbance of the material also increases accordingly within the test range of 300-320 nm, so it can be explained that the functional molecular polymer film material of the present invention responds to irradiation, and the irradiation dose it receives is proportional to its absorbance. The relevant experiments of the present invention are carried out on an irradiation accelerator system carrying a ring-shaped transmission chain. The sample enters the irradiation accelerator system through the ring-shaped transmission chain to receive irradiation. The beam energy of the electron accelerator is 10MeV, the beam power is 20kW, and the irradiation intensity is 64800kGy / h. The irradiation dose is adjusted by changing the irradiation time. After the sample leaves the accelerator system after irradiation, the UV-visible spectrum test is immediately performed.

[0034] (3) Figure 5 The relationship between the absorbance at 310 nm and the radiation dose of the functional molecular polymer film material prepared in Examples 1-3 is shown in FIG. Figure 2-4 The relationship between the absorbance of the material at 310 nm and the irradiation dose under different irradiation doses was obtained by fitting. The linear relationship between the absorbance of the functional molecular polymer film material prepared in Examples 1-3 and the irradiation dose was y=0.00405x+0.14725, y=0.00037x+0.0757 and y=0.00138x+0.0981, respectively, and R 2The absorbance of the functional molecular polymer film material is 0.97959, 0.97603 and 0.99911 respectively, which shows that there is an obvious linear relationship between the absorbance of the functional molecular polymer film material and the irradiated dose in Examples 1 to 3. Therefore, the irradiation dose can be estimated by measuring the absorbance of the functional molecular polymer film material, achieving the purpose of the present invention, that is, by detecting the change in the absorbance of the material after irradiation, the quantitative determination of the irradiation dose is achieved.

[0035] Among them, the polymer film material with the functional molecule of 4,4'-bipyridine added (Example 3) has a moderate ability to respond to irradiation and the best linear relationship. In subsequent experiments, the 4,4'-bipyridine functional molecule was selected as a representative for further research and explanation.

[0036] (4) Figure 6 The relationship between the absorbance at 310 nm and the radiation dose of the functional molecular polymer film material prepared in Example 3-5 is shown in FIG. Figure 6 It can be seen from Table 1 that there is an obvious linear relationship between the absorbance at 310 nm of the functional molecular polymer film materials prepared in Examples 3-5 and the irradiated dose, and as more functional molecules are added, the slope of the fitting curve of the absorbance at 310 nm and the radiation dose of the functional molecular polymer film materials prepared in Examples 3-5 becomes larger. Therefore, it is proved that the sensitivity of the functional molecular polymer film material of the present invention to the detection of electron beam irradiation dose can be adjusted by changing the mass of the added functional molecules, and in the wide range of the added functional molecular mass of 50 to 200 mg, the linear relationship of the functional molecular polymer film material in the detection range is maintained well.

[0037]

[0038] (5) Figure 7 The relationship between the absorbance at 310 nm and the radiation dose after the functional molecular polymer film materials prepared in Example 3 and Example 5 were placed in air for 130 days. Figure 7 It can be seen from Table 2 that after the functional molecular polymer film materials prepared in Example 3 and Example 5 were placed in the air for 130 days, the absorbance and radiation dose still maintained a good linear relationship, proving that the functional molecular polymer film materials prepared in the present invention have good stability.

[0039]

[0040] Therefore, the present invention adopts the above-mentioned polymer film material for quantitative detection of electron beam dose and its preparation method. The prepared functional molecular polymer film material has the advantages of simple synthesis method and low cost compared with the currently commercial radiation film dosimeter. Its linear dose detection range is as wide as 0.1~120 KGy, and it is an electron beam dose quantitative detection material with excellent performance.

[0041] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A polymer film material for quantitative detection of electron beam dose, characterized in that: The polymer film material comprises a functional molecule and a film matrix material, wherein the functional molecule is selected from one of 2,2'-bipyridine, 4,4'-bipiperidine and 4,4'-bipyridine, and the film matrix material is cellulose triacetate.

2. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 1, characterized in that: The following steps are involved: (1) Mix dichloromethane and anhydrous ethanol to obtain solution I; (2) Add the functional molecule to solution I and perform sonication until the functional molecule is completely dissolved to obtain solution II; (3) Add cellulose triacetate to solution II and allow to dissolve at room temperature to obtain casting solution III; (4) Pour the casting solution III onto a glass plate and apply it by scraping. After standing and curing at room temperature, a polymer film material is obtained.

3. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 2, characterized in that: The mass ratio of the functional molecule, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:10~40:15~80:100~500.

4. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 3, characterized in that: The mass ratio of functional molecules, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:40:75:

460.

5. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 2, characterized in that: In step (2), the ultrasonic dissolution time is 5 to 10 minutes.

6. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 2, characterized in that: In step (3), the dissolution time at room temperature is 6 to 8 hours.

7. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 2, characterized in that: In step (4), the coating thickness is 50-150 μm.

8. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 2, characterized in that: In step (4), the scraping speed is 40-50 cm / min.

9. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 2, characterized in that: In step (4), the curing time at room temperature is 15 to 30 minutes.

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