Polymer film material for electron beam dose quantification and method of making the same

Abstract

The application discloses a polymer film material for electron beam dose quantitative detection and a preparation method thereof, and the polymer film material comprises a functional molecule and a film base material, wherein the functional molecule is selected from one of 2,2'-dipyridyl, 4,4'-dipiperidyl and 4,4'-dipyridyl, and the film base material is triacetate cellulose. The functional molecule polymer film material of the application is used as a dosimeter for quantitatively detecting the dose of electron beam irradiation, and the measurement principle is that the absorbance of the functional molecule polymer film material increases with the increase of the electron beam irradiation dose, the absorbance can be measured by using an ultraviolet-visible spectrophotometer, and then the electron beam irradiation dose is calculated according to the absorbance. The functional molecule polymer film material prepared by the application has the advantages of simple synthesis method and low cost compared with the currently commercially available radiation film dosimeter, and the linear dose detection range is wide and reaches 0.1-120 KGy, so the functional molecule polymer film material is a kind of electron beam dose quantitative detection material with excellent performance.

Description

Technical Field

[0001] The present 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 dose 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. Their principle is to use the release of photons and electrical effects when electron-hole pairs induced by radiation recombine to detect the radiation received quickly and in real time. Indirect detectors include liquid dosimeters and solid dosimeters. Among them, solid dosimeters are dosimeters that quantify the radiation dose by using the direct ratio between the radiation dose and its after-effects produced 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 read signals, and a wide dose measurement range. They are more applicable in the detection of radiation dose, especially personal dose and environmental dose.

[0003] At present, solid-state radiation dosimeters mainly achieve the purpose of radiation detection by detecting 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 cause the electron-hole pairs generated by radiation to recombine and induce fluorescence. 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 unsatisfactory. 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 present invention aims to provide a polymer film material for quantitative electron beam dose detection and a method for preparing the same, addressing the aforementioned issue of dose accumulation signal loss during signal conversion when using luminescence testing technology to read irradiation dose. The present invention quantitatively detects irradiation dose by measuring changes in the absorbance of the material after irradiation, reducing the loss of dose accumulation signal during signal conversion. The material stores radiation dose information for a longer period of time, resulting in more stable performance, lower testing costs, and simpler operation.

[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:

[0008] (1) Mix dichloromethane and anhydrous ethanol to obtain solution I;

[0009] (2) Add the functional molecule to solution I and sonicate until the functional molecule is completely dissolved to obtain solution II;

[0010] (3) Add cellulose triacetate to solution II and allow to dissolve at room temperature to obtain casting solution III;

[0011] (4) Pour the casting solution III onto a glass plate and apply it by scraping. After standing and solidifying at room temperature, a polymer film material is obtained.

[0012] Preferably, the mass ratio of the functional molecule, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:35-45:70-80:450-500.

[0013] Preferably, the mass ratio of the functional molecule, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:40:75:460.

[0014] Preferably, in step (2), the ultrasonic dissolution time is 5 to 10 minutes.

[0015] Preferably, in step (3), the dissolution time at room temperature is 6 to 8 hours.

[0016] Preferably, in step (4), the coating thickness is 50-150 μm.

[0017] Preferably, in step (4), the scraping speed is 40-50 cm / min.

[0018] Preferably, in step (4), the curing time at room temperature is 15 to 30 minutes.

[0019] Therefore, the present invention uses the above-mentioned polymer film material for quantitative detection of electron beam dose and its preparation method, which has the following beneficial effects:

[0020] (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 output of functional molecule polymer film materials, which is conducive to commercialization.

[0021] (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.

[0022] (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 irradiation source, which effectively avoids the harm of high-dose irradiation to the detection personnel.

[0023] (4) The sensitivity of the functional molecular polymer film material of the present invention to electron beam irradiation dose detection can be controlled by changing the mass of the added functional molecules, and the linear relationship of the functional molecular polymer film material within the detection range is maintained well within a wide range of the added functional molecule mass of 50~200 mg.

[0024] (5) The functional molecular polymer film material prepared by the present invention has good stability.

[0025] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 A physical picture of the functional molecular polymer film material prepared by the present invention;

[0027] Figure 2 The UV-visible absorption spectra of Example 1 of the functional molecular polymer film material prepared in the present invention after irradiation with different β-ray doses;

[0028] Figure 3 The UV-visible absorption spectra of Example 2 of the functional molecular polymer film material prepared in the present invention after irradiation with different β-ray doses;

[0029] Figure 4 The UV-visible absorption spectra of Example 3 of the functional molecular polymer film material prepared in the present invention after irradiation with different β-ray doses;

[0030] Figure 5 The relationship between the absorbance at 310 nm and the radiation dose of Examples 1-3 of the functional molecular polymer film material prepared in the present invention;

[0031] Figure 6 The relationship between the absorbance at 310 nm and the radiation dose of Examples 3-5 of the functional molecular polymer film material prepared in the present invention;

[0032] Figure 7 This is a graph showing the relationship between absorbance at 310 nm and radiation dose for 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

[0033] 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 specific operation process, but the present invention is not limited to this embodiment.

[0034] Example 1

[0035] This embodiment provides a method for preparing a functional molecular polymer thin film material for quantitative detection of electron beam dose, comprising the following steps:

[0036] Mix 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution to obtain Solution I. Add 50 mg of 2,2'-bipyridine to Solution I and sonicate for 5 minutes to completely dissolve it, obtaining Solution II. Add 3.75 g of cellulose triacetate to Solution II and allow it to dissolve at room temperature for 6 hours to obtain a casting solution III. This casting solution III was slowly poured onto a clean glass plate using an automatic doctor blade coater and applied at a speed of 45 cm / min to a film thickness of 50 µm. After coating, allow it to cure at room temperature for 20 minutes to obtain the functional molecular polymer film material.

[0037] Example 2

[0038] 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.

[0039] This embodiment provides a method for preparing a functional molecular polymer thin film material for quantitative detection of electron beam dose, comprising the following steps:

[0040] Mix 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution to obtain Solution I. Add 50 mg of 4,4'-bipiperidine to Solution I and sonicate for 5 minutes to completely dissolve it, obtaining Solution II. Add 3.75 g of cellulose triacetate to Solution II and allow it to dissolve at room temperature for 6 hours to obtain a casting solution III. Slowly pour Casting Solution III onto a clean glass plate using an automatic doctor blade coater and apply the coating to a film thickness of 50 µm at a speed of 45 cm / min. After coating, allow the film to cure at room temperature for 20 minutes to obtain the functional molecular polymer film material.

[0041] Example 3

[0042] 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.

[0043] This embodiment provides a method for preparing a functional molecular polymer thin film material for quantitative detection of electron beam dose, comprising the following steps:

[0044] Mix 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution to obtain Solution I. Add 50 mg of 4,4'-bipyridine to Solution I and sonicate for 5 minutes to completely dissolve it, obtaining Solution II. Add 3.75 g of cellulose triacetate to Solution II and allow it to dissolve at room temperature for 6 hours to obtain a casting solution III. This casting solution III was slowly poured onto a clean glass plate using an automatic doctor blade coater and applied at a speed of 45 cm / min to a film thickness of 50 µm. After coating, allow it to cure at room temperature for 20 minutes to obtain the functional molecular polymer film material.

[0045] Example 4

[0046] The difference between this embodiment and embodiment 3 is that the amount of functional molecules added is different. The amount of functional molecules added in this embodiment is 150 mg.

[0047] This embodiment provides a method for preparing a functional molecular polymer thin film material for quantitative detection of electron beam dose, comprising the following steps:

[0048] Mix 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution to obtain Solution I. Add 150 mg of 4,4'-bipyridine to Solution I and sonicate for 5 minutes to completely dissolve it, obtaining Solution II. Add 3.75 g of cellulose triacetate to Solution II and allow it to dissolve at room temperature for 6 hours to obtain a casting solution III. This casting solution III was slowly poured onto a clean glass plate using an automatic doctor blade coater and applied at a speed of 45 cm / min to a film thickness of 50 µm. After coating, allow it to cure at room temperature for 20 minutes to obtain the functional molecular polymer film material.

[0049] Example 5

[0050] The difference between this embodiment and embodiment 3 is that the amount of functional molecules added is different. The amount of functional molecules added in this embodiment is 200 mg.

[0051] This embodiment provides a method for preparing a functional molecular polymer thin film material for quantitative detection of electron beam dose, comprising the following steps:

[0052] Mix 23 g of dichloromethane solution and 2 g of anhydrous ethanol solution to obtain Solution I. Add 200 mg of 4,4'-bipyridine to Solution I and sonicate for 5 minutes to completely dissolve it, obtaining Solution II. Add 3.75 g of cellulose triacetate to Solution II and allow it to dissolve at room temperature for 6 hours to obtain a casting solution III. This casting solution III was slowly poured onto a clean glass plate using an automatic doctor blade coater and applied at a speed of 45 cm / min to a film thickness of 50 µm. After coating, allow the film to cure at room temperature for 20 minutes to obtain the functional molecular polymer film material.

[0053] Test example

[0054] (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.

[0055] (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 in the test range of 300-320 nm. Therefore, it can be shown 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 equipped with 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.

[0056] (3) Figure 5 The graph is a relationship between the absorbance at 310 nm and the radiation dose of the functional molecular polymer film material prepared in Examples 1-3. Figure 2-4The relationship between the absorbance of the material at 310 nm and the irradiation dose under different irradiation doses was obtained by fitting. The linear relationships between the absorbance of the functional molecular polymer film materials prepared in Examples 1-3 and the irradiation dose were y=0.00405x+0.14725, y=0.00037x+0.0757 and y=0.00138x+0.0981, respectively, and R 2 The absorbance values ​​of the functional molecular polymer film materials of Examples 1-3 were 0.97959, 0.97603, and 0.99911, respectively. This indicates that there is a clear linear relationship between the absorbance and the irradiation dose of the functional molecular polymer film materials of Examples 1-3. Therefore, the irradiation dose can be estimated by measuring the absorbance of the functional molecular polymer film materials, achieving the objective of the present invention to quantitatively determine the irradiation dose by detecting changes in the absorbance of the material after irradiation.

[0057] Among them, the polymer film material with the functional molecule 4,4'-bipyridine added (Example 3) showed moderate irradiation response and the best linear relationship. In subsequent experiments, the 4,4'-bipyridine functional molecule was selected as a representative for further research and explanation.

[0058] (4) Figure 6 The graph is the relationship between the absorbance at 310 nm and the radiation dose of the functional molecular polymer film material prepared in Example 3-5. Figure 6 As can be seen from Table 1, the absorbance at 310 nm of the functional molecular polymer thin film materials prepared in Examples 3-5 all exhibited a clear linear relationship with the irradiation dose. Furthermore, the slope of the fitting curves of the absorbance at 310 nm and the radiation dose for the functional molecular polymer thin film materials prepared in Examples 3-5 increased with the addition of more functional molecules. This demonstrates that the sensitivity of the functional molecular polymer thin film materials of the present invention to electron beam irradiation dose detection can be controlled by varying the mass of the added functional molecules. Furthermore, the linear relationship of the functional molecular polymer thin film materials remains good within the detection range over a wide range of functional molecular masses, ranging from 50 to 200 mg.

[0059]

[0060] (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 As can be seen from Table 2, 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.

[0061]

[0062] Therefore, the present invention adopts the above-mentioned polymer film material for quantitative detection of electron beam dose and its preparation method. The functional molecular polymer film material prepared 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 quantitative detection material with excellent performance.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. 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 solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a polymer film material for quantitative detection of electron beam dose, 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 sonicate 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 solidifying at room temperature, a polymer film material is obtained. The functional molecule is selected from one of 2,2'-bipyridine, 4,4'-bipiperidine and 4,4'-bipyridine; and the mass ratio of the functional molecule, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:10~40:15~80:100~500.

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 mass ratio of functional molecules, anhydrous ethanol, cellulose triacetate and dichloromethane is 1:40:75:

460.

3. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 1, characterized in that: In step (2), the ultrasonic dissolution time is 5 to 10 minutes.

4. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 1, characterized in that: In step (3), the dissolution time at room temperature is 6 to 8 hours.

5. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 1, characterized in that: In step (4), the coating thickness is 50-150 μm.

6. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 1, characterized in that: In step (4), the scraping speed is 40-50 cm / min.

7. The method for preparing a polymer thin film material for quantitative detection of electron beam dose according to claim 1, characterized in that: In step (4), the curing time at room temperature is 15 to 30 minutes.

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