Flexible long-afterglow composite fluorescent material, preparation method thereof, light field consistency detection method and application of flexible long-afterglow composite fluorescent material

Abstract

The invention discloses a flexible long-afterglow composite fluorescent material, a preparation method, a light field consistency detection method and application, and relates to the technical field of radiation detection materials, and the flexible long-afterglow composite fluorescent material is prepared from the following raw materials: a scintillator, long-afterglow fluorescent powder, polyurethane, a preservative, polyacrylic acid, liquid silica gel and a curing agent. According to the invention, the luminescent material with strong capability of receiving high-energy X-rays is compounded with the long-afterglow material, and fluorescence excited by the high-energy X-rays is utilized to excite the long-afterglow material, so that the brightness of the long-afterglow material is improved, and observation and recording are facilitated; meanwhile, silica gel and other polymer composite materials are adopted for shaping, the flexibility of the silica gel enables the device to be suitable for different working scenes, the detection performance is remarkably improved, application and operation are convenient, energy is not wasted during use, and the device can be repeatedly used, can be directly observed, is visual and easy to read and is suitable for rapid detection. And data acquisition and storage can be realized in cooperation with a camera, and the system is suitable for various quality control environments.

Description

Technical Field

[0001] The present invention relates to the technical field of radiation detection materials, and particularly to a flexible long afterglow composite fluorescent material, a preparation method thereof, a method for detecting the light field uniformity, and an application thereof. Background Art

[0002] The long afterglow material is a material that can store energy under the excitation of light or X-rays and then slowly release the energy (such as the SrAl2O4:Eu,Dy material disclosed in Chinese Patent CN112111270A). Different long afterglow materials can emit visible light of different colors and are clearly visible in a relatively dark environment. It is widely used in various fields, including LEDs, X-ray imaging, display screens, etc. However, the long afterglow material has a weak ability to absorb high-energy X-rays (as described in the literature "Preparation, Property Regulation and Multifunctional Application of X-Ray Excited Long Afterglow Materials"), and the luminescence effect is poor.

[0003] The accelerator is currently the main equipment for radiotherapy. The irradiation range of the ray is invisible, and generally a lamp is used to simulate the irradiation field. The light field uniformity of the accelerator refers to the consistency between the irradiation range of the ray emitted by the accelerator and the range defined by the lamp of the simulated irradiation field. Its light field uniformity is an important quality control index to ensure the irradiation accuracy. Currently, film is generally used for inspection (as described in the literature "Application of Black and White Photographic Film in the Quality Control of Medical Linear Accelerators"). The film is placed in a cassette, and a coordinate paper is placed on it. A light field of a certain size is set, and the boundary positions are marked with high-density substances such as lead wires or lead dots. Then, it is irradiated with the accelerator ray, and it is observed whether the ray range is consistent with the light range. This method is cumbersome to operate, requires a cassette and film developing, is expensive, the marked positions are prone to blur, and the accuracy is low. Currently, slow-sensitive film has also been invented. The light field range is marked on the slow-sensitive film, and it is irradiated with the accelerator, and it is observed whether the ray range is consistent with the light range. This method is much simpler than the previous film method, but it is more expensive than the fast-sensitive film and is not suitable for daily use. There is also a method of using a two-dimensional matrix for testing (as described in the literature "Daily Quality Assurance of the Irradiation Field of Medical Electronic Linear Accelerators"). This method requires the purchase of expensive equipment, needs to be connected to a computer during normal testing, is very time-consuming, and is affected by many other factors, such as the influence of the measurement semiconductor or ionization chamber lattice density, temperature and humidity, etc. The obtained data also needs to be converted, which is not intuitive and time-consuming and laborious.

[0004] In order to solve the problems of the existing light field uniformity detection methods, such as the cumbersome technical operation and high price of the film method; the two-dimensional flat matrix relying on expensive equipment, cumbersome operation, and lack of intuitiveness, etc., it is urgent to provide a material and method for detecting the light field uniformity that is simple to operate, reusable, can be directly observed, and is suitable for rapid detection. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to provide a flexible long-afterglow composite fluorescent material, its preparation method, a method for detecting the light field uniformity and its application. The present invention combines a luminescent material scintillator with strong ability to receive high-energy X-rays with a long-afterglow material, and at the same time uses a polymer composite material such as silica gel to shape it, significantly improving the detection performance and facilitating application operation.

[0006] To solve the above technical problems, the technical solution of the present invention is as follows:

[0007] One of the purposes of the present invention is to provide a flexible long-afterglow composite fluorescent material.

[0008] The flexible long-afterglow composite fluorescent material of the present invention is prepared from raw materials including the following components:

[0009] Scintillator, long-afterglow phosphor, polyurethane, preservative, polyacrylic acid, liquid silicone and curing agent;

[0010] Based on the amount of the long-afterglow phosphor being 1 part by weight:

[0011]

[0012] In a preferred embodiment of the present invention:

[0013] Based on the amount of the long-afterglow phosphor being 1 part by weight:

[0014]

[0015] In a preferred embodiment of the present invention:

[0016] The scintillator is an inorganic scintillator, preferably lutetium yttrium silicate (LYSO) and / or gadolinium gallium garnet (GSO); and / or,

[0017] The long-afterglow phosphor is an aluminate phosphor, preferably SrAl2O4:Eu 2+ ,Dy 3+ (blue-green afterglow, afterglow time > 10h) and / or CaAl2O4:Eu 2+ ,Nd 3+ (yellow afterglow, afterglow time > 24h); and / or, the afterglow time of the long-afterglow phosphor > 10h, preferably > 24h; and / or, the excitation wavelength of the long-afterglow phosphor is 200 - 550nm, which can match the emission spectrum of the scintillator; and / or,

[0018] The polyurethane is hydroxyl-terminated polyurethane and / or isocyanate-terminated polyurethane (which can be purchased from Hyperion Materials & Technologies), and can react with the curing agent; and / or, the number-average molecular weight of the polyurethane is 5000 - 20000; it has strong performance tunability, good wear resistance, good elasticity, oil resistance and low temperature resistance, etc.; and / or,

[0019] The preservative is at least one of phenoxyethanol, sodium benzoate, and potassium sorbate; it can inhibit the growth of bacteria, fungi, and yeasts; and / or,

[0020] The number-average molecular weight of the polyacrylic acid (PAA) is 1000 - 5000; it has strong water absorption and viscosity; and / or,

[0021] The liquid silicone is addition cure silicone (which can be purchased from Huagong Materials Co., Ltd.). Preferably, the viscosity of the liquid silicone at 25°C is 1000 - 5000 mPa·s; and / or,

[0022] The curing agent is a commonly used curing agent in the art and can be purchased from Huagong Materials Co., Ltd.

[0023] The second object of the present invention is to provide a preparation method of the flexible long afterglow composite fluorescent material as described in the first object of the present invention.

[0024] The preparation method of the flexible long afterglow composite fluorescent material of the present invention, the method includes:

[0025] The components are stirred according to the dosage and then cured to obtain the composite fluorescent material.

[0026] In a preferred embodiment of the present invention:

[0027] The rotation speed of the stirring is 500 - 1500 rpm, preferably 800 - 1200 rpm, which can ensure the uniform dispersion of the components, and / or the time is 5 - 30 min, preferably 10 - 15 min, which can avoid over-shearing and heat generation; and / or,

[0028] The curing temperature is room temperature to 80°C, preferably 40 - 60°C, which can accelerate the cross-linking reaction of the silicone system, and / or the time is 12 - 72 h, preferably 24 - 48 h, which can ensure complete curing and avoid deformation.

[0029] The third object of the present invention is to provide a method for detecting the light field uniformity of the flexible long afterglow composite fluorescent material prepared by using the flexible long afterglow composite fluorescent material described in the first object of the present invention or the method described in the second object of the present invention.

[0030] The method for detecting light field consistency according to the present invention comprises:

[0031] After marking the surface of the composite fluorescent material, the light field of the instrument is opened to the size of the scale field, and then X-ray irradiation is performed, and the emission fluorescence range after X-ray irradiation is observed with the naked eye to see whether it is consistent with the scale field size.

[0032] In a preferred embodiment of the present invention:

[0033] During the light field consistency detection process, a camera is mounted to record in real time.

[0034] In a preferred embodiment of the present invention:

[0035] The X-ray irradiation dose is 50-600 cGy, preferably 200-300 cGy.

[0036] The fourth object of the present invention is to provide an application of the method for detecting light field consistency as described in the third object of the present invention in detecting light field consistency of radiation instruments.

[0037] In a preferred embodiment of the present invention:

[0038] The radiation instrument is at least one of a medical accelerator, an X-ray imaging system, and a radiation therapy simulator.

[0039] The present invention aims to solve the problems that the current light field consistency detection is not intuitive, the operation is cumbersome, and the price is high; the simple long afterglow material has a weak ability to receive high-energy X-rays, and requires a very high dose to make it emit weak light, which is not conducive to observation and recording. The luminescent material scintillator with a strong ability to receive high-energy X-rays is compounded with the long afterglow material, and the fluorescence of the scintillator excited by the high-energy X-ray is used to excite the long afterglow material, so that its brightness is improved, which is conducive to observation and recording; at the same time, a polymer composite material such as silica gel is used to shape it, and the flexibility of silica gel makes it suitable for different work scenes, significantly improving the detection performance, facilitating application and operation, not wasting energy when in use, and can be reused, can be directly observed, intuitive and easy to read, and suitable for rapid detection. With the help of a camera, data collection and storage can be achieved, which is suitable for various quality control environments.

[0040] The composite fluorescent material of the present invention has good flexibility, shows good strength when bent and stretched, has improved brightness, is visible to the naked eye, is very intuitive and convenient to detect, and is suitable for rapid detection. The composite fluorescent material can be reused, has very low cost, and has a wide range of applications, and can be applied to a variety of equipment such as accelerators and simulators. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1Photographs of the composite fluorescent material obtained in Example 1 in the bent and stretched states;

[0042] Figure 2 Schematic diagram for the detection of light field uniformity of the present invention;

[0043] Figure 3 Photographs of the composite fluorescent material diagrams obtained in Examples 1 - 3 after scale marking;

[0044] Figure 4 Photographs during the process of detecting the light field uniformity of the composite fluorescent material diagrams obtained in Examples 1 - 3. Detailed implementation manners

[0045] The following further describes the detailed implementation manners of the present invention with reference to the accompanying drawings. It should be noted here that the descriptions of these implementation manners are used to help understand the present invention, but do not constitute a limitation to the present invention. In addition, the technical features involved in the various implementation manners of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0046] The raw materials used in the embodiments of the present invention are all commercially available products.

[0047]

Example 1

[0048] The present invention adds 5 g of scintillator GSO, 5 g of long - persistent phosphor SrAl2O4:Eu 2+ ,Dy 3+ , 2 g of hydroxyl - terminated polyurethane, 2 ml of phenoxyethanol, 2 g of polyacrylic acid, 8 g of liquid silicone rubber, and 8 g of curing agent into a stirrer, stirs at 800 rpm for 10 min, transfers to a flat mold, cures at room temperature for 24 h, demolds to take out the cured composite fluorescent material, conducts scale marking, opens the accelerator light field to the size of the scale field (2×2 cm 2 ), irradiates with 200 cGy, visually observes whether the fluorescence emission range is consistent with the size of the scale field by the naked eye, sets up a camera beside to record in real - time, and can repeatedly play back to observe whether there is an error between the radiation field and the light field.

[0049]

Example 2

[0050] The present invention adds 5 g of scintillator GSO, 5 g of long - persistent phosphor SrAl2O4:Eu 2+ ,Dy 3+ , 2 g of hydroxyl - terminated polyurethane, 2 ml of phenoxyethanol, 2 g of polyacrylic acid, 10 g of liquid silicone rubber, and 10 g of curing agent into a stirrer, stirs at 1000 rpm for 10 min, transfers to a flat mold, cures at room temperature for 24 h, demolds to take out the cured composite fluorescent material, conducts scale marking, opens the accelerator light field to the size of the scale field (4×4 cm 2), irradiate with 200 cGy, visually observe whether the fluorescence emission range is consistent with the size of the scale field with the naked eye, set up a camera beside to record in real time, and it can be repeatedly played back to observe whether there is an error between the radiation field and the light field.

[0051]

Example 3

[0052] For the invention, 10 g of the scintillator GSO, 10 g of the long-afterglow phosphor SrAl2O4:Eu 2+ , Dy 3+ 10 g, 2 g of hydroxy-terminated polyurethane, 2 ml of phenoxyethanol, 2 g of polyacrylic acid, 5 g of liquid silicone, and 5 g of curing agent are added to a stirrer, stirred at 1200 rpm for 10 min, transferred to a flat-bottom mold, cured at room temperature for 48 h, the cured composite fluorescent material is taken out of the mold after demolding, scale markings are made, the accelerator light field is opened to the size of the scale field (6×6 cm 2 ), irradiate with 500 cGy, visually observe whether the fluorescence emission range is consistent with the size of the scale field with the naked eye, set up a camera beside to record in real time, and it can be repeatedly played back to observe whether there is an error between the radiation field and the light field.

[0053] From Figure 4 the light field consistency detection results, it can be seen that after the X-ray is turned off, the X-ray field can still be clearly visible by using the afterglow of the composite fluorescent material. The result is that there is a deviation between the X-ray field and the light field, and the X-ray field has a deviation to the left and needs to be adjusted. This result well proves the intuitive, practical, convenient and low-cost advantages of the present invention.

[0054]

Example 4

[0055] For the invention, 7.5 g of the scintillator LYSO, 5 g of the long-afterglow phosphor CaAl2O4:Eu 2+ , Nd 3+ 5 g, 4 g of isocyanate-terminated polyurethane, 1.5 g of sodium benzoate, 2.5 g of polyacrylic acid, 15 g of liquid silicone, and 15 g of curing agent are added to a stirrer, stirred at 800 rpm for 10 min, transferred to a flat-bottom mold, cured at room temperature for 24 h, the cured composite fluorescent material is taken out of the mold after demolding, scale markings are made, the accelerator light field is opened to the size of the scale field (6×6 cm 2 ), irradiate with 300 cGy, visually observe whether the fluorescence emission range is consistent with the size of the scale field with the naked eye, set up a camera beside to record in real time, and it can be repeatedly played back to observe whether there is an error between the radiation field and the light field.

[0056] The above has described the embodiments of the present invention in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, without departing from the principle and spirit of the present invention, various changes, modifications, substitutions and variations to these embodiments still fall within the protection scope of the present invention.

Claims

1. A flexible long afterglow composite fluorescent material, characterized in that The composite fluorescent material is prepared from raw materials including the following components: Scintillator, long-afterglow phosphor, polyurethane, preservative, polyacrylic acid, liquid silicone and curing agent; Based on 1 part by weight of the long-afterglow phosphor:

2. The composite fluorescent material according to claim 1, wherein: Based on 1 part by weight of the long-afterglow phosphor:

3. The composite fluorescent material according to claim 1 or 2, wherein: The scintillator is an inorganic scintillator, preferably lutetium yttrium silicate and / or gadolinium gallium garnet; and / or, The long afterglow phosphor is an aluminate phosphor, preferably SrAl2O4:Eu 2+ ,Dy 3+ and / or CaAl2O4:Eu 2+ ,Nd 3+ ; and / or, the afterglow time of the long afterglow phosphor > 10 h, preferably > 24 h; and / or, the excitation wavelength of the long afterglow phosphor is 200 - 550 nm; and / or, The polyurethane is hydroxyl-terminated polyurethane and / or isocyanate-terminated polyurethane; and / or, the number-average molecular weight of the polyurethane is 5000-20000; and / or, The preservative is at least one of phenoxyethanol, sodium benzoate, potassium sorbate; and / or, The number-average molecular weight of the polyacrylic acid is 1000-5000; and / or, The liquid silicone is addition-curing silicone, preferably, the viscosity of the liquid silicone at 25°C is 1000-5000 mPa·s.

4. A method for preparing a flexible long afterglow composite fluorescent material according to any one of claims 1-3, characterized in that The method includes: The components are stirred according to the dosage and then cured to obtain the composite fluorescent material.

5. The method according to claim 4, wherein: The rotation speed of the stirring is 500-1500 rpm, preferably 800-1200 rpm, and / or, the time is 5-30 min, preferably 10-15 min; and / or, The temperature of the curing is room temperature to 80°C, preferably 40-60°C, and / or, the time is 12-72 h, preferably 24-48 h.

6. A method for detecting the light field uniformity of a flexible long-afterglow composite fluorescent material prepared by using the flexible long-afterglow composite fluorescent material according to any one of claims 1-3 or the method according to claim 4 or 5, characterized in that The method includes: After scale marking is performed on the surface of the composite fluorescent material, the light field of the instrument is opened to the size of the scale field, and then X-ray irradiation is performed, and it is visually observed whether the fluorescence emission range after X-ray irradiation is consistent with the size of the scale field.

7. The method according to claim 6, wherein: During the detection of the light field consistency, a camera is mounted to record in real time.

8. The method according to claim 6, wherein: The X-ray irradiation dose is 50-600 cGy, preferably 200-300 cGy.

9. Application of a method for detecting light field consistency as claimed in claims 6-8 in the detection of light field consistency of a radiation instrument.

10. The application according to claim 9, wherein: The radiation instrument is at least one of a medical accelerator, an X-ray imaging system, a radiotherapy simulator.

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