A flexible long-afterglow composite fluorescent material, its preparation method, and a method for detecting optical field consistency, and their applications.

Abstract

This invention discloses a flexible long-afterglow composite fluorescent material, its preparation method, and a method and application for detecting optical field consistency, relating to the field of radiation detection materials technology. The composite fluorescent material is prepared from raw materials comprising the following components: a scintillator, long-afterglow phosphor, polyurethane, a preservative, polyacrylic acid, liquid silicone, and a curing agent. This invention combines a luminescent material with strong high-energy X-ray receiving capabilities with a long-afterglow material. The fluorescence excited by high-energy X-rays is then used to excite the long-afterglow material, increasing its brightness and facilitating observation and recording. Simultaneously, a polymer composite material such as silicone is used for shaping. The flexibility of silicone allows it to be applied to different working scenarios, significantly improving detection performance, facilitating application and operation, saving energy during use, being reusable, and allowing for direct observation and easy reading, making it suitable for rapid detection. Combined with a camera, data acquisition and storage can be achieved, making it suitable for various quality control environments.

Description

Technical Field

[0001] This invention relates to the field of radiation detection materials technology, and in particular to a flexible long-afterglow composite fluorescent material, its preparation method, and a method and application for detecting optical field consistency. Background Technology

[0002] Long-afterglow materials are materials that can store energy when excited by light or X-rays and then slowly release it (such as the SrAl2O4:Eu,Dy material disclosed in Chinese patent CN112111270A). Different long-afterglow materials can emit visible light of different colors, making them brightly distinguishable in dark environments. They are widely used in various fields, including LEDs, X-ray imaging, and displays. However, long-afterglow materials have a weak ability to absorb high-energy X-rays (as described in the literature "Preparation, Performance Regulation and Multifunctional Applications of X-ray Excited Long-Afterglow Materials"), resulting in poor luminescence.

[0003] Accelerators are currently the main equipment in radiotherapy. Since the radiation field is invisible, it is usually simulated using artificial light. Accelerator field consistency refers to the consistency between the radiation field emitted by the accelerator and the area defined by the artificial light in the simulated field. This consistency is a crucial quality control indicator for ensuring the accuracy of radiation. Currently, film is commonly used for inspection (as described in the literature "Application of Black and White Photographic Film in Quality Control of Medical Linear Accelerators"). The film is placed in a dark box, graph paper is placed on it, a certain size of artificial light field is set, and the boundary positions are marked with high-density materials such as lead wire or lead dots. The accelerator radiation is then applied, and the consistency between the radiation field and the artificial light field is observed. This method is cumbersome, requiring a dark box and film development, is expensive, and the marked positions are prone to blurring, resulting in low accuracy. Slow-sensitivity film has also been invented. The artificial light field is marked on slow-sensitivity film, and the accelerator is used for irradiation, observing whether the radiation field and the artificial light field are consistent. This method is much simpler than the previous film method, but it is more expensive than fast-sensitivity film and is not suitable for daily use. Another method is to use a two-dimensional matrix for testing (as described in the literature "Daily Quality Assurance of Irradiation Fields for Medical Electron Linear Accelerators"). This method requires the purchase of expensive equipment, and the testing requires connection to a computer, which is very time-consuming. It is also affected by many other factors, such as the density of the semiconductor or ionization chamber, temperature, and humidity. The data obtained also needs to be converted, which is not intuitive and is time-consuming and labor-intensive.

[0004] To address the problems of existing optical field consistency testing methods, such as the cumbersome and expensive film method and the cumbersome and unintuitive operation of two-dimensional flat panel matrix relying on expensive equipment, there is an urgent need for a material and method that is easy to operate, reusable, directly observable, and suitable for rapid detection of optical field consistency. Summary of the Invention

[0005] The technical problem to be solved by this invention is to provide a flexible long-afterglow composite fluorescent material, its preparation method, and a method and application for detecting optical field consistency. This invention combines a scintillator, a luminescent material with strong ability to receive high-energy X-rays, with a long-afterglow material, and uses high-molecular composite materials such as silicone to fix it, which significantly improves the detection performance and facilitates application and operation.

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

[0007] One of the objectives of this 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 comprising 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 used 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 used being 1 part by weight:

[0014]

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

[0016] The scintillator is an inorganic scintillator, preferably yttrium lutetium 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 is > 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 a hydroxyl-terminated polyurethane and / or an isocyanate-terminated polyurethane (available from Haibeisi Materials Co., Ltd.), capable of reacting with a curing agent; and / or, the number average molecular weight of the polyurethane is 5000-20000; possessing strong performance adjustability, good wear resistance, good elasticity, oil resistance, and low-temperature resistance; and / or,

[0019] The preservative is at least one selected from phenoxyethanol, sodium benzoate, and potassium sorbate; capable of inhibiting the growth of bacteria, fungi, and yeast; and / or,

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

[0021] The liquid silicone is addition-cure silicone (available from Hwagong 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 this field and can be purchased from Huagong Materials Co., Ltd.

[0023] A second objective of this invention is to provide a method for preparing a flexible long-afterglow composite fluorescent material as described in one objective of this invention.

[0024] The method for preparing the flexible long-afterglow composite fluorescent material of the present invention includes:

[0025] The composite fluorescent material is obtained by stirring and curing the components according to the specified dosage.

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

[0027] The stirring speed is 500-1500 rpm, preferably 800-1200 rpm, to ensure uniform dispersion of the components, and / or the stirring time is 5-30 min, preferably 10-15 min, to avoid excessive shearing that could lead to 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 12-72h, preferably 24-48h, which can ensure complete curing and avoid deformation.

[0029] A third objective of this invention is to provide a method for detecting the optical field consistency of a flexible long-afterglow composite fluorescent material prepared using the flexible long-afterglow composite fluorescent material described in one objective of this invention or the method described in another objective of this invention.

[0030] The method for optical field consistency detection according to the present invention includes:

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

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

[0033] During the optical field consistency detection process, a camera is set up 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 objective of this invention is to provide an application of the method for detecting optical field consistency as described in the third objective of this invention in the detection of optical field consistency in radiographic 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 radiotherapy simulator.

[0039] This invention addresses the problems of current optical field consistency detection methods, such as lack of intuitiveness, cumbersome operation, and high cost; and the weak ability of simple long-afterglow materials to receive high-energy X-rays, requiring very high doses to produce even a faint emission, which is not conducive to observation and recording. It combines a scintillator, a luminescent material with strong high-energy X-ray reception, with a long-afterglow material. The fluorescence of the scintillator, excited by high-energy X-rays, then excites the long-afterglow material, increasing its brightness and facilitating observation and recording. Simultaneously, it uses a polymer composite material such as silicone for shaping; the flexibility of silicone allows it to be used in various working environments, significantly improving detection performance, simplifying operation, saving energy, being reusable, and allowing for direct observation and easy reading, suitable for rapid detection. Combined with a camera, it enables data acquisition and storage, suitable for various quality control environments.

[0040] The composite fluorescent material of this invention has good flexibility, exhibits good strength when bent and stretched, and has improved brightness that is visible to the naked eye. It 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, including accelerators, simulators and other equipment. Attached Figure Description

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

[0042] Figure 2 This is a schematic diagram illustrating the optical field consistency detection process of this invention.

[0043] Figure 3 The images of the composite fluorescent materials prepared in Examples 1-3 are photographs after being marked with a scale.

[0044] Figure 4 These are photographs taken during the process of testing the optical field consistency of the composite fluorescent materials prepared in Examples 1-3. Detailed Implementation

[0045] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings. It should be noted that these descriptions are for the purpose of aiding understanding the present invention, but do not constitute a limitation thereof. Furthermore, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.

[0046] All raw materials used in the embodiments of this invention are commercially available products.

[0047]

Example 1

[0048] The invention will incorporate 5g of scintillator GSO and long-afterglow phosphor SrAl2O4:Eu. 2+ ,Dy 3+ 5g of hydroxyl-terminated polyurethane, 2g of phenoxyethanol, 2ml of polyacrylic acid, 2g of liquid silicone, and 8g of curing agent are added to a stirrer and stirred at 800 rpm for 10 minutes. The mixture is then transferred to a flat-bottomed mold and cured at room temperature for 24 hours. The cured composite fluorescent material is then demolded and marked with graduations. The accelerator light field is opened to the size of the graduation field (2×2cm). 2 Irradiation with 200 cGy is performed, and the emission fluorescence range can be visually observed to see if it matches the size of the scale field. A camera is set up next to it to record in real time, and the data can be repeatedly played back to observe whether there is any error between the emission field and the light field.

[0049]

Example 2

[0050] The invention will incorporate 5g of scintillator GSO and long-afterglow phosphor SrAl2O4:Eu. 2+ ,Dy 3+ 5g of hydroxyl-terminated polyurethane, 2g of phenoxyethanol, 2ml of polyacrylic acid, 10g of liquid silicone, and 10g of curing agent are added to a stirrer and stirred at 1000rpm for 10min. The mixture is then transferred to a flat-bottomed mold and cured at room temperature for 24h. The cured composite fluorescent material is then demolded and marked with graduations. The accelerator light field is opened to the size of the graduation field (4×4cm). 2Irradiation with 200 cGy is performed, and the emission fluorescence range can be visually observed to see if it matches the size of the scale field. A camera is set up next to it to record in real time, and the data can be repeatedly played back to observe whether there is any error between the emission field and the light field.

[0051]

Example 3

[0052] The invention will incorporate 10g of scintillator GSO and long-afterglow phosphor SrAl2O4:Eu. 2+ ,Dy 3+ 10g of hydroxyl-terminated polyurethane, 2g of phenoxyethanol, 2g of polyacrylic acid, 5g of liquid silicone, and 5g of curing agent are added to a stirrer and stirred at 1200 rpm for 10 minutes. The mixture is then transferred to a flat-bottomed mold and cured at room temperature for 48 hours. The cured composite fluorescent material is then demolded and marked with graduations. The accelerator light field is opened to the size of the graduation field (6×6cm). 2 Irradiation with 500 cGy is performed, and the emission fluorescence range can be visually observed to see if it matches the size of the scale field. A camera is set up next to it to record in real time, and the data can be repeatedly played back to observe whether there is any error between the emission field and the light field.

[0053] Depend on Figure 4 The results of the optical field consistency test show that even after the X-rays are turned off, the X-ray field remains clearly visible thanks to the afterglow of the composite fluorescent material. The results also indicate a deviation between the X-ray field and the lamp field, with the X-ray field deviating to the left, requiring adjustment. This result effectively demonstrates the intuitive, practical, convenient, and low-cost advantages of this invention.

[0054]

Example 4

[0055] The invention will incorporate 7.5g of scintillator LYSO and long-afterglow phosphor CaAl2O4:Eu. 2+ ,Nd 3+ 5g of precipitated isocyanate-terminated polyurethane, 4g of sodium benzoate, 1.5g of polyacrylic acid, 2.5g of liquid silicone, 15g of curing agent, and 15g of solvent are added to a stirrer and stirred at 800 rpm for 10 minutes. The mixture is then transferred to a flat-bottomed mold and cured at room temperature for 24 hours. The cured composite fluorescent material is then demolded and marked with graduations. The accelerator light field is opened to the size of the graduation field (6×6cm). 2 Irradiation with 300 cGy is performed, and the emission fluorescence range can be visually observed to see if it matches the size of the scale field. A camera is set up next to it to record in real time, and the data can be repeatedly played back to observe whether there is any error between the emission field and the light field.

[0056] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention, and these variations 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 comprising the following components: Scintillator, long-afterglow phosphor, polyurethane, preservative, polyacrylic acid, liquid silicone and curing agent; Based on the amount of the long-afterglow phosphor used being 1 part by weight: The scintillator is yttrium lutetium silicate and / or gadolinium gallium garnet; The long afterglow phosphor is SrAl2O4:Eu 2+ ,Dy 3+ and / or CaAl2O4:Eu 2+ ,Nd 3 +.

2. The composite fluorescent material according to claim 1, characterized in that: Based on the amount of the long-afterglow phosphor used being 1 part by weight:

3. The composite fluorescent material according to claim 1 or 2, characterized in that: The afterglow time of the long-afterglow phosphor is >10h; and / or, the excitation wavelength of the long-afterglow phosphor is 200-550nm; and / or, The polyurethane is a hydroxyl-terminated polyurethane and / or an isocyanate-terminated polyurethane; and / or, the number-average molecular weight of the polyurethane is 5000-20000; and / or, The preservative is at least one selected from phenoxyethanol, sodium benzoate, and potassium sorbate; and / or... The polyacrylic acid has a number-average molecular weight of 1000-5000; and / or, The liquid silicone is an addition-type silicone.

4. The composite fluorescent material according to claim 3, characterized in that: The afterglow time of the long-afterglow phosphor is >24h; and / or, The viscosity of the liquid silicone at 25°C is 1000-5000 mPa·s.

5. A method for preparing a flexible long-afterglow composite fluorescent material as described in any one of claims 1-4, characterized in that... The method includes: The composite fluorescent material is obtained by stirring and curing the components according to the specified dosage.

6. The method according to claim 5, characterized in that: The stirring speed is 500-1500 rpm, and / or the time is 5-30 min; and / or, The curing temperature is room temperature to 80°C, and / or the curing time is 12-72 hours.

7. The method according to claim 6, characterized in that: The stirring speed is 800-1200 rpm, and / or the time is 10-15 min; and / or, The curing temperature is 40-60℃, and / or the time is 24-48h.

8. A method for detecting the optical field uniformity of a flexible long-afterglow composite fluorescent material prepared using the flexible long-afterglow composite fluorescent material according to any one of claims 1-4 or the method according to any one of claims 5-7, characterized in that... The method includes: After marking the surface of the composite fluorescent material, the instrument's light field is opened to the size of the marked field, and then X-ray irradiation is performed. The emission fluorescence range after X-ray irradiation is observed by the naked eye to see if it is consistent with the size of the marked field.

9. The method according to claim 8, characterized in that: During the optical field consistency detection process, a camera is set up to record in real time.

10. The method according to claim 8, characterized in that: The X-ray irradiation dose is 50-600 cGy.

11. The method according to claim 10, characterized in that: The X-ray irradiation dose is 200-300 cGy.

12. The application of the method for detecting optical field consistency as described in any one of claims 8-11 in the detection of optical field consistency in radiographic instruments.

13. The application according to claim 12, characterized in that: The radiation instrument is at least one of a medical accelerator, an X-ray imaging system, and a radiotherapy simulator.

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