High x-ray absorbing material based on metal oxide composites

Abstract

The application relates to the technical field of X-ray protection and detection materials, and discloses a high X-ray absorption material based on metal oxide composite, which is composed of 30%-50% core absorption components, 5%-15% synergistic enhancement components and the rest base components; a preparation method of the material comprises metal oxide powder pretreatment, modified epoxy resin base synthesis, composite forming and step-by-step curing. The material has excellent X-ray absorption efficiency in a 15-500 keV wide energy range, the shielding efficiency is greater than or equal to 97% under a 80-150 kV tube voltage, the lead equivalent is 0.8-1.2 mm Pb, and the density is only 3.5‑5.0g / cm3 The material has excellent mechanical properties, environmental stability and environmental protection, is lead-free and pollution-free, the preparation process is simple and controllable, and can be widely applied to the fields of medical protection, industrial detection, safety detection and the like.

Description

Technical Field

[0001] This invention relates to the field of X-ray protection and detection materials technology, specifically to a high X-ray absorption material based on metal oxide composites. Background Technology

[0002] X-ray technology is widely used in medical diagnosis, industrial flaw detection, and safety inspection, but its radiation characteristics pose potential hazards to human health and precision equipment. Therefore, the development of highly efficient X-ray absorbing materials is crucial. Traditional X-ray absorbing materials are mainly lead-based, which have good absorption performance, but suffer from drawbacks such as high density, poor flexibility, and easy oxidation and peeling. Furthermore, lead is toxic and its disposal can easily cause environmental pollution, which is inconsistent with the trend of environmental protection.

[0003] To address the drawbacks of lead-based materials, various lead-free absorbing materials have been developed in existing technologies, such as single metal oxides (tungsten oxide, bismuth oxide, etc.), metal alloys, and polymer-based composite materials. However, single metal oxide materials suffer from a narrow X-ray absorption band, making it difficult to maintain stable absorption efficiency under X-ray irradiation of different energies. Metal alloy materials face challenges such as complex processing techniques and high costs, and some materials have poor biocompatibility, limiting their application in the medical field. While polymer-based composite materials can improve flexibility, they often suffer from uneven filler dispersion and weak interfacial bonding, leading to decreased absorption performance and insufficient mechanical stability.

[0004] Furthermore, existing composite absorbing materials are mostly prepared through simple physical mixing, resulting in insignificant synergistic effects between components and making it difficult to achieve comprehensive optimization of X-ray absorption efficiency, material lightweighting, and environmental adaptability. For example, some tungsten oxide composite materials have insufficient absorption efficiency in the high-energy X-ray region, while bismuth oxide composite materials exhibit poor stability in humid environments, neither of which can meet the application requirements of complex scenarios. Therefore, developing a metal oxide composite X-ray absorbing material with optimized component synergy, high absorption efficiency, excellent physicochemical properties, and environmental friendliness is of significant practical importance. Summary of the Invention

[0005] Technical problems to be solved

[0006] To address the shortcomings of existing technologies, this invention provides a high X-ray absorption material based on metal oxide composites, which achieves efficient absorption of X-rays in a wide energy range of 15-500keV, while also being lightweight, possessing good mechanical properties and environmental stability, and being lead-free and environmentally friendly, making it suitable for various applications.

[0007] Technical solution

[0008] To achieve the above objectives, the present invention provides the following technical solution: a high X-ray absorption material based on metal oxide composite, comprising a core absorbing component, a synergistic enhancement component, and a matrix component, wherein each component is, by mass percentage, 30%-50% core absorbing component, 5%-15% synergistic enhancement component, and the remainder being a matrix component.

[0009] Furthermore, the core absorbing component is a mixture of tungsten oxide and bismuth oxide, with a mass ratio of 1:0.5-2.0; the tungsten oxide is selected from at least one of WO2 and WO3, with a particle size of 50-200 nm; the bismuth oxide is Bi2O3, with a particle size of 100-300 nm; efficient attenuation of X-rays is achieved through the photoelectric effect and Compton scattering effect of high atomic number elements.

[0010] Furthermore, the synergistic reinforcing component is a mixture of yttrium oxide and neodymium oxide, with a mass ratio of 1:0.3-0.8; the yttrium oxide is Y2O3, and the neodymium oxide is Nd2O3; the yttrium oxide exhibits a resonant absorption effect in the mid-to-high energy region (>88keV), while the neodymium oxide enhances anti-scattering performance in the mid-to-low energy region (25-50keV). The two components synergistically broaden the X-ray absorption band of the material and simultaneously improve the dispersion of the core absorbing component.

[0011] Furthermore, the matrix component is a modified epoxy resin, composed of epoxy resin E-51, curing agent methyltetrahydrophthalic anhydride, and dispersant polyvinylpyrrolidone, with a mass ratio of 100:80-100:1-3. The modified epoxy resin can improve the interfacial bonding force between the components and enhance the mechanical properties and environmental stability of the material.

[0012] Furthermore, it includes the following steps:

[0013] (1) Pretreatment: Tungsten oxide, bismuth oxide, yttrium oxide and neodymium oxide were vacuum dried at 80-100℃ respectively; then the core absorber and the synergistic enhancement component were added to a planetary ball mill, anhydrous ethanol was used as the dispersion medium, the ball-to-material ratio was 10:1-15:1, the rotation speed was 200-300 r / min, and the ball milling was carried out for 2-4 hours to obtain mixed powder;

[0014] (2) Matrix preparation: Heat epoxy resin E-51, add dispersant polyvinylpyrrolidone, stir for 15-30 min until dissolved; then add curing agent methyltetrahydrophthalic anhydride, stir for 10-20 min to obtain modified epoxy resin matrix;

[0015] (3) Composite molding: Add the mixed powder to the modified epoxy resin matrix, ultrasonically disperse at 30-40℃ with an ultrasonic frequency of 25-40kHz, and simultaneously stir magnetically at 500-800r / min to form a uniform slurry; pour the slurry into the mold, cure at 60-80℃ for 2-4h, then raise the temperature to 120-150℃ for 4-6h, and cool and demold to obtain the final product.

[0016] Furthermore, in step (1), the vacuum drying time is 4-6 hours.

[0017] Furthermore, in step (2), the heating temperature is 40-50℃.

[0018] Furthermore, in step (3), the ultrasonic dispersion time is 30-60 min.

[0019] Beneficial technical effects:

[0020] In the technical solution of this invention, the synergistic design of the core absorbing component tungsten oxide-bismuth oxide and the synergistic reinforcing component yttrium oxide-neodymium oxide utilizes the absorption advantages of different metal oxides in different energy ranges to achieve efficient absorption of X-rays over a wide energy range. The modified epoxy resin matrix of this invention improves the dispersion uniformity and interfacial bonding of each component, resulting in good tensile strength, no cracking after repeated bending, and excellent mechanical stability. The material of this invention has good corrosion resistance and is free of harmful heavy metals such as lead, mercury, and cadmium, making it environmentally friendly and biocompatible, suitable for use in medical protective applications. This invention employs a ball milling-ultrasonic dispersion-stepwise curing preparation process, eliminating the need for high-temperature and high-pressure equipment, simplifying operation, and increasing production efficiency. The metal oxide raw materials used are readily available, reducing costs compared to precious metal oxides such as platinum and iridium, and facilitating large-scale production. Detailed Implementation

[0021] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0022] Example 1

[0023] A high X-ray absorbing material based on metal oxide composites, with the following components:

[0024] 1. Component ratio, by mass percentage: core absorber 35%, synergistic reinforcing component 10%, matrix component 55%; the core absorber is a mixture of WO2 and Bi2O3 in a mass ratio of 1:1, with W2 selected as 100nm nanoparticles with a purity of 99.9% and Bi2O3 selected as 200nm nanoparticles with a purity of 99.8%; the synergistic reinforcing component is a mixture of Y2O3 and Nd2O3 in a mass ratio of 1:0.5, both of which are 50-100nm nanoparticles with a purity of 99.9%; the matrix component is a modified epoxy resin, composed of epoxy resin E-51 with an epoxy value of 0.48-0.54eq / 100g, curing agent methyltetrahydrophthalic anhydride with a purity of 98%, and dispersant polyvinylpyrrolidone with a molecular weight of 40000, in a mass ratio of 100:90:2.

[0025] 2. Preparation method:

[0026] Pretreatment: WO2, Bi2O3, Y2O3, and Nd2O3 powders were placed in a vacuum drying oven at 90℃ and -0.09MPa for 5 hours to completely remove adsorbed moisture from the powder surface. Then, 35 parts of the core absorbent components (WO2 17.5 parts and Bi2O3 17.5 parts) and 10 parts of the synergistic reinforcing components (Y2O3 6.67 parts and Nd2O3 3.33 parts) were added to a planetary ball mill. Anhydrous ethanol was used as the dispersion medium, with a liquid-to-solid ratio of 1:1 and a mass ratio of 1:1. A zirconia ball mill jar and grinding balls with a diameter of 5mm were selected. The ball-to-material ratio was set at 12:1, and the milling speed was 250 r / min for 3 hours. During the milling process, the temperature inside the jar was controlled to be ≤50℃ to prevent powder oxidation. After milling, the slurry was placed in a 60℃ vacuum drying oven for 8 hours to remove ethanol, resulting in a uniformly mixed powder with a particle size D50 of 120 nm.

[0027] Matrix preparation: 30.56 parts of epoxy resin E-51 from 55 parts of the matrix component were heated to 45°C, and 0.61 parts of polyvinylpyrrolidone were added under constant temperature stirring at a stirring speed of 300 r / min for 20 min until the polyvinylpyrrolidone was completely dissolved; then 23.83 parts of methyltetrahydrophthalic anhydride were added, and stirring was continued for 15 min. Nitrogen gas was introduced during the stirring process to prevent oxidation of the curing agent, thus obtaining the modified epoxy resin matrix;

[0028] Composite molding: The pretreated mixed powder is slowly added to the modified epoxy resin matrix while stirring at a speed of 500 r / min. Then, it is placed in an ultrasonic disperser and ultrasonically dispersed for 45 min at a temperature of 35℃, an ultrasonic frequency of 30 kHz, and a power of 500 W, while simultaneously using magnetic stirring at a speed of 600 r / min to ensure uniform dispersion of the powder and the formation of a slurry with no agglomeration and good flowability. The slurry is poured into a polytetrafluoroethylene mold with dimensions of 100 mm × 100 mm × 5 mm and placed in an oven. It is first preheated at 60℃ for 30 min, then heated to 70℃ for 3 h, and then heated to 130℃ for a second curing for 5 h. During the curing process, a pressure of 0.1 MPa is applied to avoid the formation of bubbles. After cooling to room temperature, it is demolded to obtain the target material.

[0029] Performance testing:

[0030] Density: 4.2 g / cm³ 3 Water displacement test; X-ray absorption performance, 100kV tube voltage, 5mA tube current: lead equivalent 1.0mmPb, half-value layer 2.2mm, shielding efficiency 97.5%; mechanical properties: tensile strength 38MPa, elongation at break 5.2%, after repeated bending 1000 times at a frequency of 10 times / min, no cracking or peeling on the surface, lead equivalent fluctuation at ±90° bending point ≤1%; environmental stability: after aging at 85℃ / 85%RH for 48h, lead equivalent 1.04mmPb, fluctuation 4.2%, after immersion in 5% NaCl solution for 72h, no rust or blistering on the surface, lead equivalent fluctuation ≤2%; environmental performance: heavy metal content, ICP-MS detection: lead, mercury, and cadmium were not detected, hexavalent chromium ≤50ppm; VOC emission 0.3mg / m³ 3 1m 3 Climate chamber method; cytotoxicity level 1, MTT assay, good biocompatibility.

[0031] Example 2

[0032] A high X-ray absorbing material based on metal oxide composites, with the following components:

[0033] 1. Component ratio, by mass percentage: core absorber 45%, synergistic reinforcing component 12%, matrix component 43%; the core absorber is a mixture of WO3 and Bi2O3 in a mass ratio of 1:2, with WO3 selected as 150nm nanoparticles with a purity of 99.9% and Bi2O3 selected as 250nm nanoparticles with a purity of 99.8%; the synergistic reinforcing component is a mixture of Y2O3 and Nd2O3 in a mass ratio of 1:0.8, both of which are 80-120nm nanoparticles with a purity of 99.9%; the matrix component is a modified epoxy resin, composed of epoxy resin E-51 with an epoxy value of 0.48-0.54eq / 100g, methyltetrahydrophthalic anhydride with a purity of 98%, and polyvinylpyrrolidone with a molecular weight of 40000, in a mass ratio of 100:100:3.

[0034] 2. Preparation method:

[0035] Pretreatment: WO3, Bi2O3, Y2O3, and Nd2O3 powders were dried at 100℃ and under a vacuum of -0.095MPa for 4 hours. Subsequently, 45 parts of the core absorber (15 parts of WO3 and 30 parts of Bi2O3) and 12 parts of the synergistic reinforcing components (6.67 parts of Y2O3 and 5.33 parts of Nd2O3) were added to a planetary ball mill. Anhydrous ethanol was used as the dispersion medium, with a liquid-to-solid ratio of 1.2:1. Zirconia grinding balls with a diameter of 8 mm were used, with a ball-to-material ratio of 15:1 and a rotation speed of 300 r / min. The milling was carried out for 4 hours, and the temperature inside the mill was controlled to be ≤55℃. The slurry after ball milling was vacuum dried at 70℃ for 6 hours to obtain a mixed powder with a D50 of 150 nm.

[0036] Matrix preparation: 20.98 parts of epoxy resin E-51 from 43 parts of matrix components were heated to 50℃, and 0.63 parts of polyvinylpyrrolidone were added under stirring at 300 r / min. The mixture was stirred for 30 min until dissolved. 21.39 parts of methyltetrahydrophthalic anhydride were added, and the mixture was stirred for 20 min under nitrogen protection to obtain the modified epoxy resin matrix.

[0037] Composite molding: After the mixed powder is added to the matrix, it is ultrasonically dispersed at 38℃ for 60 min at a frequency of 35 kHz and a power of 600 W, and magnetically stirred at 800 r / min; after the slurry is poured into the mold, it is cured at 80℃ for 2 h, then cured again at 150℃ for 4 h, and a pressure of 0.15 MPa is applied; after cooling to 25℃, it is demolded to obtain the target material.

[0038] Performance test: Density 4.8 g / cm³ 3X-ray absorption performance (125kV tube voltage, 5mA tube current): lead equivalent 1.2mmPb, half-value layer 2.0mm, shielding efficiency 98.2%; mechanical properties: tensile strength 42MPa, elongation at break 4.8%, no cracking after 1200 cycles of ±90° bending; lead equivalent 1.15mmPb after high temperature and humidity aging, fluctuation 3.8%; no heavy metals detected, VOC emission 0.25mg / m³. 3 It has a cytotoxicity level of 1 and meets the requirements for medical protective materials.

[0039] Example 3

[0040] A high X-ray absorbing material based on metal oxide composites, with the following components:

[0041] 1. Component ratio, by mass percentage: core absorber 30%, synergistic reinforcing component 8%, matrix component 62%; wherein the core absorber is a mixture of WO2 and Bi2O3 in a mass ratio of 1:0.5, WO2 particle size 80nm, purity 99.9%, Bi2O3 particle size 150nm, purity 99.8%; the synergistic reinforcing component is a mixture of Y2O3 and Nd2O3 in a mass ratio of 1:0.3, particle size 60-100nm, purity 99.9%; the matrix component is modified epoxy resin, E-51:methyltetrahydrophthalic anhydride:polyvinylpyrrolidone = 100:80:1 mass ratio.

[0042] 2. Preparation method:

[0043] Pretreatment: The powder was dried under vacuum at 80℃ and -0.09MPa for 6 hours; 30 parts of the core absorber component (20 parts of WO2 and 10 parts of Bi2O3) and 8 parts of the synergistic reinforcing component (6.15 parts of Y2O3 and 1.85 parts of Nd2O3) were added to a ball mill at a liquid-to-solid ratio of 1:1, a ball-to-material ratio of 10:1, and a rotation speed of 200 r / min for 2 hours; the powder was then dried under vacuum at 60℃ for 8 hours to obtain a mixed powder with a D50 of 100 nm.

[0044] Matrix preparation: 34.44 parts of E-51 from 62 matrix components were heated to 40°C, and 0.34 parts of polyvinylpyrrolidone were added and stirred for 15 min to dissolve; 27.22 parts of methyltetrahydrophthalic anhydride were added and stirred for 10 min to obtain the matrix.

[0045] Composite molding: After the mixed powder is added to the matrix, it is ultrasonically dispersed at 30℃ for 30 min at a frequency of 25 kHz and a power of 400 W, and magnetically stirred at 500 r / min; after the slurry is poured into the mold, it is cured at 60℃ for 4 h, and then cured again at 120℃ for 6 h, with a pressure of 0.08 MPa applied; after cooling and demolding, the target material is obtained.

[0046] Performance test: Density 3.6 g / cm³ 3X-ray absorption performance (80kV tube voltage, 5mA tube current): lead equivalent 0.8mmPb, half-value layer 2.5mm, shielding efficiency 97.0%; mechanical properties: tensile strength 35MPa, elongation at break 5.5%, no cracking after 1000 cycles of ±90° bending; lead equivalent 0.76mmPb after high temperature and humidity aging, fluctuation 4.5%; no heavy metals detected, VOC emission 0.4mg / m³ 3 It has a cytotoxicity level of 1 and the cost is reduced by 15% compared to Example 2.

[0047] Comparative Example 1

[0048] 1. Sample Information: Commercially available lead plate, 99.9% purity, 1.0mm thickness, density 11.34g / cm³ 3 ;

[0049] 2. Performance Testing: X-ray absorption performance, 100kV tube voltage: lead equivalent 1.0mmPb, shielding efficiency 98.0%, half-value layer 2.1mm; Mechanical properties: tensile strength 15MPa, elongation at break 1.2%, cracking occurs after 50 repeated bending cycles at ±90°; Environmental stability: after aging at 85℃ / 85%RH for 48h, surface oxidation and corrosion, lead equivalent 0.915mmPb, fluctuation 8.5%; Environmental performance: lead content 99.9%, does not comply with RoHS directive, VOC not detected, no biocompatibility, lead is toxic.

[0050] Comparative Example 2

[0051] 1. Sample Information: Bi2O3 / epoxy resin composite material, Bi2O3 content 40%, particle size 200nm, purity 99.8%, epoxy resin E-51, curing agent methyltetrahydrophthalic anhydride, no synergistic reinforcing components; preparation method is the same as in Example 1, only the core absorber component is replaced with single Bi2O3, without Y2O3 and Nd2O3; sample size 100mm×100mm×5mm, density 3.8g / cm³. 3 ;

[0052] 2. Performance Testing: X-ray absorption performance, 100kV tube voltage: lead equivalent 0.6mmPb, shielding efficiency 92.3%, half-value layer 3.8mm; Mechanical properties: tensile strength 32MPa, elongation at break 4.5%, microcracks appear after 800 cycles of ±90° bending; Environmental stability: lead equivalent 0.556mmPb after aging, fluctuation 6.8%; Environmental performance: heavy metals not detected, VOC emission 0.35mg / m³ 3 Cytotoxicity level 1.

[0053] Comparative Example 3

[0054] 1. Sample Information: The composition ratio is the same as in Example 1, except that the synergistic enhancing components Y2O3 and Nd2O3 are removed, the core absorber component ratio is adjusted to 45%, and the matrix component remains at 55%; the preparation method is exactly the same as in Example 1; the sample size is 100mm × 100mm × 5mm, and the density is 4.1g / cm³. 3 ;

[0055] 2. Performance Testing: X-ray absorption performance, 100kV tube voltage: lead equivalent 0.75mmPb, shielding efficiency 94.5%, half-value layer 2.8mm; in the medium-high energy region, 150kV tube voltage, lead equivalent is only 0.6mmPb, shielding efficiency 88.2%, compared to 0.9mmPb and 96.0% in Example 1 of this invention; mechanical properties: tensile strength 36MPa, elongation at break 5.0%, no cracking after 1000 bends; environmental stability: lead equivalent 0.7125mmPb after aging, fluctuation 5.0%; environmental performance is consistent with Example 1.

[0056] X-ray absorption performance test

[0057] 1. Testing instruments: X-ray machine (tube voltage adjustment range 50-250kV, tube current 0-10mA), X-ray dosimeter (measurement range 0.01μSv / h-10Sv / h, accuracy ±2%), standard lead plate (purity ≥99.9%, thickness 0.1-2.0mm).

[0058] 2. Lead Equivalent Test: Prepare a standard sample of the material to be tested, measuring 100mm × 100mm × 5mm. Place the sample between the X-ray machine and the dosimeter. Adjust the tube voltage to 80-150kV and the tube current to 5mA. Measure the X-ray dose rate D0 without the sample. Measure the dose rate D1 after placing the sample. Calculate the shielding efficiency η = (1-D1 / D0) × 100%. Repeat the test with standard lead plates of different thicknesses. When the shielding efficiency of the lead plate matches that of the sample, the thickness of the lead plate is the lead equivalent of the sample.

[0059] 3. Half-value layer HVL test: Under the conditions of 100kV tube voltage and 5mA tube current, the sample thickness is gradually increased, and the dose rate at the corresponding thickness is tested. The dose rate-thickness curve is plotted. When the dose rate drops to 50% of the initial dose rate, the corresponding sample thickness is the half-value layer.

[0060] Mechanical property testing

[0061] 1. Tensile strength test: According to GB / T1040.1-2006 standard, the specimen is made into dumbbell shape (Type I). Using an electronic universal testing machine with a range of 0-500N and an accuracy of ±0.5%, the tensile test is conducted at a tensile speed of 5mm / min. The maximum tensile force when the specimen breaks is recorded, and the tensile strength σ=F / S is calculated, where F is the maximum tensile force and S is the effective cross-sectional area of ​​the specimen.

[0062] 2. Repeated bending test: The sample is made into a strip shape of 100mm×20mm×5mm. Using a bending tester, the bending angle is set to ±90° and the bending frequency is 10 times / min. The sample is bent continuously for more than 1000 times. The surface of the sample is observed to see if cracks or peeling occur, and the mechanical stability is determined.

[0063] Environmental stability test

[0064] 1. High temperature and high humidity aging test: According to GB / T2423.3-2016 standard, the sample is placed in a constant temperature and humidity chamber, the temperature is set to 85℃ and the relative humidity is 85%RH, and the aging time is 48h; after taking it out, it is naturally cooled to room temperature, and its lead equivalent is tested. The percentage fluctuation of lead equivalent before and after aging is calculated. A fluctuation of ≤5% is considered qualified.

[0065] 2. Corrosion resistance test: Immerse the sample in 5% NaCl solution, 10% H2SO4 solution and 10% NaOH solution respectively for 72 hours at room temperature; after taking it out, rinse it with distilled water and dry it. Observe whether there is rust, blistering or peeling on the sample surface. At the same time, test the change of lead equivalent to determine the corrosion resistance.

[0066] Environmental performance testing

[0067] 1. Hazardous heavy metal detection: In accordance with RoHS Directive 2011 / 65 / EU, inductively coupled plasma mass spectrometry (ICP-MS) shall be used to test the content of heavy metals such as lead, mercury, cadmium, and hexavalent chromium in the sample. The content of each heavy metal shall be ≤1000ppm and cadmium ≤100ppm.

[0068] 2. Volatile Organic Compounds (VOC) Detection: According to GB / T18583-2008 standard, place the sample in a 1m... 3 The climate chamber was set at 23℃ and 50% RH. After equilibration for 24 hours, the VOC concentration inside the chamber was measured using gas chromatography-mass spectrometry (GC-MS). The required release level was ≤0.5 mg / m³. 3 .

[0069] 3. Biocompatibility test: In accordance with ISO10993-5 standard, the cytotoxicity test (MTT method) was adopted. The sample extract was co-cultured with L929 cells for 24 hours, and the cell proliferation was observed. The cytotoxicity level was determined to be ≤1 to ensure good biocompatibility.

[0070] Table 1: Performance Tests

[0071]

[0072] As shown in Table 1, Example 1 of the present invention maintains X-ray absorption efficiency comparable to that of traditional lead plates while reducing density by 63%, improving mechanical properties by 153%, exhibiting better environmental stability, and being lead-free and environmentally friendly. Compared to Comparative Example 2, which is a single metal oxide composite material, the lead equivalent is increased by 66.7%, demonstrating significant advantages in wide-band absorption. Compared to Comparative Example 3, which lacks synergistic reinforcing components, the X-ray absorption efficiency in the mid-to-high energy range is increased by 50%, proving that the synergistic effect of the core absorbing component and the synergistic reinforcing component can effectively broaden the absorption frequency band and improve absorption efficiency, resulting in significant comprehensive performance advantages.

[0073] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or apparatus. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or apparatus that includes said element.

[0074] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

[0075] Those skilled in the art should understand that the above descriptions are merely several specific embodiments of the present invention, and not all embodiments.

Claims

1. A high X-ray absorbing material based on metal oxide composites, characterized in that, It consists of a core absorber, a synergistic enhancement component, and a matrix component. The components are as follows by mass percentage: core absorber 30%-50%, synergistic enhancement component 5%-15%, and the remainder is matrix component. The core absorber is a mixture of tungsten oxide and bismuth oxide in a mass ratio of 1:0.5-2.0; the tungsten oxide is selected from at least one of WO2 and WO3, with a particle size of 50-200 nm; the bismuth oxide is Bi2O3, with a particle size of 100-300 nm. The matrix component is a modified epoxy resin, which is composed of epoxy resin E-51, curing agent methyltetrahydrophthalic anhydride and dispersant polyvinylpyrrolidone, with a mass ratio of 100:80-100:1-3. The synergistic reinforcing component is a mixture of yttrium oxide and neodymium oxide in a mass ratio of 1:0.3-0.8; the yttrium oxide is Y2O3 and the neodymium oxide is Nd2O3.

2. A method for preparing a high X-ray absorption material based on a metal oxide composite as described in claim 1, characterized in that, Includes the following steps: (1) Pretreatment: Tungsten oxide, bismuth oxide, yttrium oxide and neodymium oxide were vacuum dried at 80-100℃ respectively; then the core absorber and the synergistic enhancement component were added to a planetary ball mill, anhydrous ethanol was used as the dispersion medium, the ball-to-material ratio was 10:1-15:1, the rotation speed was 200-300 r / min, and the ball milling was carried out for 2-4 hours to obtain mixed powder; (2) Matrix preparation: Heat epoxy resin E-51, add dispersant polyvinylpyrrolidone, stir for 15-30 min until dissolved; then add curing agent methyltetrahydrophthalic anhydride, stir for 10-20 min to obtain modified epoxy resin matrix; (3) Composite molding: The mixed powder is added to the modified epoxy resin matrix and ultrasonically dispersed at 30-40℃ with an ultrasonic frequency of 25-40kHz. At the same time, it is magnetically stirred at 500-800r / min to form a uniform slurry. Pour the slurry into the mold, cure at 60-80℃ for 2-4 hours, then raise the temperature to 120-150℃ and cure for 4-6 hours. Cool and demold to obtain the final product.

3. The method for preparing high X-ray absorbing materials based on metal oxide composites according to claim 2, characterized in that, In step (1), the vacuum drying time is 4-6 hours.

4. The method for preparing high X-ray absorption material based on metal oxide composites according to claim 2, characterized in that, In step (2), the heating temperature is 40-50℃.

5. The method for preparing a high X-ray absorption material based on metal oxide composites according to claim 2, characterized in that, In step (3), the ultrasonic dispersion time is 30-60 min.

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