Energy-degrading x-ray attenuating fiber, method of making and use thereof

Abstract

This invention belongs to the field of X-ray protection technology, and relates to a fiber with split-energy cyclic attenuation of X-rays, its preparation method, and its application. The fiber has radiation-shielding particles in both its outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, i.e., a metal element with an atomic number ≤ 60 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, i.e., a metal element with an atomic number ≥ 61 in the periodic table. The preparation method involves impregnating the fiber containing radiation-shielding particles in a coating containing radiation-shielding particles, followed by drying, thus obtaining the fiber with split-energy cyclic attenuation of X-rays. Application: Lead-free fabrics are woven from the fiber with split-energy cyclic attenuation of X-rays. The preparation method of this invention is simple, and the resulting lead-free fabric has excellent radiation protection performance.

Description

Technical Field

[0001] This invention belongs to the field of X-ray protection technology, and relates to a fiber that can cyclically attenuate X-rays by splitting energy, its preparation method and application. Background Technology

[0002] Radiation is a common phenomenon in daily life. For example, various electronic products such as mobile phones and computers emit radiation. In medical applications, X-rays are frequently used for diagnostic examinations and radiotherapy. Studies have shown that a single X-ray exposure is equivalent to several months of radiation exposure in a normal environment. Because X-rays have short wavelengths and strong penetrating power, they ionize the body upon entry, causing biological changes such as ionization and damage to proteins, enzymes, or cell membranes, leading to disease and harmful side effects. X-ray protective clothing can effectively reduce radiation hazards to medical personnel and patients; therefore, the long-term and high-efficiency protective performance of X-ray protective clothing is crucial.

[0003] Current X-ray protective clothing is mainly lead-based (mostly micro-lead), made of lead plates integrated into the outer shell of the textile garment. The protective fabric made of lead plates is over 5mm thick, not breathable, and quite stiff. For example, a lead apron with a lead equivalent of 0.5mmPb weighs 4.95kg, which can negatively impact medical personnel performing delicate movements. Furthermore, lead-based protective clothing has poor mechanical properties, such as poor resilience and fatigue resistance, making it prone to breakage at frequently bent areas like the elbows and wrists, thus compromising its protective function. In addition, lead is highly toxic and harmful to human health. The production of lead also generates a series of waste gases and wastewater, causing widespread pollution and negatively impacting the environment. Therefore, further research is needed to develop an environmentally friendly, lead-free material for effective X-ray protection.

[0004] In recent years, many existing technologies have disclosed the preparation and design routes of lead-free clothing, but most lead-free clothing has low radiation protection performance.

[0005] For example, patent application CN109461511B discloses a method for preparing X-ray protective fabric and X-ray protective clothing. It involves attaching nano-tantalum and tungsten oxide particles to silk threads and setting a coating with nano-tantalum and tungsten oxide on the surface of the fabric woven from the silk threads. However, when the coating thickness is 0.5 mm, the lead equivalent is only 0.24 mmPb, which is not good enough for the protection of some special parts.

[0006] For example, patent application CN105624821B discloses a barium sulfate / polyvinyl alcohol composite fiber and its preparation method. This composite fiber is manufactured by blending ultrafine barium sulfate with polyvinyl alcohol and then using a wet spinning process. The prepared composite fiber has a dry breaking strength of 2.0–8.0 cN / dtex, a dry breaking elongation of 15–40%, and an initial modulus of 60–100 cN / dtex. However, the radiation-shielding particles in this patent are barium sulfate, such as… Figure 2 As shown, barium sulfate only has a good shielding effect against low and medium energy X-rays. Barium sulfate has a weak absorption region and does not have a good shielding effect against high energy X-rays.

[0007] Therefore, it is necessary to study a fiber with excellent radiation protection properties, and then to produce lead-free fabrics with excellent radiation protection properties from it. Summary of the Invention

[0008] The purpose of this invention is to solve the problems existing in the prior art and to provide a fiber with excellent radiation protection performance that can cyclically attenuate X-rays and its preparation method, thereby obtaining a lead-free fabric with excellent radiation protection performance that can cyclically attenuate X-rays.

[0009] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0010] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, a metal element with an atomic number ≤ 60 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, a metal element with an atomic number ≥ 61 in the periodic table.

[0011] X-rays contain both high-energy and low-energy X-rays. When X-rays irradiate a fiber, only low-energy X-rays react with the low-atomic-number metal elements on the fiber's surface and are thus consumed. High-energy X-rays, on the other hand, enter the inner layer of the fiber and collide with the high-atomic-number metal elements there, undergoing a photoelectric effect (i.e., when X-rays interact with matter, all of their energy is transferred to the shell electrons of the matter's atoms, freeing them from the atomic nucleus and becoming free electrons, while the X-rays themselves are absorbed by the matter's atoms), thus being consumed. Simultaneously, high-energy X-rays are repeatedly reflected and scattered within the inner layer of the fiber, cyclically colliding with and undergoing a photoelectric effect with the high-atomic-number metal elements there, thus being consumed.

[0012] The design concept of the fiber for split-energy cyclic attenuation of X-rays in this invention is as follows:

[0013] High-energy X-rays are far more harmful to the human body than low-energy X-rays. Therefore, the fiber must contain metal elements with high atomic numbers to consume high-energy X-rays. If the high-atomic-number metal elements are located on the surface of the fiber, the high-energy X-rays will be reflected or scattered on the surface of the fiber and will be directed into the air or onto the human body, thus causing harm. Therefore, this invention controls the high-atomic-number metal elements to be located only in the inner layer of the fiber.

[0014] When a high atomic number metal element is located only in the inner layer of a fiber, if the inner layer of the fiber also contains a low atomic number metal element, some of the high-energy X-rays in the inner layer of the fiber will collide with the low atomic number metal element and thus cannot be effectively consumed. Therefore, the inner layer of the fiber cannot contain a low atomic number metal element.

[0015] When a high atomic number metal element is located only in the inner layer of a fiber and the inner layer of the fiber does not contain a low atomic number metal element, if the surface layer of the fiber does not contain a low atomic number metal element, a large number of low-energy X-rays will enter the inner layer of the fiber along with high-energy X-rays. The low-energy X-rays will collide with the high atomic number metal element. The low-energy X-rays cannot be consumed and will also steal the opportunity for high-energy X-rays to collide with the high atomic number metal element, so the high-energy X-rays cannot be fully consumed.

[0016] like Figure 2 As shown, for element W, 69.53 keV is its absorption edge. The absorption coefficient is small to the left of the absorption edge, so X-rays with energies lower than this are unlikely to knock out electrons in this layer. The absorption coefficient is large to the right of the absorption edge, so it is easier to knock out electrons and consume them through the photoelectric effect. Therefore, when high-energy X-rays such as 100 keV penetrate the structure of this invention, the radiation-shielding particles A on the surface are difficult to consume, while the radiation-shielding particles B inside the fiber undergo the photoelectric effect and can be consumed repeatedly. If the structure of this invention were not designed, there might not be any high atomic number metal elements in the path of high-energy X-rays such as 100 keV, so they would not be consumed and would pass through.

[0017] As a preferred technical solution:

[0018] The fiber described above, which cyclically attenuates X-rays by dividing energy, has a low atomic number metal element of barium or lanthanum, and a high atomic number metal element of bismuth, tungsten, gadolinium, or samarium.

[0019] The fiber described above, which cyclically attenuates X-rays by splitting energy, comprises radiation-shielding particles A being at least one of barium salt and lanthanum oxide; and radiation-shielding particles B being at least one of bismuth oxide, tungsten oxide, gadolinium oxide, and samarium oxide.

[0020] The fiber described above, which is a type of split-energy cyclic attenuation X-ray, has a barium salt of at least one selected from barium sulfate, barium chloride, and barium phosphate, and a lanthanum oxide of lanthanum oxide.

[0021] As described above, the fiber that cyclically attenuates X-rays by splitting energy has radiation-shielding particles B in spherical shape with a particle size of 50-500 nm; radiation-shielding particles A in spherical shape with a particle size of 200-500 nm; in this invention, the diameters of both types of radiation-shielding particles are at the nanoscale. Nanoparticles have a large specific surface area and a high probability of being consumed by collisions with X-rays.

[0022] The fiber described above for split-energy cyclic attenuation of X-rays has a surface layer thickness of 5–50 μm and a surface layer content of 30–40 wt% of radiation-shielding particles A; the inner layer diameter (or equivalent circle diameter if the inner layer cross-section is not circular) is 0.3–0.6 mm and the inner layer content of radiation-shielding particles B is 55–65 wt%.

[0023] The fiber described above, which cyclically attenuates X-rays, has an outer substrate of waterborne polyurethane and an inner substrate of at least one of thermoplastic polyurethane, polyamide, polyvinyl chloride, and polyvinyl alcohol.

[0024] The present invention also provides a method for preparing a fiber for split-energy cyclic attenuation of X-rays as described in any of the preceding claims, wherein the fiber containing radiation-shielding particles is repeatedly impregnated in a coating containing radiation-shielding particles and then dried to obtain the fiber for split-energy cyclic attenuation of X-rays, wherein the radiation-shielding particles in the fiber are all radiation-shielding particles B, and the radiation-shielding particles in the coating are all radiation-shielding particles A.

[0025] As a preferred technical solution:

[0026] As described above, the fiber containing radiation-shielding particles is obtained by wet spinning. The fiber prepared by wet spinning has pores inside. For continuous fibers, the pores inside are more likely to deform and break when stretched. Coating the fiber will form a non-porous continuous polymer on the fiber surface, which is less likely to deform and break when stretched, thus greatly improving the strength per unit area.

[0027] A lead-free fabric for partial energy cyclic attenuation of X-rays, woven from a fiber for partial energy cyclic attenuation of X-rays as described in any of the preceding claims.

[0028] The present invention provides a lead-free fabric for split-energy cyclic attenuation of X-rays as described above, which is a woven fabric with a multi-layer structure, wherein the number of layers in the multi-layer structure is at least 2.

[0029] The fabric of the present invention has a multi-layer structure. When X-rays pass through the fabric, each layer can attenuate once, and the multiple layers can cyclically attenuate. At the same time, the fabric of the present invention is a woven fabric, which is a high-density fabric and has a good protective effect.

[0030] As a preferred technical solution:

[0031] The lead-free fabric described above, which cyclically attenuates X-rays, has a warp density of 400–600 threads / 10cm, a weft density of 400–700 threads / 10cm, and a density of 0.7–1.1 g / cm³. 3 With a lead equivalent of 0.35–0.55 mmPb, it achieves a shielding efficiency of over 93% against X-rays with an energy of 130 keV.

[0032] Beneficial effects:

[0033] (1) As Figure 1 As shown, the fiber for cyclic attenuation of X-rays prepared by this invention can ensure that high atomic number metal elements are uniformly distributed inside the fiber. When X-rays are injected, the probability of high-energy X-rays colliding with high atomic number metal elements is increased, thereby enhancing the shielding effect.

[0034] (2) In this invention, low-energy X-rays are consumed through the surface layer of the fiber first, and high-energy X-rays are consumed through the inner layer of the fiber. One layer of fiber can be attenuated twice, two layers of fiber can be attenuated four times, and the same applies to multiple layers of fiber. Therefore, after weaving a fabric with a multi-layer structure, a split-energy cyclic attenuation structure is constructed.

[0035] (3) The fiber surface layer of the split-energy cyclic attenuation X-ray prepared by the present invention will form a continuous polymer without pores, which can reduce the weak links in the internal pores of the fiber and improve the mechanical properties of the fiber. Attached Figure Description

[0036] Figure 1 This is a schematic cross-sectional view of the fiber for split-energy cyclic attenuation of X-rays prepared according to the present invention.

[0037] Figure 2 Images showing the absorption coefficients of different metallic elements for X-rays;

[0038] Figure 3 This is an electron microscope image of the fiber with split-energy cyclic attenuation X-rays prepared in Example 1 of the present invention. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0040] The test methods for the relevant performance indicators in the following embodiments and comparative examples are as follows:

[0041] Shielding efficiency against 130keV X-rays: The lead equivalent of the lead-free fabrics in each embodiment and comparative example was tested according to GBZ / T 147-2002. The X-ray tube voltage was 130keV, and the thickness of the filter copper plate was 0.25mm. The shielding efficiency against 130keV X-rays was calculated using the following formula:

[0042] η = n0 - n d n0-n b ×100%;

[0043] In the formula: η represents the shielding efficiency (%) for X-rays with an energy of 130 keV; n0 is the dose rate without lead-free fabric; n d The dose rate after adding lead-free fabric; n b This is the baseline rate.

[0044] Fiber stress and strain: Following GB / T 14337-2022 "Test Method for Tensile Properties of Short Chemical Fibers", a certain amount of fiber is randomly selected from the short fiber sample, ensuring that the fibers do not overlap or cross each other. Appropriate pretreatment, such as humidification or heating, is performed on the sample according to the fiber properties and test requirements. The length of the fiber sample is measured to determine its length range and average length. Test conditions: The test is conducted under constant temperature conditions, typically 20±2℃; the relative humidity should be 65%±3%. Before starting the stretching, a certain pre-tension should be applied to the fiber sample to eliminate slack and bending in the fixture. As the fiber sample is stretched, the load and elongation should be recorded. A load-elongation curve is plotted, and characteristic points at each stage are recorded, such as the yield point, maximum load point, and breaking point.

[0045] Lead equivalent: The lead equivalent values ​​of the lead-free fabrics of each embodiment and comparative example were tested at a tube voltage of 60 to 120 keV. The test values ​​should be no less than 5, and the minimum value was taken as the lead equivalent of the lead-free fabric.

[0046] Example 1

[0047] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, metal element with the number 56 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, metal elements with the numbers 83 and 74 in the periodic table, respectively.

[0048] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0049] (1) Preparation of raw materials;

[0050] Radiation-protecting particle A: Barium sulfate, spherical in shape, with an average particle size of 200 nm;

[0051] Radiation-resistant particles B: a mixture of bismuth oxide and tungsten oxide in a mass ratio of 1:1, spherical in shape, with an average particle size of 100 nm;

[0052] Solvent: DMF (N,N-dimethylformamide), manufactured by Shanghai Aladdin Biochemical Technology Co., Ltd., brand name D111998;

[0053] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0054] Thermoplastic polyurethane: Manufacturer is Dongguan Jinheng Plastics Co., Ltd., grade 3685AU;

[0055] (2) Prepare fibers containing radiation-resistant particles;

[0056] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, thermoplastic polyurethane is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0057] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.1 mL / min, wet spinning machine needle 22G;

[0058] The obtained fiber containing radiation-shielding particles has a stress of 12 MPa and a strain of 500%.

[0059] (3) Prepare coatings containing radiation-resistant particles;

[0060] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0061] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed in the coating containing radiation-shielding particles obtained in step (3) 4 times, and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0062] The final fabricated fiber with split-energy cyclic attenuation of X-rays (such as...) Figure 3The outer layer (as shown) has a thickness of 50 μm and contains 40 wt% of radiation-shielding particles A; the inner layer has a diameter of 0.3 mm and contains 65 wt% of radiation-shielding particles B; the fiber for splitting energy cyclic attenuation of X-rays has a stress of 20 MPa and a strain of 800%.

[0063] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with three layers.

[0064] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 600 threads / 10cm, a weft density of 700 threads / 10cm, and a density of 1.1 g / cm³. 3 With a lead equivalent of 0.55 mmPb, it achieves a shielding efficiency of 98% against X-rays with an energy of 130 keV.

[0065] Comparative Example 1

[0066] A method for preparing a fiber that can cyclically attenuate X-rays is basically the same as in Example 1, except that the radiation-shielding particle B in step (2) of Example 1 is replaced with a mixture of radiation-shielding particles A and B of equal mass (the mass ratio of radiation-shielding particles A to radiation-shielding particles B is 1:1).

[0067] A lead-free fabric for partial energy cyclic attenuation of X-rays is basically the same as in Example 1, except that the fibers for partial energy cyclic attenuation of X-rays in Example 1 are replaced with the fibers for partial energy cyclic attenuation of X-rays in Comparative Example 1.

[0068] The lead-free fabric for partial energy cyclic attenuation of X-rays was finally produced with a lead equivalent of 0.31 mmPb and a shielding efficiency of 85% for X-rays with an energy of 130 keV.

[0069] Comparing Comparative Example 1 and Example 1, it can be seen that the shielding efficiency of the X-ray splitting cyclic attenuation fiber for high-energy X-rays is reduced because the inner layer of the fiber in Comparative Example 1 contains both radiation-shielding particles A and B. This is because some of the high-energy X-rays in the inner layer of the fiber will collide with metal elements with low atomic numbers and thus cannot be effectively consumed.

[0070] Comparative Example 2

[0071] A method for preparing a fiber that cyclically attenuates X-rays is basically the same as in Example 1, except that: in step (1), radiation-shielding particles A are not prepared; in step (3), water-based polyurethane is stirred to obtain a coating; and in step (4), the coating containing radiation-shielding particles in Example 1 is replaced with an equal mass of the coating in step (3) of this comparative example.

[0072] A fabric for cyclically attenuating X-rays is basically the same as in Example 1, except that the split-energy cyclically attenuating X-ray fibers of Example 1 are replaced with the cyclically attenuating X-ray fibers of Comparative Example 2.

[0073] The final fabric for cyclically attenuating X-rays has a lead equivalent of 0.37 mmPb and a shielding efficiency of 81% for X-rays with an energy of 130 keV.

[0074] Comparing Comparative Example 2 and Example 1, it can be seen that since the coating in Comparative Example 2 does not contain radiation-shielding particles A, the shielding efficiency against X-rays with an energy of 130 keV is reduced. This is because low-energy X-rays cannot be consumed on the surface, and a large number of low-energy X-rays enter the inner layer of the fiber along with high-energy X-rays. Low-energy X-rays will collide with metal elements with high atomic numbers. Since low-energy X-rays cannot be consumed, they will also steal the opportunity for high-energy X-rays to collide with metal elements with high atomic numbers, and high-energy X-rays cannot be fully consumed.

[0075] Example 2

[0076] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, metal element with the number 56 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, metal element with the number 83 in the periodic table.

[0077] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0078] (1) Preparation of raw materials;

[0079] Radiation-protecting particle A: Barium chloride, spherical in shape, with an average particle size of 300 nm;

[0080] Radiation-protecting particle B: Bismuth oxide, spherical in shape, with an average particle size of 50 nm;

[0081] Solvent: DMSO (dimethyl sulfoxide), manufactured by Shanghai Mairui Biochemical Technology Co., Ltd., brand name M23322;

[0082] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0083] The inner substrate is polyamide, manufactured by Suzhou Qianhui Plastic Products Co., Ltd., and its grade is PA6-EPR27.

[0084] (2) Prepare fibers containing radiation-resistant particles;

[0085] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, polyurethane is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0086] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.2 mL / min, wet spinning machine needle 18G;

[0087] The obtained fiber containing radiation-shielding particles has a stress of 11 MPa and a strain of 480%.

[0088] (3) Prepare coatings containing radiation-resistant particles;

[0089] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0090] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed in the coating containing radiation-shielding particles obtained in step (3) three times, and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0091] The final fiber for partial energy cyclic attenuation of X-rays has a surface layer thickness of 45 μm and a content of 30 wt% of radiation-shielding particles A; the inner layer has a diameter of 0.6 mm and a content of 55 wt% of radiation-shielding particles B; the fiber for partial energy cyclic attenuation of X-rays has a stress of 17 MPa and a strain of 680%.

[0092] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with two layers.

[0093] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 400 threads / 10cm, a weft density of 400 threads / 10cm, and a density of 0.7 g / cm³. 3 With a lead equivalent of 0.35 mmPb, it achieves a shielding efficiency of 93% against X-rays with an energy of 130 keV.

[0094] Example 3

[0095] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, metal element number 56 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, metal element number 74 in the periodic table.

[0096] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0097] (1) Preparation of raw materials;

[0098] Radiation-protecting particle A: Barium phosphate, spherical in shape, with an average particle size of 500 nm;

[0099] Radiation-protecting particles B: Tungsten oxide, spherical in shape, with an average particle size of 200 nm;

[0100] Solvent: DMF, manufactured by Shanghai Aladdin Biochemical Technology Co., Ltd., brand name D111998;

[0101] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0102] The inner layer substrate is polyvinyl chloride, manufactured by Dongguan Jinheng Plastics Co., Ltd., and the grade is PVC16-2000 mesh.

[0103] (2) Prepare fibers containing radiation-resistant particles;

[0104] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, polyvinyl chloride is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0105] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.1 mL / min, wet spinning machine needle 19G;

[0106] The obtained fiber containing radiation-shielding particles has a stress of 8 MPa and a strain of 350%.

[0107] (3) Prepare coatings containing radiation-resistant particles;

[0108] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0109] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed in the coating containing radiation-shielding particles obtained in step (3) once, and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0110] The final fiber for partial energy cyclic attenuation of X-rays has a surface layer thickness of 15 μm and a content of 35 wt% of radiation-shielding particles A; the inner layer has a diameter of 0.5 mm and a content of 60 wt% of radiation-shielding particles B; the fiber for partial energy cyclic attenuation of X-rays has a stress of 14 MPa and a strain of 550%.

[0111] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with three layers.

[0112] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 450 threads / 10cm, a weft density of 550 threads / 10cm, and a density of 0.99 g / cm³. 3 With a lead equivalent of 0.48 mmPb, it achieves a shielding efficiency of 95% against X-rays with an energy of 130 keV.

[0113] Example 4

[0114] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, metal element number 56 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, metal element number 64 in the periodic table.

[0115] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0116] (1) Preparation of raw materials;

[0117] Radiation-resistant particles A: a mixture of barium chloride and barium phosphate in a mass ratio of 1:1, spherical in shape, with an average particle size of 400 nm;

[0118] Radiation-protecting particle B: Gadolinium oxide, spherical in shape, with an average particle size of 500 nm;

[0119] Solvent: DMF, manufactured by Shanghai Aladdin Biochemical Technology Co., Ltd., brand name D111998;

[0120] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0121] The inner substrate is polyvinyl alcohol, manufactured by Shanghai Chenqi Chemical Technology Co., Ltd., with the grade PVA0588.

[0122] (2) Prepare fibers containing radiation-resistant particles;

[0123] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, polyvinyl alcohol is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0124] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.3 mL / min, wet spinning machine needle 20G;

[0125] The obtained fiber containing radiation-shielding particles has a stress of 8 MPa and a strain of 320%.

[0126] (3) Prepare coatings containing radiation-resistant particles;

[0127] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0128] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed in the coating containing radiation-shielding particles obtained in step (3) once, and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0129] The final fiber for partial energy cyclic attenuation of X-rays has a surface layer thickness of 5 μm and a content of 35 wt% of radiation-shielding particles A; the inner layer has a diameter of 0.4 mm and a content of 55 wt% of radiation-shielding particles B; the fiber for partial energy cyclic attenuation of X-rays has a stress of 13 MPa and a strain of 440%.

[0130] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with two layers.

[0131] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 550 threads / 10cm, a weft density of 450 threads / 10cm, and a density of 0.75 g / cm³. 3 With a lead equivalent of 0.37 mmPb, it achieves a shielding efficiency of 94% against X-rays with an energy of 130 keV.

[0132] Example 5

[0133] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, metal element with the number 56 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, metal elements with the numbers 83 and 64 in the periodic table, respectively.

[0134] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0135] (1) Preparation of raw materials;

[0136] Radiation-resistant particles A: a mixture of barium sulfate, barium chloride, and barium phosphate in a mass ratio of 1:1:1, spherical in shape, with an average particle size of 300 nm;

[0137] Radiation-resistant particles B: a mixture of bismuth oxide and gadolinium oxide in a 1:1 mass ratio, spherical in shape, with an average particle size of 300 nm;

[0138] Solvent: DMSO, manufactured by Shanghai Mairui Biochemical Technology Co., Ltd., brand name M23322;

[0139] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0140] Thermoplastic polyurethane: Manufacturer is Hybes Materials Co., Ltd., grade TPU-9380A;

[0141] (2) Prepare fibers containing radiation-resistant particles;

[0142] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, thermoplastic polyurethane is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0143] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.2 mL / min, wet spinning machine needle 21G;

[0144] The obtained fiber containing radiation-shielding particles has a stress of 8.5 MPa and a strain of 430%.

[0145] (3) Prepare coatings containing radiation-resistant particles;

[0146] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0147] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed twice in the coating containing radiation-shielding particles obtained in step (3), and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0148] The final fiber for partial energy cyclic attenuation of X-rays has a surface layer thickness of 30 μm and a content of 40 wt% of radiation-shielding particles A; the inner layer has a diameter of 0.35 mm and a content of 60 wt% of radiation-shielding particles B; the fiber for partial energy cyclic attenuation of X-rays has a stress of 16 MPa and a strain of 580%.

[0149] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with three layers.

[0150] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 580 threads / 10cm, a weft density of 650 threads / 10cm, and a density of 1.05 g / cm³. 3 With a lead equivalent of 0.52 mmPb, it achieves a shielding efficiency of 96% against X-rays with an energy of 130 keV.

[0151] Example 6

[0152] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, that is, metal element with the number 57 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, that is, metal elements with the numbers 83 and 74 in the periodic table, respectively.

[0153] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0154] (1) Preparation of raw materials;

[0155] Radiation-protecting particle A: Lanthanum oxide, spherical in shape, with an average particle size of 200 nm;

[0156] Radiation-resistant particles B: a mixture of bismuth oxide and tungsten oxide in a mass ratio of 1:1, spherical in shape, with an average particle size of 100 nm;

[0157] Solvent: DMF, manufactured by Shanghai Aladdin Biochemical Technology Co., Ltd., brand name D111998;

[0158] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0159] Thermoplastic polyurethane: Manufacturer is Hybes Materials Co., Ltd., grade TPU-9380A;

[0160] (2) Prepare fibers containing radiation-resistant particles;

[0161] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, thermoplastic polyurethane is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0162] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.1 mL / min, wet spinning machine needle 22G;

[0163] The obtained fiber containing radiation-shielding particles has a stress of 9.5 MPa and a strain of 380%.

[0164] (3) Prepare coatings containing radiation-resistant particles;

[0165] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0166] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed in the coating containing radiation-shielding particles obtained in step (3) three times, and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0167] The final fiber for split-energy cyclic attenuation of X-rays has a surface layer thickness of 40 μm and a content of 40 wt% of radiation-shielding particles A; the inner layer has a diameter of 0.3 mm and a content of 65 wt% of radiation-shielding particles B; the fiber for split-energy cyclic attenuation of X-rays has a stress of 18 MPa and a strain of 640%.

[0168] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with three layers.

[0169] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 600 threads / 10cm, a weft density of 700 threads / 10cm, and a density of 1.1 g / cm³.3 With a lead equivalent of 0.49 mmPb, it achieves a shielding efficiency of 97% against X-rays with an energy of 130 keV.

[0170] Example 7

[0171] A fiber that cyclically attenuates X-rays by dividing energy is a fiber with radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are denoted as radiation-shielding particle A, and the metal elements in radiation-shielding particle A are metal elements with low atomic numbers, that is, metal elements with serial numbers 56 and 57 in the periodic table. The radiation-shielding particles in the inner layer are denoted as radiation-shielding particle B, and the metal elements in radiation-shielding particle B are metal elements with high atomic numbers, that is, metal elements with serial numbers 62 and 64 in the periodic table.

[0172] The method for preparing the fiber with split-energy cyclic attenuation of X-rays as described above comprises the following steps:

[0173] (1) Preparation of raw materials;

[0174] Radiation-resistant particles A: a mixture of lanthanum oxide and barium chloride in a mass ratio of 1:1, spherical in shape, with an average particle size of 200 nm;

[0175] Radiation-resistant particles B: a mixture of samarium oxide and gadolinium oxide in a mass ratio of 1:1, spherical in shape, with an average particle size of 100 nm;

[0176] Solvent: DMF, manufactured by Shanghai Aladdin Biochemical Technology Co., Ltd., brand name D111998;

[0177] Waterborne polyurethane: Manufacturer is Shenzhen Yoshida Chemical Co., Ltd., and the grade is waterborne polyurethane F0402;

[0178] Thermoplastic polyurethane: Manufacturer is Hybes Materials Co., Ltd., grade TPU-9380A;

[0179] (2) Prepare fibers containing radiation-resistant particles;

[0180] After mixing radiation-resistant particles B with a solvent, the mixture is first subjected to ultrasonic treatment to ensure that the radiation-resistant particles B are evenly dispersed in the solvent. Then, thermoplastic polyurethane is added and the mixture is stirred on a magnetic stirrer for 12 hours to prepare a spinning solution. The spinning solution is then allowed to stand for 30 minutes to remove bubbles and is then extruded into fibers using a wet spinning machine to obtain fibers containing radiation-resistant particles.

[0181] The process parameters for preparing fibers containing radiation-resistant particles are: wet spinning machine extrusion speed 0.1 mL / min, wet spinning machine needle 22G;

[0182] The obtained fiber containing radiation-shielding particles has a stress of 11 MPa and a strain of 440%.

[0183] (3) Prepare coatings containing radiation-resistant particles;

[0184] Radiation-resistant particles A were added to waterborne polyurethane and stirred at 2000 r / min for 6 hours at 25°C to obtain a coating containing radiation-resistant particles.

[0185] (4) The fiber containing radiation-shielding particles obtained in step (2) is repeatedly immersed in the coating containing radiation-shielding particles obtained in step (3) three times, and then dried to obtain the fiber that can cyclically attenuate X-rays.

[0186] The final fiber for partial energy cyclic attenuation of X-rays has a surface layer thickness of 45 μm and a content of radiation-shielding particles A of 40 wt%; the inner layer has a diameter of 0.3 mm and a content of radiation-shielding particles B of 60 wt%; the fiber for partial energy cyclic attenuation of X-rays has a stress of 17 MPa and a strain of 640%.

[0187] A lead-free fabric for partial energy cyclic attenuation of X-rays is woven from the fibers prepared above for partial energy cyclic attenuation of X-rays. It is a multi-layered woven fabric with three layers.

[0188] The final lead-free fabric for partial energy cyclic attenuation X-rays has a warp density of 600 threads / 10cm, a weft density of 700 threads / 10cm, and a density of 1.15 g / cm³. 3 It has a lead equivalent of 0.47 mmPb and a shielding efficiency of 95% against X-rays with an energy of 130 keV.

Claims

1. A fiber for attenuating X-rays in a power-dividing cycle, characterized by, The fiber has radiation-shielding particles in both the outer and inner layers. The radiation-shielding particles in the outer layer are designated as radiation-shielding particle A, and the metal element in radiation-shielding particle A is a metal element with a low atomic number, such as barium or lanthanum. The radiation-shielding particles in the inner layer are designated as radiation-shielding particle B, and the metal element in radiation-shielding particle B is a metal element with a high atomic number, such as bismuth, tungsten, gadolinium, or samarium. Radiation-resistant particle A is at least one of barium salt and lanthanum oxide, wherein the barium salt is at least one of barium sulfate, barium chloride and barium phosphate, and the lanthanum oxide is lanthanum oxide; radiation-resistant particle B is at least one of bismuth oxide, tungsten oxide, gadolinium oxide and samarium oxide.

2. The energy-degrading x-ray attenuating fiber of claim 1, wherein, Radiation-resistant particle B is spherical with a particle size of 50~500nm; radiation-resistant particle A is spherical with a particle size of 200~500nm.

3. The fiber for split-energy cyclic attenuation of X-rays according to claim 2, characterized in that, The outer layer has a thickness of 5~50μm and contains 30~40wt% of radiation-shielding particles A; the inner layer has a diameter of 0.3~0.6mm and contains 55~65wt% of radiation-shielding particles B.

4. The energy-degrading x-ray attenuating fiber of claim 1, wherein, The surface layer substrate is waterborne polyurethane; the inner layer substrate is at least one of thermoplastic polyurethane, polyamide, polyvinyl chloride and polyvinyl alcohol.

5. A method of producing a fiber for attenuating X-rays in an energy-attenuating cycle according to any one of claims 1 to 4, characterized by, After impregnating fibers containing radiation-shielding particles in a coating containing radiation-shielding particles and drying them, fibers capable of cyclically attenuating X-rays are obtained. In this process, the radiation-shielding particles in the fibers are all radiation-shielding particles B, and the radiation-shielding particles in the coating are all radiation-shielding particles A.

6. A lead-free fabric attenuating X-rays in an energy-dependent manner, characterized in that It is woven from a fiber that cyclically attenuates X-rays according to any one of claims 1 to 4.

7. The non-lead fabric for attenuating X-rays of an energy-dispersive cycle according to claim 6, wherein It is a woven fabric with a multi-layer structure, and the number of layers in the multi-layer structure is at least 2; The warp density is 400-600 per 10 cm, the weft density is 400-700 per 10 cm, and the density is 0.7-1.15 g / cm 3 The lead equivalent is 0.35-0.55 mm Pb, and the shielding efficiency for X-rays with an energy of 130 keV is 93% or more.

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