Lead-based zeolite fiber composite material and preparation method thereof

Abstract

The present invention belongs to the technical field of X-ray radiation protection materials, and in particular relates to a lead-based zeolite fiber composite material and a preparation method thereof. Among them, a lead-based zeolite fiber composite material includes a lead-based zeolite and a fiber line, the lead-based zeolite is attached to the surface of the fiber line, the lead-based zeolite includes zeolite and lead element, the content of zeolite accounts for 25-50wt% of the zeolite fiber line, and the mass fraction of the lead element in the lead-based zeolite is 8%-13%. The preparation process of the present invention is simple, the lead-based zeolite in the prepared lead-based zeolite fiber composite material basically does not fall off under conditions of severe vibration, and the retention rate is greater than 96%. The prepared lead-based zeolite fiber composite material is soft, breathable, and has a high shielding rate against X-rays.

Description

Technical Field

[0001] The present invention belongs to the technical field of X-ray radiation protection materials, and in particular relates to a lead-based zeolite fiber composite material and a preparation method thereof. Background Art

[0002] With the rapid development of social economy and atomic energy science, people's lives have become more convenient and intelligent, and electromagnetic radiation has become increasingly widespread in daily life or work. Many workers are exposed to strong electromagnetic radiation in their daily work, such as computer operators, near-field workers in transmitter rooms of radio, television, communications, navigation, radar, etc., people who operate medical equipment such as radio frequency and microwaves for a long time, and workers in power generation and high-voltage transmission and substations.

[0003] While electromagnetic waves bring enormous benefits to people's lives, they also pose certain risks to human health. Long-term exposure to strong radiation sources can cause memory loss, dizziness, hair loss, changes in blood composition and function, and even fertility problems. In severe cases, they can also cause leukemia, bone tumors, and other diseases, posing a serious threat to human life. Therefore, it is essential for workers who are exposed to strong electromagnetic radiation for a long time to take daily precautions against electromagnetic radiation.

[0004] However, the most effective X-ray shielding materials currently used are heavy metals such as lead plates. However, protective equipment made of lead plates has poor air permeability, is bulky, and is uncomfortable and inconvenient to wear for long periods of time. Therefore, it is of great significance to develop protective materials that are light, flexible, breathable, and effective. Summary of the Invention

[0005] In order to overcome the bulkiness and poor air permeability of existing radiation protection materials, the present application provides a lead-based zeolite fiber composite material and a preparation method thereof.

[0006] In a first aspect, the present application provides a lead-based zeolite fiber composite material, which adopts the following technical solution:

[0007] A lead-based zeolite fiber composite material includes a lead-based zeolite and a fiber line. The lead-based zeolite is attached to the surface of the fiber line. The lead-based zeolite includes zeolite and lead elements. The content of the zeolite accounts for 25-50wt% of the zeolite fiber line, and the mass fraction of the lead element in the lead-based zeolite is 8%-13%.

[0008] Zeolite is a molecular sieve skeleton composed of Si, Al, P, B, Ga, and Ge as the most basic unit structure, which is then combined with shared oxygen atoms to form a three-dimensional network structure.

[0009] Through the above technical solution, zeolite with a microporous channel structure is loaded onto natural fibers with good elasticity, toughness and spinnability. The composite material composed of zeolite and fiber lines has a large specific surface area and pore material exchange capacity. The balanced metal charge ions outside the zeolite skeleton structure are then replaced with lead ions through ion exchange to prepare a lead-based zeolite fiber composite material. The lead-based zeolite fiber composite material prepared in this application is light in weight and has a simple preparation process. The lead-based zeolite fiber composite material has a three-dimensional network structure, and the rays are repeatedly absorbed by the lead in the three-dimensional network structure, so that the lead-based zeolite fiber composite material has a high shielding rate for X-rays.

[0010] Preferably, the particle size of the lead-based zeolite is 0.5-20 μm.

[0011] Through the above technical solution, when the lead-based zeolite particle size is too large, the lead-based zeolite adsorbs more lead, the weight increases, and the lead-based zeolite easily falls off from the lead-based zeolite fiber composite material, resulting in a decrease in the retention rate of the lead-based zeolite on the fiber; when the lead-based zeolite particle size is too large, the zeolite's adsorption capacity for lead elements is insufficient, which reduces the shielding rate of the lead-based zeolite fiber composite material against X-rays.

[0012] Preferably, the lead-based zeolite fiber composite material further includes a polymer coating, the polymer coating is attached to the surface of the zeolite fiber line, and the polymer coating is a polymer coating.

[0013] Through the above technical solution, on the one hand, by attaching a polymer coating to the surface of the fiber line to which the lead-based zeolite is attached, the bonding strength of the lead-based zeolite on the fiber line is improved, so that the lead-based zeolite has a higher retention rate on the fiber line.

[0014] On the other hand, since the adsorption of ions by zeolite includes physical adsorption and chemical adsorption, physical adsorption will undergo a certain degree of desorption under conditions such as high temperature. In order to reduce the desorption of lead-based zeolite fiber composite materials at higher temperatures, a polymer coating is attached to the surface of the lead-based zeolite. The polymer coating blocks the pores on the surface of the lead-based zeolite, thereby improving the stability of the adsorbed metal ions in the lead-based zeolite, so that the lead-based zeolite fiber composite materials continue to have a high shielding rate against X-rays.

[0015] Preferably, the polymer coating is a polymer coating containing anions.

[0016] Through the above technical solution, the polymer containing the anion polymer coating can better combine with the cation-containing lead-based zeolite during the process of forming the coating, so that the polymer coating is tightly attached to the lead-based zeolite and the bonding strength between the two is improved, which reduces the lead element from the lead-based zeolite after desorption of the lead-based zeolite, and makes the lead-based zeolite fiber composite material have a higher shielding rate for X-rays.

[0017] Preferably, the anionic polymer coating is polymerized from 20-30 parts of acrylic acid monomers and 2-4 parts of acrylonitrile; the acrylic acid monomers are one or more of acrylic acid, methacrylic acid, methyl methacrylate, and butyl acrylate.

[0018] Through the above technical solution, a coating network structure is formed by polymerization of acrylic monomers and acrylonitrile, which further improves the bonding strength between the anionic polymer coating and the lead-based zeolite, and further improves the shielding rate of the lead-based zeolite fiber composite material against X-rays.

[0019] Preferably, the lead-based zeolite further comprises silver ions, and the mass fraction of the silver ions in the lead-based zeolite is 3.8%-6%.

[0020] Through the above technical solution, since the polymer coating is formed on the zeolite fiber line at 55-65°C, the lead-based zeolite may fall off or be desorbed due to the large difference in thermal shrinkage between the lead-based zeolite and the fiber line.

[0021] By adsorbing silver ions on lead-based zeolite, the thermal conductivity of the lead-based zeolite is improved. At higher temperatures, the lead-based zeolite fiber composite material, on the one hand, makes the lead-based zeolite and the fiber line have a more consistent thermal shrinkage rate, and the lead-based zeolite maintains a higher retention rate on the fiber line; on the other hand, the temperature inside the lead-based zeolite is reduced more quickly, thereby reducing the desorption of the adsorbed metal ions by the zeolite, so that the lead-based zeolite fiber composite material still has a high shielding rate for X-rays after experiencing higher temperatures.

[0022] In addition, the lead element and the silver element work together to further improve the X-ray shielding rate of the lead-based zeolite fiber composite material.

[0023] Preferably, when the lead-based zeolite fiber composite material is shaken for 2 hours at a rotation speed of ≥120 r / min, the retention rate of the lead-based zeolite on the fiber line is >96%.

[0024] Through the above technical solution, the lead-based zeolite fiber composite material obtained has a higher lead-based zeolite retention rate, so that the lead-based zeolite fiber composite material has an excellent shielding rate for X-rays.

[0025] In a second aspect, the present application provides a method for preparing a lead-based zeolite fiber composite material.

[0026] A method for preparing a lead-based zeolite fiber composite material comprises the following steps:

[0027] ① Adding the zeolite fiber line to a treatment solution and ultrasonically treating it for 3-6 hours; the treatment solution comprises lead nitrate with a molar concentration of 0.3-0.8 mol / L and water;

[0028] ② Take out the soaked zeolite fiber line, wash it with deionized water, and dry it.

[0029] By adopting the above technical solution, the zeolite fiber wire is impregnated with a treatment liquid containing lead ions, and the ion exchange properties of zeolite are utilized to load the lead ions on the zeolite fiber wire, so that the prepared lead-based zeolite fiber composite material has an excellent shielding rate against X-rays. At the same time, the preparation process is simple and the preparation cycle is short.

[0030] Preferably, the treatment solution further comprises silver nitrate with a molar concentration of 0.1-0.3 mol / L.

[0031] By adopting the above technical solution, the zeolite is loaded with silver ions and lead ions at the same time, further improving the shielding rate of the lead-based zeolite fiber composite material against X-rays.

[0032] Preferably, the lead-based zeolite fiber composite material further comprises an anionic polymer coating;

[0033] The preparation process of the anionic polymer coating is as follows:

[0034] The zeolite fiber line is immersed in the coating mixture at a bath ratio of 1:(8-12), and then the temperature is raised to 55-65°C and ultrasonicated for 1-3 hours to prepare a polymer coating on the surface of the zeolite fiber line;

[0035] The preparation process of the coating mixture is as follows:

[0036] 30-35 parts of deionized water and 10-15 parts of ethylene glycol monoethyl ether are stirred and mixed to prepare a first solvent mixture;

[0037] Mixing acrylic monomer and acrylonitrile uniformly to prepare a second mixed solution;

[0038] Dissolve 0.1-0.3 parts of an initiator in 1-2 parts of acetone, stir, and prepare an initiator solution, and divide the initiator solution into a first initiator solution and a second initiator solution;

[0039] The first mixed solution was heated to 60-70° C., the second mixed solution and the first initiator solution were added, and the mixture was kept warm for 0.5-1 h to prepare a third mixed solution;

[0040] The temperature of the third mixed solution was lowered to 20-35° C., the second initiator solution was added, and then the pH was adjusted to 6-7 to prepare a coating mixed solution.

[0041] By adopting the above technical solution, silver ions and anionic polymer coatings are introduced into the zeolite fiber line to further improve the shielding rate of the lead-based zeolite fiber composite material against X-rays.

[0042] In summary, this application has the following beneficial effects:

[0043] 1. A lead-based zeolite fiber composite material includes lead-based zeolite and fiber lines. The lead-based zeolite is attached to the surface of the fiber lines. The lead-based zeolite includes zeolite and lead elements. The content of zeolite accounts for 25-50wt% of the zeolite fiber lines. The mass fraction of the lead element in the lead-based zeolite is 8%-13%. The preparation process of the present invention is simple. The lead-based zeolite in the prepared lead-based zeolite fiber composite material basically does not fall off under conditions of severe vibration, and the retention rate is greater than 96%. The prepared lead-based zeolite fiber composite material is soft, breathable, and has a high shielding rate for X-rays.

[0044] 2. The lead-based zeolite fiber composite material also includes a polymer coating, which is attached to the surface of the zeolite fiber line. On the one hand, the polymer coating improves the bonding strength of the lead-based zeolite on the fiber line, so that the lead-based zeolite has a higher retention rate on the fiber line; on the other hand, the polymer coating blocks the pores on the surface of the lead-based zeolite, thereby improving the stability of the metal ions adsorbed in the lead-based zeolite, so that the lead-based zeolite fiber composite material has a higher shielding rate against X-rays.

[0045] 3. Lead-based zeolite also includes silver ions. On the one hand, after the zeolite adsorbs silver ions, the thermal conductivity of the lead-based zeolite is improved, so that during the preparation of the polymer coating, the lead-based zeolite is reduced from detaching from the fiber line under heating conditions, and the desorption of the adsorbed metal ions by the zeolite is reduced, so that the lead-based zeolite fiber composite material has a higher shielding rate against X-rays. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 is a scanning electron microscope image of the lead-based zeolite fiber composite material of Example 1;

[0047] Figure 2 This is a scanning electron microscope image of the lead-based zeolite fiber composite material of Example 5. DETAILED DESCRIPTION

[0048] Preparation examples of raw materials and / or intermediates

[0049] Preparation Example 1

[0050] A coating mixture, using the raw material components shown in Table 1, is prepared as follows:

[0051] Stirring and mixing deionized water and ethylene glycol monoethyl ether to prepare a first solvent mixture;

[0052] Mixing acrylic monomer and acrylonitrile uniformly to prepare a second mixed solution;

[0053] Dissolve the initiator in acetone and stir to prepare an initiator solution, and divide the initiator solution into a first initiator solution and a second initiator solution;

[0054] The first mixed solution was heated to 60° C., and the second mixed solution and the first initiator solution were evenly added dropwise for 0.5 h. After the addition was complete, the mixture was kept warm for 1.5 h to prepare a third mixed solution.

[0055] The temperature of the third mixed solution was lowered to 35° C., and the second initiator solution was added. Then, the pH of the system was adjusted to 6 with 0.08 mol / L sodium bicarbonate solution to prepare a coating mixed solution. The coating mixed solution was placed at a temperature of 20° C., sealed and stored away from light for later use.

[0056] Preparation Example 2-6

[0057] A coating mixture is different from Preparation Example 1 in that the types and weight settings of raw materials used are different, and the preparation process of the coating mixture is different, as shown in Table 1.

[0058] Table 1 Types and weights of raw materials in Preparation Examples 1-6, and their preparation process settings

[0059]

[0060]

[0061] Preparation Example 7

[0062] A coating mixture is prepared, which differs from the preparation in Example 1 in that an equal amount of butyl acrylate is used in place of acrylic acid in the second mixture.

[0063] Preparation Example 8

[0064] A coating mixture, which differs from Preparation Example 1 in that acrylonitrile is not used in the second mixture.

[0065] Preparation Example 9

[0066] A coating mixed liquid, which is different from Preparation Example 1 in that the content of acrylonitrile in the second mixed liquid is 3 kg.

[0067] Preparation Example 10

[0068] A coating mixed liquid, which is different from Preparation Example 1 in that the content of acrylonitrile in the second mixed liquid is 4 kg.

[0069] Preparation Example 11

[0070] A zeolite fiber yarn, the preparation method of which comprises the following steps:

[0071] ① Prepare a zeolite precursor solution by composing the starting materials according to the following molar ratio: 10Na2O:Al2O3:9SiO2:300H2O. This zeolite precursor solution is then mixed with glycolide polymer fibers at a mass ratio of 1:200.

[0072] ② The glycolide polymer fiber and the uniformly mixed zeolite precursor solution were heat-treated at 90° C. for 24 h to prepare a zeolite fiber line with a zeolite content of 37 wt%.

[0073] Preparation Example 12

[0074] A zeolite fiber yarn, the preparation method of which comprises the following steps:

[0075] ① Prepare a zeolite precursor solution using the following molar ratio of 3 Na2O:Al2O3:2SiO2:120H2O as the starting material. This zeolite precursor solution is then mixed with polyester fiber at a mass ratio of 1:70.

[0076] ② The polyester fiber and the uniformly mixed zeolite precursor solution were heat-treated at 80° C. for 4 h to prepare a zeolite fiber line with a zeolite content of 50 wt%.

[0077] Preparation Example 13

[0078] A zeolite fiber yarn, the preparation method of which comprises the following steps:

[0079] ① Prepare a zeolite precursor solution using the following molar ratio of 10 Na₂O:Al₂O₃:9 SiO₂:200 H₂O as the starting materials. Mix the zeolite precursor solution with cotton fiber at a mass ratio of 1:25.

[0080] ② The cotton fiber and the uniformly mixed zeolite precursor solution were heat-treated at 90° C. for 24 h to prepare a zeolite fiber yarn with a zeolite content of 25 wt%.

[0081] Preparation Example 14

[0082] A zeolite fiber yarn, the preparation method of which comprises the following steps:

[0083] ① Prepare a zeolite precursor solution using the following molar ratio of 10 Na₂O:Al₂O₃:9 SiO₂:300 H₂O as the starting materials. This zeolite precursor solution is then mixed with lactide polymer fibers at a mass ratio of 1:50.

[0084] ② The lactide polymer fiber and the uniformly mixed zeolite precursor solution were heat-treated at 90° C. for 30 h to prepare a zeolite fiber line with a zeolite content of 26 wt%.

[0085] In other embodiments, the fiber lines 10-12 in the preparation examples can be selected from any one or more of rayon fiber, acetate fiber, carboxymethyl cellulose, linen fiber, wool, wood fiber, polyamide fiber (PA), polypropylene fiber (PP), polyethylene fiber (PE), polyvinyl chloride fiber (PVC), polyacrylonitrile fiber, and viscose fiber.

[0086] In other embodiments, the zeolite 10-12 in the preparation example can be replaced by aluminosilicate molecular sieves, phosphate molecular sieves, borate molecular sieves, or heteroatom molecular sieves.

[0087] Example

[0088] Example 1

[0089] A lead-based zeolite fiber composite material comprises a lead-based zeolite and a fiber line. The lead-based zeolite is attached to the surface of the fiber line. The lead-based zeolite comprises zeolite and lead elements.

[0090] The preparation steps of the lead-based zeolite fiber composite material are as follows, and the raw material components used are shown in Table 1:

[0091] ① Immerse the zeolite fiber yarn prepared in Preparation Example 11 in a treatment solution with a bath ratio of 1:6 and ultrasonically treat for 3 hours; the treatment solution comprises 0.3 mol / L lead nitrate and water;

[0092] ② The impregnated zeolite fiber line was taken out, washed with deionized water, and dried at 50° C. for 8 h to prepare a lead-based zeolite fiber composite material.

[0093] Example 2-3

[0094] A lead-based zeolite fiber composite material, which differs from Example 1 in that: the preparation of the zeolite fiber line, the concentration of lead nitrate, the preparation process parameter settings are different, and the particle size of the prepared lead-based zeolite is different, as shown in Table 2.

[0095] Table 2 Preparation of zeolite fiber yarns, concentration of lead nitrate, preparation process parameters and particle size setting list of the prepared lead-based zeolite in Examples 1-3

[0096] distinguish Example 1 Example 2 Example 3 Example 4 Lead nitrate concentration / (mol / L) 0.3 0.6 0.8 0.3 Zeolite fiber yarn Preparation Example 11 Preparation Example 12 Preparation Example 13 Preparation Example 14 Bath ratio 1:6 1:8 1:10 1:6 Processing time / h 3 5 6 3 D90 particle size of lead-based zeolite / μm 0.5 15 20 0.01

[0097] Example 5

[0098] A lead-based zeolite fiber composite material is different from Example 1 in that: the treatment liquid further includes silver nitrate with a molar concentration of 0.3 mol / L, and the lead-based zeolite fiber composite material further includes a polymer coating.

[0099] The preparation process of the polymer coating is as follows:

[0100] The zeolite fiber line was immersed in the coating mixture of Preparation Example 1 at a bath ratio of 1:8, and then heated to 65° C. and subjected to ultrasound for 1 hour to prepare a polymer coating on the surface of the zeolite fiber line.

[0101] Examples 6-7

[0102] A lead-based zeolite fiber composite material differs from Example 5 in that the concentration of silver nitrate in the treatment solution is set differently, the preparation of the coating mixture is different, and the process parameters for preparing the polymer coating are set differently, as shown in Table 3.

[0103] Table 3 Concentration of silver nitrate in the lead-based zeolite fiber composite material of Examples 5-7, preparation of the coating mixture, and process parameter settings for preparing the polymer coating

[0104] distinguish Example 5 Example 6 Example 7 Silver nitrate concentration / (mol / L) 0.3 0.2 0.1 Coating mixture Preparation Example 1 Preparation Example 2 Preparation Example 3 Bath ratio 1:8 1:10 1:12 Temperature / ℃ 65 60 55 Time / h 1 2 3

[0105] Example 8

[0106] A lead-based zeolite fiber composite material, which differs from Example 5 in that silver nitrate is not used in the treatment liquid.

[0107] Example 9

[0108] A lead-based zeolite fiber composite material, which differs from Example 5 in that no coating mixture is used in the treatment liquid.

[0109] Example 10

[0110] A lead-based zeolite fiber composite material is different from Example 5 in that the coating mixture is placed at a temperature of 65° C. for 1 hour before the zeolite fiber line is immersed in the coating mixture.

[0111] Examples 11-17

[0112] A lead-based zeolite fiber composite material, which differs from Example 5 in that the treatment liquid adopts Preparation Examples 4-10 in sequence.

[0113] Comparative Example

[0114] Comparative Example 1

[0115] A lead-based zeolite fiber composite material, which differs from Example 1 in that lead nitrate is not used in the treatment liquid.

[0116] Comparative Example 2

[0117] A lead-based zeolite fiber composite material is different from Example 1 in that the preparation of the zeolite fiber line is different. The preparation process of the zeolite fiber line is as follows:

[0118] ① Prepare zeolite precursor solution according to the following molar ratio: 5.5Na2O:1.65K2O:Al2O3:

[0119] A zeolite precursor solution was synthesized from 2.2SiO2:122H2O as the starting material. The zeolite precursor solution was mixed with silk fibers at a mass ratio of 1:10.

[0120] ② The silk fibers and the uniformly mixed zeolite precursor solution were heat-treated at 100° C. for 12 h to prepare a zeolite fiber yarn with a zeolite content of 15 wt%.

[0121] Comparative Example 3

[0122] A lead-based zeolite fiber composite material is different from Example 1 in that the preparation of the zeolite fiber line is different. The preparation process of the zeolite fiber line is as follows:

[0123] ① Prepare a zeolite precursor solution using the following molar ratio of 10 Na₂O:Al₂O₃:9 SiO₂:400 H₂O as the starting materials. This zeolite precursor solution is then mixed with bamboo fiber in a 1:2 weight ratio.

[0124] ② The bamboo fiber and the uniformly mixed zeolite precursor solution were heat-treated at 150° C. for 96 h to prepare a zeolite fiber yarn with a zeolite content of 80 wt%.

[0125] Performance testing

[0126] Test 1: Test method for the content of lead and silver elements: At room temperature (20+5°C), weigh 20 mL of the treatment liquid after treating zeolite fiber, 20 mL each (the treatment liquid is stirred for 10 minutes before each liquid collection), and use an atomic absorption spectrophotometer to determine the ion concentrations of lead ions and silver ions in the treatment liquid after treating zeolite fiber. The concentrations of the treatment liquid before treatment are known.

[0127] Q1=(C0-C2)*V / M*100%;

[0128] Q2=(C1-C3)*V / M*100%

[0129] Wherein: Q1 is the mass fraction of lead element in lead-based zeolite, unit: mg / g;

[0130] Q2 is the mass fraction of silver in lead-based zeolite, unit: mg / g;

[0131] The concentration of lead ions in the pretreatment solution of C0 treated zeolite fiber, unit: mg / L;

[0132] The concentration of silver ions in the pretreatment solution of zeolite fiber treated with C1, unit: mg / L;

[0133] The concentration of lead ions in the post-treatment solution of C2 treated zeolite fibers, unit: mg / L;

[0134] The concentration of silver ions in the post-treatment solution of C3 treated zeolite fibers, unit: mg / L;

[0135] V is the volume of the treatment liquid, unit: L;

[0136] M is the mass of lead-based zeolite, unit: g.

[0137] M was detected by TGA, and the content of lead-based zeolite in the lead-based zeolite fiber composite material immersed in the treatment liquid was calculated according to the ash content.

[0138] Test samples: The lead-based zeolite fiber composite materials of Examples 1-17 were used as test samples, and the lead-based zeolite fiber composite materials of Comparative Examples 1-3 were used as control samples.

[0139] Test results: The content of lead and silver elements in the lead-based zeolite fiber composite materials of Examples 1-17 and Comparative Examples 1-3 are shown in Table 4.

[0140] Table 4 List of test results of lead and silver content in lead-based zeolite fiber composite materials of Examples 1-17 and Comparative Examples 1-3

[0141]

[0142] Test 2: Retention Rate I

[0143] Test method: The lead-based zeolite fiber composite material was shaken on a shaker for 2 hours at a speed of 300 r / min, and the retention rate of the lead-based zeolite on the fiber was calculated.

[0144] Retention rate = (M1-M2) / M1*100%, M1 is the weight of the fabric before shock, and M2 is the weight of the fabric after shock.

[0145] Test samples: The lead-based zeolite fiber composite materials of Examples 1-17 were used as test samples, and the lead-based zeolite fiber composite materials of Comparative Examples 1-3 were used as control samples.

[0146] Test 3: Retention Rate II

[0147] Test method: The lead-based zeolite fiber composite material was shaken on a shaker for 2 hours, the water temperature was set to 55°C, and the rotation speed was 300 r / min, and the retention rate of the lead-based zeolite on the fiber was calculated.

[0148] Retention rate = (M1-M2) / M1*100%, M1 is the weight of the fabric before shock, and M2 is the weight of the fabric after shock.

[0149] Test samples: The lead-based zeolite fiber composite materials of Examples 1-17 were used as test samples, and the lead-based zeolite fiber composite materials of Comparative Examples 1-3 were used as control samples.

[0150] Test 4: Shielding Rate I

[0151] Test method: The shielding efficiency of the fiber material was measured using an X-ray detector (PTW32005). Test environment: Ambient temperature: 20±2°C, relative humidity: 50%, test voltage: 50kV.

[0152] Test Samples: The lead-based zeolite fiber composite materials of Examples 1-17 and Comparative Examples 1-3 were woven using a loom into a plain weave fabric with a linear density of 50 x 50. The samples were then stacked into seven layers (approximately 1.5 ± 0.1 mm thick) for testing. The fabrics produced in Examples 1-17 served as test samples, while the fabrics produced in Comparative Examples 1-3 served as control samples.

[0153] Test 5: Shielding Rate II

[0154] Test method: The shielding efficiency of the fiber material was measured using an X-ray detector (PTW32005). Test environment: Ambient temperature: 20±2°C, relative humidity: 50%, test voltage: 50kV.

[0155] Test samples: The lead-based zeolite fiber composite materials of Examples 1-17 and Comparative Examples 1-3 were woven into a plain weave fabric with a linear density of 50*50 using a textile machine, and the fabric was shaken on a shaker for 2 hours. The water temperature of the shaker was set to 55°C and the rotation speed was 300 r / min, and then the test was carried out.

[0156] The samples to be tested were stacked into 7 layers (thickness of about 1.5±0.1 mm) for testing. The fabrics prepared in Examples 1-17 were used as test samples, and the fabrics prepared in Comparative Examples 1-3 were used as control samples.

[0157] Test results: The retention rate I, retention rate II, shielding rate I and shielding rate II of the lead-based zeolite fiber composite materials of Examples 1-17 and Comparative Examples 1-3 are shown in Table 5.

[0158] Table 5 Results of the retention rate I, retention rate II, shielding rate I and shielding rate II of the fabrics made from the lead-based zeolite fiber composite materials of Examples 1-17 and Comparative Examples 1-3

[0159]

[0160]

[0161] Combining Examples 1-17 and Comparative Examples 1-3 and Table 5, it can be seen that:

[0162] Although the retention rates I and II of Examples 1-4 are not much different from those of Comparative Example 1, the shielding rates I and II of Examples 1-4 are significantly better than those of Comparative Example 1. This is because the zeolite in Comparative Example 1 has not been treated with lead ions and the lead ion content is relatively low, resulting in poor shielding rates I and II. The retention rates I and II of Comparative Document 2 are worse than those of Examples 1-4, which may be due to the lower zeolite content.

[0163] The retention rates I, II, I and II of Examples 1-4 are significantly better than those of Comparative Example 3. This may be because the zeolite content of Comparative Example 3 is relatively high. After adsorbing more lead ions, the weight of the lead-based zeolite is heavier, causing the lead-based zeolite to fall off the fiber line, resulting in lower retention rates I, II, I and II of Comparative Example 3. When the zeolite content is roughly the same, the lead content and the X-ray retention rate of Example 4 are lower than those of Example 1. This may be because the particle size of the lead-based zeolite in Example 4 is smaller. Under the premise that the metal ions can fully impregnate the lead-based zeolite, the lead-based zeolite with a smaller particle size has more incomplete pores, resulting in a reduced adsorption of lead ions, making the lead content and the X-ray shielding rate of Example 4 lower than those of Example 1.

[0164] The retention rate I, retention rate II, shielding rate I and shielding rate II of Examples 5-17 are better than those of Examples 1-4, indicating that by wrapping the polymer coating on the zeolite fiber line and loading silver ions on the zeolite fiber line, the shielding rate of the zeolite fiber composite material against X-rays and the retention rate of the lead-based zeolite on the fiber line are further improved.

[0165] The X-ray shielding rate of Examples 5-7 is better than that of Examples 8-9 and Example 1. The possible reason is that the lead ions in the zeolite are used in combination with the silver ions, which improves the X-ray shielding rate of the lead-based zeolite. The silver ions improve the thermal conductivity of the lead-based zeolite and the compatible polymer coating, thereby improving the retention rate of the lead-based zeolite on the fiber fabric and the X-ray shielding rate.

[0166] The X-ray shielding rate of Example 10 is lower than that of Example 5, indicating that Example 5 uses a polymer coating formed by first adsorbing the oligomer in the coating mixture on the lead-based zeolite and then heating to initiate a polymerization reaction. The zeolite fiber composite material prepared has a good X-ray shielding rate and a lead-based zeolite retention rate on the fiber line. This may be because the oligomer is adsorbed on the surface of the lead-based zeolite. During the subsequent heating polymerization process, the metal ions will not be separated from the lead-based zeolite, resulting in a higher retention rate of the metal ions in the lead-based zeolite. On the other hand, compared with Example 10, in which the oligomer first reacts and then is compounded with the lead-based zeolite and the fiber line, the polymer coating formed by first compounding the oligomer with the lead-based zeolite and the fiber line and then polymerizing has a better wrapping property for the lead-based zeolite and the fiber line.

[0167] The shielding rates of Examples 5-7 and Examples 12-13 are better than those of Example 11 and Example 14. The test results show that when acrylic acid and methyl methacrylate are used in combination in the polymer coating, the zeolite fiber composite material has a good shielding rate for X-rays and a retention rate of lead-based zeolite; this may be because the anions in the polymer coating can enhance the adsorption capacity between the polymer coating and the lead-based zeolite and fiber line adsorbed with cations, so that the polymer coating has a higher bonding strength with the lead-based zeolite and fiber line; however, if the polymer coating contains more anions, the water resistance of the polymer coating decreases, which will weaken the bonding force between the polymer coating and the lead-based zeolite and fiber line.

[0168] The shielding rate of Example 5 is better than that of Examples 15-17. The test results show that the polymer coating contains an appropriate amount of multifunctional substances, which can improve the shielding rate of the zeolite fiber composite material against X-rays and the retention rate of the lead-based zeolite; this may be because acrylonitrile contains unsaturated double bonds and isocyanate groups, which can cross-link the coating into a network structure in the polymer coating, thereby enhancing the bonding strength between the polymer coating and the lead-based zeolite and fiber line. However, if the acrylonitrile content is too high, the elasticity of the polymer coating decreases, and the wrapping of the lead-based zeolite and fiber line is reduced. If the acrylonitrile content is too low, the retention rate of the lead-based zeolite and the improvement of the shielding rate of the zeolite fiber composite material against X-rays are not obvious.

[0169] Test 6: Air permeability test method: Use an air permeability meter to measure air permeability, usually expressed as air permeability, that is, the amount of air passing through a unit area of the test sample per unit time under the condition of maintaining a certain pressure difference on both sides of the test sample. It is calculated according to the formula: BP (mL / cm 2 ·s)=V / AF*T;Where: V is the volume of air passing through the test sample in T seconds (mL); AF is the area of the test sample (cm 2 The air permeability of the test sample is characterized by measuring the air flow rate passing vertically through the sample per unit time under a specified pressure.

[0170] Test Samples: The lead-based zeolite fiber composite materials of Examples 1-7 were woven using a textile machine into a plain weave fabric with a linear density of 50 x 50. The test samples were stacked into 7 layers (thickness approximately 1.5 ± 0.1 mm) for testing. The fabrics produced in Examples 1-7 were used as test samples.

[0171] Test results: The air permeability of the fabrics prepared in Examples 1-7 is shown in Table 6.

[0172] Table 6 Air permeability test results of fabrics prepared in Examples 1-7

[0173]

[0174] Combining Examples 1-7 and Table 6 shows that the air permeability of Examples 5-6 is roughly equivalent to that of Examples 1-4, and is better than that of Example 10. This may be because the oligomers used in this application are first adsorbed on the lead-based zeolite and fiber line, and then polymerized to form a polymer that is better wrapped on the lead-based zeolite and fiber line, and the polymer coating has little effect on the air permeability of the lead-based zeolite fiber composite material.

[0175] The specific embodiments of this application are merely explanations of this application and are not limitations of this application. After reading this specification, those skilled in the art may make non-creative modifications to this embodiment as needed, but as long as they are within the scope of the claims of this application, they are protected by patent law.

Claims

1. A lead-based zeolite fiber composite material, characterized in that: The invention comprises a lead-based zeolite and a fiber line, wherein the lead-based zeolite is attached to the surface of the fiber line, the lead-based zeolite comprises zeolite and lead element, and the lead-based zeolite and the fiber line are used to prepare a zeolite fiber line, wherein the content of the zeolite accounts for 25-50wt% of the zeolite fiber line, and the mass fraction of the lead element in the lead-based zeolite is 8%-13%; the lead-based zeolite fiber composite material also comprises a polymer coating, which is attached to the surface of the zeolite fiber line; the polymer coating is a polymer coating containing anions; the anionic polymer coating is polymerized from 20-30 parts of an acrylic monomer and 2-4 parts of acrylonitrile; the acrylic monomer is one or more of acrylic acid, methacrylic acid, methyl methacrylate, and butyl acrylate; the lead-based zeolite also comprises silver ions, and the mass fraction of the silver ions in the lead-based zeolite is 3.8%-6%.

2. The lead-based zeolite fiber composite material according to claim 1, characterized in that: The D90 particle size of the lead-based zeolite is 0.5-20 μm.

3. The lead-based zeolite fiber composite material according to claim 1, characterized in that: When the lead-based zeolite fiber composite material is shaken for 2 hours at a rotation speed of ≥120 r / min, the retention rate of the lead-based zeolite on the fiber line is greater than 96%.

4. The method for preparing the lead-based zeolite fiber composite material according to any one of claims 1 to 3, characterized in that: The following steps are involved: ① Immerse the zeolite fiber in a treatment solution and perform ultrasonic treatment for 3-6 hours; the treatment solution comprises lead nitrate with a molar concentration of 0.3-0.8 mol / L, silver nitrate with a molar concentration of 0.1-0.3 mol / L, and water; ② Take out the soaked zeolite fiber line, wash it with deionized water, and dry it.

5. The method for preparing a lead-based zeolite fiber composite material according to claim 4, characterized in that: The preparation process of the polymer coating is as follows: The zeolite fiber line is immersed in the coating mixture at a bath ratio of 1:(8-12), and then the temperature is raised to 55-65°C and ultrasonicated for 1-3 hours to prepare a polymer coating on the surface of the zeolite fiber line; The preparation process of the coating mixture is as follows: 30-35 parts of deionized water and 10-15 parts of ethylene glycol monoethyl ether are stirred and mixed to prepare a first solvent mixture; Mixing acrylic monomer and acrylonitrile uniformly to prepare a second mixed solution; Dissolve 0.1-0.3 parts of an initiator in 1-2 parts of acetone, stir, and prepare an initiator solution, and divide the initiator solution into a first initiator solution and a second initiator solution; The first mixed solution was heated to 60-70° C., the second mixed solution and the first initiator solution were added, and the mixture was kept warm for 0.5-1 h to prepare a third mixed solution; The temperature of the third mixed solution was lowered to 20-35° C., the second initiator solution was added, and then the pH was adjusted to 6-7 to prepare a coating mixed solution.

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