WO2020252861A1 - High-z-element-natural leather composite x-ray shielding material and preparation method therefor - Google Patents

High-z-element-natural leather composite x-ray shielding material and preparation method therefor Download PDF

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WO2020252861A1
WO2020252861A1 PCT/CN2019/098976 CN2019098976W WO2020252861A1 WO 2020252861 A1 WO2020252861 A1 WO 2020252861A1 CN 2019098976 W CN2019098976 W CN 2019098976W WO 2020252861 A1 WO2020252861 A1 WO 2020252861A1
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composite material
natural leather
preparation
prepared
rays
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PCT/CN2019/098976
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French (fr)
Chinese (zh)
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廖学品
王亚平
李倩
王亚楠
周建飞
曾运航
黄鑫
石碧
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四川大学
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Publication of WO2020252861A1 publication Critical patent/WO2020252861A1/en

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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C13/00—Manufacture of special kinds or leather, e.g. vellum
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes

Definitions

  • the invention belongs to the technical field of functional materials and their preparation, and particularly relates to a natural leather-based X-ray shielding material with light weight, low scattering, high shielding performance and high mechanical strength and a preparation method thereof.
  • ionizing radiation is increasingly used in people's daily life, such as medical imaging, radiotherapy, metal flaw detection and material characterization.
  • ionizing radiation often appears as a by-product (Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5717–5726.).
  • DNA will be damaged to varying degrees, causing cell mutations, which will lead to symptoms such as vomiting, diarrhea, cataracts and cancer (Huo Lei, Liu Jianli, Ma Yonghe.
  • Ionizing radiation refers to radiation that carries enough energy to get rid of the bondage of the nucleus of the electrons, thereby ionizing atoms or molecules (Wang Jianlong, He Shijun. Basic Course of Radiation Protection [M]. Beijing: Tsinghua University Press, 2012.).
  • Ionizing radiation can be divided into direct ionizing radiation and indirect ionizing radiation according to the nature of the radiation that causes ionization.
  • the former mainly includes alpha rays composed of He 2+ and beta rays composed of electrons or positrons.
  • Indirect ionizing radiation mainly includes X-rays, ⁇ -rays and neutron rays. They are all electrically neutral, so their direct interaction with substances is weak, but when they interact with substances, they can ionize and excite substance molecules, forming chemically active ones. Unstable free radicals cause serious harm to the human body. Therefore, the effective shielding of indirect ionizing radiation is directly related to whether humans can safely use ionizing radiation.
  • X-rays are the indirect ionizing radiation that people are most exposed to in daily life. It mainly interacts with matter through three methods: photoelectric effect, Compton scattering and Rayleigh scattering. In essence, it mainly interacts with atomic extranuclear electrons (Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5717–5726.). The current theory believes that the attenuation effect of matter on X-rays is proportional to the density of the material and the fourth power of the atomic number (Lusic H, Grinstaff M W. X-ray-Computed Tomography Contrast Agents[J]. Chemical Reviews, 2013, 113(3): 1641–1666.) Therefore, in order to shield X-rays, bulk materials composed of high-Z elements are mainly used.
  • the purpose of the present invention is to provide a light-weight, low-scattering, high-Z element-loaded natural leather-based composite X-ray shielding material for the problems in the prior art.
  • the composite X-ray shielding material of the present invention is a composite material of high-Z element nanoparticles and natural leather, wherein the high-Z element is at least one of elements with 37 ⁇ atomic number ⁇ 92, and the natural leather is made of cowhide, Tanned sheepskin or pigskin. After testing, the 1 mm thick composite material has an efficiency of 66% when shielding X-rays with an average energy of 60-100 keV.
  • Another object of the present invention is to provide a method for preparing the above-mentioned natural leather-based composite material.
  • the technical solutions adopted by the present invention are as follows:
  • the natural leather is used as the skeleton, and a large number of active functional groups on the natural leather are combined with high-Z element ions to obtain a natural leather-based composite material loaded with high-Z element nanoparticles. Specifically, it includes the following steps:
  • the natural leather used in the above method is leather produced with cowhide, sheepskin or pigskin as raw materials according to a conventional tanning process.
  • the high-Z element salt used is a soluble salt containing elements with atomic numbers 37 to 92.
  • the solvent used includes but is not limited to common organic solvents such as water or ethanol and acetone.
  • the concentration of the salt solution used is 1-50 wt%, and the mass ratio of the salt solution to the leather is 5 to 200:1.
  • the reaction pH used is 3 ⁇ 8.
  • the reaction temperature used is 10-60°C.
  • the reaction time used is 0.5 ⁇ 24 h.
  • reaction methods used include but are not limited to ultrasound assistance, shaker shaking, and overturning shaking.
  • the solvent removal methods used include, but are not limited to, natural air drying, organic solvent dehydration, high temperature solvent removal, freeze drying, and reduced pressure solvent removal.
  • the present invention has the following beneficial effects:
  • the method provided by the present invention is to load high-Z element salt in a natural leather with a multi-level fiber structure.
  • This method uses the amino, carboxyl, hydroxyl, amide and other active groups in the natural leather to combine with high Z nanoparticles interact and fix them in natural leather.
  • This method can effectively avoid agglomeration of nanoparticles.
  • the method can load high-Z element nanoparticles more stably and highly dispersed.
  • the method provided by the present invention is to first dissolve the high-Z element salt in an appropriate solvent, then immerse the solution in natural leather, and finally remove the solvent to obtain a natural leather-based nanocomposite material. Since the salt solution is a homogeneous system, it can more easily and uniformly penetrate into the natural leather, so the method can achieve a larger load and the particle size of the nanoparticles is also smaller.
  • the present invention uses soluble high-Z element salt to load high-Z element nanoparticles in natural leather. Therefore, as long as the high-Z element has a corresponding soluble salt, it can be easily loaded. Therefore, this method is extremely powerful Universality, almost applicable to all loads of high Z elements.
  • the high-Z element of the present invention refers to an element with an atomic number Z ⁇ 37. Compared with the Z ⁇ 56 in the prior art, the high-Z element has a wider application range, lower cost, and more general applicability.
  • the composite material prepared by the present invention can be applied to X-ray shielding. Since the high-Z elements are loaded by immersing the corresponding salt solution in natural leather and then removing the solvent, it can be obtained by controlling the conditions for removing the solvent. Amorphous nano-salt particles can avoid secondary radiation problems like bulk shielding materials or shielding materials made of nano-oxides, which not only protects the target object, but also does not affect the surrounding environment.
  • the composite material prepared by the present invention makes full use of the multi-layer structure of natural leather.
  • natural leather X-rays interact with high-Z element nanoparticles to attenuate and absorb X-rays.
  • the composite material prepared by the invention can achieve the same X-ray shielding effect under the condition of lower density, and its performance is better.
  • the density of the composite material prepared by the present invention is below 1.10 g cm - 3 , which is less than 10% of the traditional bulk material, and the weight is lighter.
  • it can also be used as a moving target. The protection, the application range is wider.
  • the present invention uses natural leather with a natural multilayer structure as a basic material, so it still has excellent mechanical properties at a higher loading of high Z element salt.
  • the prepared 1.0 mm thick composite material has a tensile strength of 25 MPa and a tear strength of 70 N mm – 1 , which is more than 10 times that of the polymer matrix composite material.
  • the water vapor permeability of the composite material prepared by the present invention is 1727 g mm m – 2 d – 1 kPa – 1 , which is more than 100 times higher than that of common polymer-based composite materials. Therefore, the composite material prepared by the present invention has good wearability.
  • the method provided by the present invention has a relatively simple preparation process, mild reaction conditions, does not require special processing equipment, and is easy for industrialized scale-up production.
  • Figure 1 is a scanning electron microscope image of the nano-silver nitrate-sheep skin composite prepared in Example 2.
  • Example 2 is a scanning electron microscope image of the nano-lanthanum nitrate-pigskin composite material prepared in Example 6.
  • Example 3 is a scanning electron microscope image and an element surface scan image of the nano cesium iodide-cowhide composite material prepared in Example 11.
  • Example 4 is a scanning electron microscope image and an element surface scan image of the nano bismuth molybdate-cowhide composite material prepared in Example 14.
  • Example 5 is an X-ray diffraction pattern of the nano sodium tungstate-cowhide composite material and lead flake prepared in Example 9.
  • Example 6 is a graph showing the shielding performance of the nano-potassium iodide-sheep skin composite material prepared in Example 4 against X-rays with an average energy of 16, 33, 48, 65, and 83 keV.
  • Example 7 is a graph showing the shielding performance of the nano-lead nitrate-sheep skin composite material prepared in Example 10 against X-rays with average energy of 16, 33, 48, 65, and 83 keV.
  • Example 8 is a graph showing the shielding performance of the nano-lead tungstate-pigskin composite material prepared in Example 13 against X-rays with average energy of 16, 33, 48, 65, and 83 keV.
  • Example 9 is a graph showing the shielding performance of the nano cesium iodide-cowhide composite material prepared in Example 11 against X-rays with an average energy of 16, 33, 48, 65, and 83 keV. It can be seen from the figure that the prepared composite material has strong shielding performance against X-rays in different energy ranges.
  • Figure 10 shows the shielding of the 1 mm, 2 mm thick nano bismuth iodide-sheep skin composite material and 0.1 mm, 0.25 mm lead sheets prepared in Example 12 against X-rays with an average energy of 16, 33, 48, 65, 83 keV Performance graph.
  • Example 11 is a stress-strain image of the nano-barium chloride-cowhide composite material prepared in Example 5.
  • Figure 12 shows the stress-elongation image of nano-strontium chloride-cowhide composite material.
  • the test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32
  • the shielding efficiency of mm Al X-rays reached 95%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 36%.
  • the tear strength was tested, and the stress-elongation image of the nano-strontium chloride-pigskin composite material as shown in Figure 12 was obtained. It can be seen from the figure that the prepared composite material has excellent tear strength.
  • the inspection of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32
  • the shielding efficiency of mm Al X-rays reached 68%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 17%.
  • the material is scanned by electron microscope, and the scanning electron microscope image of the nano-silver nitrate-sheep skin composite material as shown in Figure 1 is obtained. It can be seen from the figure that a large number of silver nitrate nanoparticles are loaded on the sheepskin fiber, and the distribution is relatively dense, and the size of the nanoparticles is small.
  • the results of scanning electron microscopy prove that silver nitrate has been successfully loaded in sheepskin by the method of the present invention.
  • the composite material has a shielding efficiency of 73% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al.
  • the X-ray shielding efficiency of 0.24 mm Cu reaches 24%.
  • the tear strength of the material is 53 N mm – 1 , which shows that the prepared composite material has excellent tear strength.
  • the prepared composite material was tested, and the shielding performance graph of the nano-potassium iodide-sheep skin composite material to X-rays with average energy of 16, 33, 48, 65, and 83 keV as shown in Figure 6 was obtained.
  • the prepared composite material has strong shielding performance against X-rays in different energy ranges. In particular, the shielding efficiency of X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al reached 96%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 61%. %.
  • the water vapor permeability of the material is 1691 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
  • the test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32
  • the shielding efficiency of mm Al X-rays reached 70%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 31%.
  • the tensile strength was tested, and the stress-strain image of the nano-barium chloride-cowhide composite material was obtained as shown in Figure 11. It can be seen from the figure that the prepared composite material has excellent tensile strength.
  • the test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32
  • the shielding efficiency of mm Al X-rays reached 86%
  • the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 35%.
  • the material is scanned by electron microscope, and the scanning electron microscope image of the nano-lanthanum nitrate-pigskin composite material is obtained as shown in Figure 2. It can be seen from the figure that a large number of lanthanum nitrate nanoparticles are loaded on the pigskin fiber, and the distribution is relatively dense. The particle size of the nanoparticles presents two different sizes, but the whole is 100%. Below nm. Scanning electron microscopy results prove that lanthanum nitrate has been successfully loaded in pig skin by the method of the present invention.
  • the composite material has a shielding efficiency of 72% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al.
  • the shielding efficiency of X-ray with 0.24 mm Cu reached 21%.
  • the water vapor permeability of the material is 1418 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
  • the test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32
  • the shielding efficiency of mm Al X-rays reached 63%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 24%.
  • the tensile strength of the material is 19 MPa, which shows that the prepared composite material has excellent tensile strength.
  • the composite material has a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al.
  • the X-ray shielding efficiency of 0.24 mm Cu reached 42%.
  • X-ray diffraction was performed on the material and the lead flakes to obtain the X-ray diffraction pattern of the nano sodium tungstate-cowhide composite material and the lead flakes as shown in Figure 5. It can be seen from the figure that the lead sheet will produce strong reflections at certain angles. Compared with the lead sheet, the prepared composite material has no obvious diffraction peaks within the range of angles that the instrument can test, so the secondary is significantly reduced. The occurrence of radiation.
  • the material After testing, the material has a tensile strength of 22 MPa, a tear strength of 69 N mm – 1 , and a water vapor permeability of 1713 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent mechanical properties And water vapor permeability.
  • the prepared composite material was tested, and the shielding performance graph of the nano-lead nitrate-sheep skin composite material to X-rays with average energy of 16, 33, 48, 65, 83 keV as shown in Figure 7 was obtained, which can be seen from the figure.
  • the prepared composite material has strong shielding performance against X-rays in different energy ranges.
  • the inspection of the prepared composite material shows that the composite material has a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al.
  • the shielding efficiency of X-ray with a value of 0.24 mm Cu reaches 48%.
  • the water and gas permeability of the material is 1618 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
  • the prepared composite material was tested, and the shielding performance graph of the nano cesium iodide-cowhide composite material against X-rays with average energy of 16, 33, 48, 65, and 83 keV was obtained as shown in Figure 9. It can be seen that the prepared composite material has strong shielding performance against X-rays in different energy ranges. Especially for an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 99%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 64%.
  • the obtained composite material was made into 1mm thick and 2mm thick using a sheeting machine, and then tested separately.
  • the lead sheet was used as a comparison to obtain 1 mm and 2 mm thick nano-bismuth iodide as shown in Figure 10.
  • the shielding efficiency of Cu X-rays reached 85%; the shielding efficiency of 2 mm thick composite materials against X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al reached 100%, with an average energy of 48 The shielding efficiency of X-rays with keV and half-value layer of 0.24 mm Cu reached 94%.
  • the prepared composite material has strong shielding performance against X-rays of different energy ranges.
  • the X-ray shielding performance of the 1 mm thick composite material has exceeded the X-ray shielding performance of the 0.1 mm lead sheet and the 2 mm thick composite material. It has exceeded the 0.25 mm lead sheet.
  • the tensile strength of the material is 20 MPa
  • the tearing strength is 65 N mm – 1
  • the water vapor permeability is 1602 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent mechanical properties And water vapor permeability.
  • the prepared composite material was tested, and the shielding performance graph of the nano-lead tungstate-pigskin composite material against X-rays with average energy of 16, 33, 48, 65, 83 keV was obtained as shown in Figure 8. It can be seen that the prepared composite material has strong shielding performance against X-rays in different energy ranges. In particular, the inspection of the prepared composite material shows that the composite material has a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The shielding efficiency of X-ray with a value layer of 0.24 mm Cu reaches 58%. After testing, the water vapor permeability of the material is 1727 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
  • the scanning electron microscopy and element surface scanning of the material were performed to obtain the scanning electron microscopy image and the element surface scanning image of the nano bismuth molybdate-cowhide composite material as shown in Figure 4. It can be seen from the figure that the distribution of bismuth and molybdenum is the same as the fiber structure, which proves that both high-Z elements have been successfully loaded in leather.
  • the resultant composite material was tested and found that the composite material had a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The shielding efficiency of X-rays with a layer of 0.24 mm Cu reached 72%.
  • the tensile strength of the material is 22 MPa
  • the tearing strength is 55 N mm – 1
  • the water vapor permeability is 1680 g mm m – 2 d – 1 kPa – 1 , which shows that the prepared composite material has excellent mechanical strength And water vapor permeability.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

A preparation method for a high-Z-element-natural leather composite material, comprising: immersing leather produced by a conventional tanning process in a salt solution containing a high Z element, and using a large amount of active functional groups in the leather to combine with high-Z-element ions so as to obtain a high-Z-element nanoparticle-natural leather composite X-ray shielding material. The preparation process has the advantages of being simple and controllable, having a rich raw material source, low prices, and mild reaction conditions, not needing special processing equipment, and facilitating industrial scale-up production. The prepared high-Z-element-natural leather composite material has a low density and a light mass, and the material has an excellent shielding performance and reduces secondary radiation. The material not only solves the shortcomings of poor mechanical properties of conventional polymer shielding materials, but also provides good wearing comfortability.

Description

一种高Z元素–天然皮革复合X射线屏蔽材料及其制备方法A high-Z element-natural leather composite X-ray shielding material and preparation method thereof 技术领域Technical field
本发明属于功能材料及其制备技术领域，具体涉及一种轻质、低散射、高屏蔽性能及高机械强度的天然皮革基X射线屏蔽材料及其制备方法。The invention belongs to the technical field of functional materials and their preparation, and particularly relates to a natural leather-based X-ray shielding material with light weight, low scattering, high shielding performance and high mechanical strength and a preparation method thereof.
背景技术Background technique
随着核物理的发展，电离辐射被越来越多地应用在人们的日常生活中，如医学显像、放射治疗、金属探伤及材料表征。同时，在自然界以及工业生产中，电离辐射也常常会作为一种副产物出现（Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5717–5726.）。但是，人体若长时间暴露在电离辐射下时，DNA会受到不同程度的破坏，引起细胞的变异，进而导致呕吐、腹泻、白内障及癌症等症状（霍雷, 刘剑利, 马永和. 辐射剂量与防护[M]. 北京: 电子工业出版社, 2015.），因此，所有种类的电离辐射都被世界卫生组织国际癌症研究机构列为了一类致癌物（International Agency for Research on Cancer. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans[M]. Lyon: WHO Press, 2012, 100D.）。With the development of nuclear physics, ionizing radiation is increasingly used in people's daily life, such as medical imaging, radiotherapy, metal flaw detection and material characterization. At the same time, in nature and industrial production, ionizing radiation often appears as a by-product (Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5717–5726.). However, if the human body is exposed to ionizing radiation for a long time, DNA will be damaged to varying degrees, causing cell mutations, which will lead to symptoms such as vomiting, diarrhea, cataracts and cancer (Huo Lei, Liu Jianli, Ma Yonghe. Radiation Dose and Protection [M]. Beijing: Electronic Industry Press, 2015.), therefore, all types of ionizing radiation are listed as a carcinogen by the International Agency for Research on Cancer of the World Health Organization (International Agency for Research on Cancer. IARC Monographs on the Evaluation of Carcinogenic Risks to Humans[M]. Lyon: WHO Press, 2012, 100D.).
电离辐射是指所携带的能量足以使电子摆脱原子核的束缚，从而使原子或分子发生电离的辐射（王建龙, 何仕均. 辐射防护基础教程[M]. 北京: 清华大学出版社, 2012.）。电离辐射根据导致电离的辐射本质可以分为直接电离辐射与间接电离辐射，其中前者主要包括由He 2+构成的α射线及由电子或正电子构成的β射线。α射线在空气中射程仅有1 cm，对人体的危害可以忽略不计；β射线在空气中的射程虽然较α射线大，但其能量低、对空气的电离作用小，可以简便地使用屏蔽设施或材料进行屏蔽（陈万金, 陈燕俐, 蔡捷. 辐射及其安全防护技术[M]. 北京: 化学工业出版社, 2006.）。间接电离辐射主要包含X射线、γ射线以及中子射线，它们都呈电中性，因此与物质的直接作用较弱，但是它们与物质作用时可以使物质分子电离及激发，形成化学性质活泼的不稳定的自由基，进而对人体造成严重危害，因此对间接电离辐射的有效屏蔽直接关系到人类是否能够安全地利用电离辐射。 Ionizing radiation refers to radiation that carries enough energy to get rid of the bondage of the nucleus of the electrons, thereby ionizing atoms or molecules (Wang Jianlong, He Shijun. Basic Course of Radiation Protection [M]. Beijing: Tsinghua University Press, 2012.). Ionizing radiation can be divided into direct ionizing radiation and indirect ionizing radiation according to the nature of the radiation that causes ionization. The former mainly includes alpha rays composed of He 2+ and beta rays composed of electrons or positrons. The range of alpha rays in the air is only 1 cm, and the harm to the human body is negligible; although the range of beta rays in the air is greater than that of alpha rays, its energy is low and the ionization effect on the air is small, so shielding facilities can be easily used Or materials for shielding (Chen Wanjin, Chen Yanli, Cai Jie. Radiation and its safety protection technology[M]. Beijing: Chemical Industry Press, 2006.). Indirect ionizing radiation mainly includes X-rays, γ-rays and neutron rays. They are all electrically neutral, so their direct interaction with substances is weak, but when they interact with substances, they can ionize and excite substance molecules, forming chemically active ones. Unstable free radicals cause serious harm to the human body. Therefore, the effective shielding of indirect ionizing radiation is directly related to whether humans can safely use ionizing radiation.
X射线是人们日常生活中接触最多的间接电离辐射，它主要通过光电效应、康普顿散射和瑞利散射三种方式与物质发生作用，本质上主要是与原子的核外电子发生作用（Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5717–5726.）。目前的理论认为物质对X射线的衰减效果与材料密度和原子序数的四次方成正比（Lusic H, Grinstaff M W. X-ray-Computed Tomography Contrast Agents[J]. Chemical Reviews, 2013, 113(3): 1641–1666.），因此，要想屏蔽X射线，主要使用高Z元素组成的块体材料。X-rays are the indirect ionizing radiation that people are most exposed to in daily life. It mainly interacts with matter through three methods: photoelectric effect, Compton scattering and Rayleigh scattering. In essence, it mainly interacts with atomic extranuclear electrons (Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection[J]. ACS Applied Materials & Interfaces, 2012, 4(11): 5717–5726.). The current theory believes that the attenuation effect of matter on X-rays is proportional to the density of the material and the fourth power of the atomic number (Lusic H, Grinstaff M W. X-ray-Computed Tomography Contrast Agents[J]. Chemical Reviews, 2013, 113(3): 1641–1666.) Therefore, in order to shield X-rays, bulk materials composed of high-Z elements are mainly used.
技术问题technical problem
虽然块体材料对X射线具有较好的屏蔽性能，但其极为笨重，仅适合用做固定场合的辐射屏蔽，而无法用作移动目标的防护。因此，大量学者将含有高Z元素的纳米氧化物与高分子材料通过不同工艺制成高分子基纳米复合材料并将其用于X射线屏蔽（Kim Y, Park S, Seo Y. Enhanced X-ray Shielding Ability of Polymer–Nonleaded Metal Composites by Multilayer Structuring[J]. Industrial & Engineering Chemistry Research, 2015, 54(22): 5968–5973. Chai H, Tang X, Ni M et al. Preparation and properties of novel, flexible, lead-free X-ray-shielding materials containing tungsten and bismuth(III) oxide[J]. Journal of Applied Polymer Science, 2016, 133(10): 43012. Li Q, Wei Q, Zheng W et al. Enhanced Radiation Shielding with Conformal Light-Weight Nanoparticle–Polymer Composite[J]. ACS Applied Materials & Interfaces, 2018, 10(41): 35510–35515.）。但是，目前所制备的高分子基纳米复合材料仍存在以下问题：(1) 由于相容性较差，合成高分子与高Z元素氧化物纳米粒子的混合不均匀； (2)所使用的高Z元素氧化物纳米粒子具有固定的晶型，会在特定角度产生较强的二次辐射，可能对周边其他人员造成危害；(3) 所制备的复合材料的机械强度不高，且会随着高Z元素纳米粒子载量的增大而下降；(4) 所制备的复合材料缺乏孔隙结构，透水气性较差，可穿戴性不足。 Although the bulk material has good shielding performance against X-rays, it is extremely bulky and is only suitable for radiation shielding in fixed occasions, and cannot be used as a protection for moving targets. Therefore, a large number of scholars have made polymer-based nanocomposites of nano-oxides and polymer materials containing high-Z elements through different processes and used them for X-ray shielding (Kim Y, Park S, Seo Y. Enhanced X-ray Shielding Ability of Polymer–Nonleaded Metal Composites by Multilayer Structuring[J]. Industrial & Engineering Chemistry Research, 2015, 54(22): 5968–5973. Chai H, Tang X, Ni M et al . Preparation and properties of novel, flexible , lead-free X-ray-shielding materials containing tungsten and bismuth(III) oxide[J]. Journal of Applied Polymer Science, 2016, 133(10): 43012. Li Q, Wei Q, Zheng W et al . Enhanced Radiation Shielding with Conformal Light-Weight Nanoparticle–Polymer Composite[J]. ACS Applied Materials & Interfaces, 2018, 10(41): 35510–35515.). However, currently prepared polymer-based nanocomposites still have the following problems: (1) Due to poor compatibility, the mixing of synthetic polymers and high-Z element oxide nanoparticles is not uniform; (2) The high Z element oxide nanoparticles have a fixed crystal form, which will produce strong secondary radiation at a specific angle, which may cause harm to other people around; (3) The mechanical strength of the prepared composite material is not high, and it will follow The loading of high-Z element nanoparticles increases and decreases; (4) The prepared composite material lacks pore structure, has poor water and gas permeability and insufficient wearability.
技术解决方案Technical solutions
本发明的目的是针对现有技术存在的问题，提供一种轻质、低散射的高Z元素负载的天然皮革基复合X射线屏蔽材料。The purpose of the present invention is to provide a light-weight, low-scattering, high-Z element-loaded natural leather-based composite X-ray shielding material for the problems in the prior art.
为实现上述目的，本发明采用的技术方案如下：In order to achieve the above objectives, the technical solutions adopted by the present invention are as follows:
本发明的复合X射线屏蔽材料是高Z元素纳米粒子与天然皮革的复合材料，其中，所述高Z元素为37≤原子序数≤92的元素中的至少一种，所述天然皮革由牛皮、羊皮或猪皮鞣制而成。经检测，1 mm厚的该复合材料在对平均能量为60~100 keV的X射线进行屏蔽时，效率高达66%。The composite X-ray shielding material of the present invention is a composite material of high-Z element nanoparticles and natural leather, wherein the high-Z element is at least one of elements with 37≤atomic number≤92, and the natural leather is made of cowhide, Tanned sheepskin or pigskin. After testing, the 1 mm thick composite material has an efficiency of 66% when shielding X-rays with an average energy of 60-100 keV.
本发明的另一目的是提供上述天然皮革基复合材料的制备方法。为实现上述目的，本发明采用的技术方案如下：Another object of the present invention is to provide a method for preparing the above-mentioned natural leather-based composite material. In order to achieve the above objectives, the technical solutions adopted by the present invention are as follows:
其以天然皮革为骨架，利用天然皮革上大量活性官能团与高Z元素离子结合，进而获得负载高Z元素纳米粒子的天然皮革基复合材料。具体来说，包括以下步骤： The natural leather is used as the skeleton, and a large number of active functional groups on the natural leather are combined with high-Z element ions to obtain a natural leather-based composite material loaded with high-Z element nanoparticles. Specifically, it includes the following steps:
(1) 取高Z元素盐配置成一定浓度的溶液，调整溶液pH值至适当范围。(1) Take the high-Z element salt and configure it into a solution with a certain concentration, and adjust the pH value of the solution to an appropriate range.
(2) 将适量皮革置于上述配置的溶液中，在固定温度下反应一定时间。(2) Put an appropriate amount of leather in the solution of the above configuration, and react for a certain time at a fixed temperature.
(3) 将皮革从上述溶液中移出，并进行脱溶剂处理。(3) Remove the leather from the above solution, and conduct a solvent removal treatment.
(4) 若有必要，可以重复上述(1)–(3)步以提高高Z元素负载量。(4) If necessary, you can repeat the steps (1)-(3) above to increase the loading of high Z elements.
上述方法中所使用的天然皮革是以牛皮、羊皮或猪皮为原料按照常规鞣制工艺生产的皮革。The natural leather used in the above method is leather produced with cowhide, sheepskin or pigskin as raw materials according to a conventional tanning process.
所使用的高Z元素盐是包含原子序数37~92的元素的可溶性盐。The high-Z element salt used is a soluble salt containing elements with atomic numbers 37 to 92.
所使用的溶剂包括但不限于水或乙醇、丙酮等常见有机溶剂。The solvent used includes but is not limited to common organic solvents such as water or ethanol and acetone.
所使用的盐溶液浓度为1~50 wt%，盐溶液与皮革的质量比为5~200:1。The concentration of the salt solution used is 1-50 wt%, and the mass ratio of the salt solution to the leather is 5 to 200:1.
所使用的反应pH值为3~8。The reaction pH used is 3~8.
所使用的反应温度为10~60 ℃。The reaction temperature used is 10-60°C.
所使用的反应时间为0.5~24 h。The reaction time used is 0.5~24 h.
所使用的反应方式包括但不限于超声辅助、摇床振荡、翻转振荡。The reaction methods used include but are not limited to ultrasound assistance, shaker shaking, and overturning shaking.
所使用的脱溶剂方法包括但不限于自然风干、有机溶剂脱水、高温脱溶剂、冷冻干燥、减压脱溶剂。The solvent removal methods used include, but are not limited to, natural air drying, organic solvent dehydration, high temperature solvent removal, freeze drying, and reduced pressure solvent removal.
有益效果Beneficial effect
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
(1) 本发明提供的方法是将高Z元素盐负载在具有多层级纤维结构的天然皮革中复合，该方法利用天然皮革中的氨基、羧基、羟基、酰胺基等活性基团，来与高Z纳米粒子相互作用，进而将其固定在天然皮革中，该方法可以有效避免纳米粒子的团聚。相比传统制备方法，本方法可以更加稳定和高分散地负载高Z元素纳米粒子。(1) The method provided by the present invention is to load high-Z element salt in a natural leather with a multi-level fiber structure. This method uses the amino, carboxyl, hydroxyl, amide and other active groups in the natural leather to combine with high Z nanoparticles interact and fix them in natural leather. This method can effectively avoid agglomeration of nanoparticles. Compared with the traditional preparation method, the method can load high-Z element nanoparticles more stably and highly dispersed.
(2) 本发明提供的方法是先将高Z元素盐溶于适当的溶剂中，再将溶液浸渍到天然皮革中，最后脱除溶剂得到天然皮革基纳米复合材料。由于盐溶液是均相体系，可以更加容易且均一地渗透到天然皮革中，因此本方法可以实现更大的负载量，纳米粒子的粒径也更小。(2) The method provided by the present invention is to first dissolve the high-Z element salt in an appropriate solvent, then immerse the solution in natural leather, and finally remove the solvent to obtain a natural leather-based nanocomposite material. Since the salt solution is a homogeneous system, it can more easily and uniformly penetrate into the natural leather, so the method can achieve a larger load and the particle size of the nanoparticles is also smaller.
(3) 本发明是利用可溶性高Z元素盐将高Z元素纳米粒子负载于天然皮革中，因此只要高Z元素有对应的可溶性盐，就可以很容易地被负载，故本方法具有极强的普适性，几乎可以适用于所有高Z元素的负载。此外，本发明的高Z元素指原子序数Z≥37的元素，其相对于现有技术中的Z≥56而言，其适用范围更广，成本更低，更具普适性。(3) The present invention uses soluble high-Z element salt to load high-Z element nanoparticles in natural leather. Therefore, as long as the high-Z element has a corresponding soluble salt, it can be easily loaded. Therefore, this method is extremely powerful Universality, almost applicable to all loads of high Z elements. In addition, the high-Z element of the present invention refers to an element with an atomic number Z≥37. Compared with the Z≥56 in the prior art, the high-Z element has a wider application range, lower cost, and more general applicability.
(4) 本发明制备的复合材料可以应用于X射线屏蔽，由于高Z元素是通过将相应盐溶液浸渍到天然皮革中再脱除溶剂而进行负载，因此通过控制脱除溶剂的条件，可以得到非晶态的纳米盐粒，因而可以避免像块体屏蔽材料或者纳米氧化物制备的屏蔽材料产生二次辐射的问题，既保护了目标对象，又不会对周围环境产生影响。(4) The composite material prepared by the present invention can be applied to X-ray shielding. Since the high-Z elements are loaded by immersing the corresponding salt solution in natural leather and then removing the solvent, it can be obtained by controlling the conditions for removing the solvent. Amorphous nano-salt particles can avoid secondary radiation problems like bulk shielding materials or shielding materials made of nano-oxides, which not only protects the target object, but also does not affect the surrounding environment.
(5) 本发明制备的复合材料充分利用了天然皮革的多层级结构，在天然皮革中X射线与高Z元素纳米粒子发生多次作用对X射线进行衰减和吸收，与块体材料相比，本发明制备的复合材料可以在更低密度的情况下达到同样的X射线屏蔽效果，其性能更为优良。此外，本发明所制备的复合材料的密度均在1.10 g cm – 3以下，不到传统块体材料的10%，重量更轻，除可用做固定场合的辐射屏蔽外，还可以用作移动目标的防护，应用范围更广。 (5) The composite material prepared by the present invention makes full use of the multi-layer structure of natural leather. In natural leather, X-rays interact with high-Z element nanoparticles to attenuate and absorb X-rays. Compared with bulk materials, The composite material prepared by the invention can achieve the same X-ray shielding effect under the condition of lower density, and its performance is better. In addition, the density of the composite material prepared by the present invention is below 1.10 g cm - 3 , which is less than 10% of the traditional bulk material, and the weight is lighter. In addition to being used as a radiation shield for fixed occasions, it can also be used as a moving target. The protection, the application range is wider.
(6) 本发明使用具有天然多层级结构的天然皮革作为基础材料，因此在较高的高Z元素盐负载量时仍然具有优异的机械性能。所制备的1.0 mm厚的复合材料抗张强度高达25 MPa，撕裂强度可达到70 N mm – 1，是高分子基复合材料10倍以上。同时，本发明制备的复合材料的透水气性为1727 g mm m – 2 d – 1 kPa – 1，高出常见的高分子基复合材料100倍以上。因此，本发明制备的复合材料具有良好的可穿戴性。 (6) The present invention uses natural leather with a natural multilayer structure as a basic material, so it still has excellent mechanical properties at a higher loading of high Z element salt. The prepared 1.0 mm thick composite material has a tensile strength of 25 MPa and a tear strength of 70 N mm – 1 , which is more than 10 times that of the polymer matrix composite material. At the same time, the water vapor permeability of the composite material prepared by the present invention is 1727 g mm m – 2 d – 1 kPa – 1 , which is more than 100 times higher than that of common polymer-based composite materials. Therefore, the composite material prepared by the present invention has good wearability.
(7) 本发明提供的方法制备工艺较为简单，反应条件温和，不需要特殊的加工设备，易于工业化放大生产。(7) The method provided by the present invention has a relatively simple preparation process, mild reaction conditions, does not require special processing equipment, and is easy for industrialized scale-up production.
附图说明Description of the drawings
图1为实施例2制备得到的纳米硝酸银–羊皮复合材料的扫描电镜图像。Figure 1 is a scanning electron microscope image of the nano-silver nitrate-sheep skin composite prepared in Example 2.
图2为实施例6制备得到的纳米硝酸镧–猪皮复合材料的扫描电镜图像。2 is a scanning electron microscope image of the nano-lanthanum nitrate-pigskin composite material prepared in Example 6.
图3为实施例11制备得到的纳米碘化铯–牛皮复合材料的扫描电镜图像及元素面扫描图像。3 is a scanning electron microscope image and an element surface scan image of the nano cesium iodide-cowhide composite material prepared in Example 11.
图4为实施例14制备得到的纳米钼酸铋–牛皮复合材料的扫描电镜图像及元素面扫描图像。4 is a scanning electron microscope image and an element surface scan image of the nano bismuth molybdate-cowhide composite material prepared in Example 14.
图5为实施例9制备得到的纳米钨酸钠–牛皮复合材料和铅片的X射线衍射图。5 is an X-ray diffraction pattern of the nano sodium tungstate-cowhide composite material and lead flake prepared in Example 9.
图6为实施例4制备得到的纳米碘化钾–羊皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图。6 is a graph showing the shielding performance of the nano-potassium iodide-sheep skin composite material prepared in Example 4 against X-rays with an average energy of 16, 33, 48, 65, and 83 keV.
图7为实施例10制备得到的纳米硝酸铅–羊皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图。7 is a graph showing the shielding performance of the nano-lead nitrate-sheep skin composite material prepared in Example 10 against X-rays with average energy of 16, 33, 48, 65, and 83 keV.
图8为实施例13制备得到的纳米钨酸铅–猪皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图。8 is a graph showing the shielding performance of the nano-lead tungstate-pigskin composite material prepared in Example 13 against X-rays with average energy of 16, 33, 48, 65, and 83 keV.
图9为实施例11制备得到的纳米碘化铯–牛皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图。从图中可见所制备的复合材料对不同能量段的X射线都有较强的屏蔽性能。9 is a graph showing the shielding performance of the nano cesium iodide-cowhide composite material prepared in Example 11 against X-rays with an average energy of 16, 33, 48, 65, and 83 keV. It can be seen from the figure that the prepared composite material has strong shielding performance against X-rays in different energy ranges.
图10为实施例12制备的1 mm、2 mm厚的纳米碘化铋–羊皮复合材料与0.1 mm、0.25mm铅片对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图。Figure 10 shows the shielding of the 1 mm, 2 mm thick nano bismuth iodide-sheep skin composite material and 0.1 mm, 0.25 mm lead sheets prepared in Example 12 against X-rays with an average energy of 16, 33, 48, 65, 83 keV Performance graph.
图11为实施例5制备得到的纳米氯化钡–牛皮复合材料的应力–应变图像。11 is a stress-strain image of the nano-barium chloride-cowhide composite material prepared in Example 5.
图12为的纳米氯化锶–牛皮复合材料的应力–伸长图像。Figure 12 shows the stress-elongation image of nano-strontium chloride-cowhide composite material.
本发明的最佳实施方式The best mode of the invention
下面给出实施例对本发明进行具体的描述，有必要在此指出的是，本实施例只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制，对于本领域的技术人员根据上述发明内容所做的一些非本质的改进与调整，也视为落在本发明的保护范围内。以下实施例中所涉及的份数均按质量进行计算。The following examples are given below to describe the present invention in detail. It is necessary to point out that this example is only used to further illustrate the present invention and cannot be understood as a limitation of the protection scope of the present invention. For those skilled in the art based on the above Some non-essential improvements and adjustments made by the content of the invention are also deemed to fall within the protection scope of the invention. The parts involved in the following examples are all calculated by mass.
实施例1Example 1
称取1份SrCl 2·6H 2O溶于15份去离子水，使用HCl将溶液pH调整为3.0，取1份1.0 mm厚的铬鞣牛皮于该配制好的盐溶液中，在20 ℃下使用超声辅助反应0.5 h，然后将样品置于60 ℃烘箱干燥，即可得到纳米氯化锶–牛皮复合材料。 Weigh 1 part of SrCl 2 ·6H 2 O dissolved in 15 parts of deionized water, use HCl to adjust the pH of the solution to 3.0, take 1 part of 1.0 mm thick chrome tanned cowhide in the prepared salt solution, and place it at 20 ℃ Use ultrasound to assist the reaction for 0.5 h, and then place the sample in an oven at 60 ℃ to dry, to obtain nano-strontium chloride-cowhide composite material.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了95%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了36%。再对其撕裂强度进行检测，得到如图12所示的纳米氯化锶–猪皮复合材料的应力–伸长图像。从图中可见所制备的复合材料具有优异的撕裂强度。The test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 95%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 36%. Then the tear strength was tested, and the stress-elongation image of the nano-strontium chloride-pigskin composite material as shown in Figure 12 was obtained. It can be seen from the figure that the prepared composite material has excellent tear strength.
实施例2Example 2
称取2份AgNO 3溶于198份去离子水，使用HCl将溶液pH调整为4.0，取1份0.7 mm厚的铬鞣羊皮于该配制好的盐溶液中，在35 ℃下翻转振荡反应1 h，然后将样品浸泡于过量丙酮中脱水，即可得到纳米硝酸银–羊皮复合材料。 Weigh 2 parts of AgNO 3 dissolved in 198 parts of deionized water, use HCl to adjust the pH of the solution to 4.0, take 1 part of 0.7 mm thick chrome tanned sheepskin in the prepared salt solution, turn over and shake at 35 ℃ for reaction 1 h, then soak the sample in excess acetone for dehydration to obtain nano-silver nitrate-sheepskin composite material.
对制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了68%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了17%。再对该材料进行电镜扫描，得到如图1所示的纳米硝酸银–羊皮复合材料的扫描电镜图像。由图可知，羊皮纤维上负载了大量硝酸银纳米粒子，其分布较为致密，且纳米粒子的粒径较小。扫描电镜的结果证明，硝酸银通过本发明所述的方法已经成功地负载在羊皮中。The inspection of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 68%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 17%. Then the material is scanned by electron microscope, and the scanning electron microscope image of the nano-silver nitrate-sheep skin composite material as shown in Figure 1 is obtained. It can be seen from the figure that a large number of silver nitrate nanoparticles are loaded on the sheepskin fiber, and the distribution is relatively dense, and the size of the nanoparticles is small. The results of scanning electron microscopy prove that silver nitrate has been successfully loaded in sheepskin by the method of the present invention.
实施例3Example 3
称取36份SnCl 4溶于84份丙酮，取1份1.5 mm厚的铬鞣猪皮于该配制好的盐溶液中，在10 ℃下使用摇床振荡反应2 h，然后将样品置于真空干燥箱中干燥，即可得到纳米氯化锡–猪皮复合材料。 Weigh 36 parts of SnCl 4 dissolved in 84 parts of acetone, take 1 part of 1.5 mm thick chrome-tanned pigskin in the prepared salt solution, shake the reaction on a shaker at 10 ℃ for 2 h, and then place the sample in a vacuum Dry in a drying box to obtain nano-tin chloride-pigskin composite material.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了73%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了24%。经检测，材料的撕裂强度为53 N mm – 1，可见所制备的复合材料具有优异的撕裂强度。 Inspection of the prepared composite material shows that the composite material has a shielding efficiency of 73% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The X-ray shielding efficiency of 0.24 mm Cu reaches 24%. After testing, the tear strength of the material is 53 N mm – 1 , which shows that the prepared composite material has excellent tear strength.
实施例4Example 4
称取60份KI溶于90份去离子水，使用NaOH将溶液pH调整为6.0，取1份1.0 mm厚的铬鞣羊皮于该配制好的盐溶液中，在15 ℃下使用超声辅助反应3 h，然后将样品置于阴凉通风处自然风干，即可得到纳米碘化钾–羊皮复合材料。Weigh 60 parts of KI and dissolve in 90 parts of deionized water, use NaOH to adjust the pH of the solution to 6.0, take 1 part of 1.0 mm thick chrome-tanned sheepskin in the prepared salt solution, and use ultrasound to assist reaction 3 at 15 ℃ h, then put the sample in a cool and ventilated place to air dry naturally, then nano potassium iodide-sheepskin composite material can be obtained.
对所制得的复合材料进行检测，得到如图6所示的纳米碘化钾–羊皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图，从图中可见所制备的复合材料对不同能量段的X射线都有较强的屏蔽性能。尤其是对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了96%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了61%。经检测，材料的透水气性为1691 g mm m – 2 d – 1 kPa – 1，说明所制备的复合材料具有优异的透水气性。 The prepared composite material was tested, and the shielding performance graph of the nano-potassium iodide-sheep skin composite material to X-rays with average energy of 16, 33, 48, 65, and 83 keV as shown in Figure 6 was obtained. The prepared composite material has strong shielding performance against X-rays in different energy ranges. In particular, the shielding efficiency of X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al reached 96%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 61%. %. After testing, the water vapor permeability of the material is 1691 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
实施例5Example 5
称取5份BaCl 2·6H 2O溶于95份去离子水，使用HCl将溶液pH调整为5.0，取1份1.5 mm厚的铬鞣牛皮于该配制好的盐溶液中，在60 ℃下使用摇床振荡反应4 h，然后将样品冷冻干燥，即可得到纳米氯化钡–牛皮复合材料。 Weigh 5 parts of BaCl 2 ·6H 2 O dissolved in 95 parts of deionized water, use HCl to adjust the pH of the solution to 5.0, take 1 part of 1.5 mm thick chrome tanned cowhide in the prepared salt solution, and place it at 60 ℃ Use a shaker to shake the reaction for 4 hours, and then freeze-dry the sample to obtain nano-barium chloride-cowhide composite material.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了70%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了31%。再对其抗张强度进行检测，得到如图11所示的纳米氯化钡–牛皮复合材料的应力–应变图像。从图中可见所制备的复合材料具有优异的抗张强度。The test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 70%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 31%. Then the tensile strength was tested, and the stress-strain image of the nano-barium chloride-cowhide composite material was obtained as shown in Figure 11. It can be seen from the figure that the prepared composite material has excellent tensile strength.
实施例6Example 6
称取16份La(NO 3) 3·6H 2O溶于64份乙醇，取1份1.0 mm 厚的铬鞣猪皮于该配制好的盐溶液中，在45 ℃下使用摇床振荡反应12 h，然后将样品置于真空干燥箱中干燥，即可得到纳米硝酸镧–猪皮复合材料。 Weigh 16 parts of La(NO 3 ) 3 ·6H 2 O dissolved in 64 parts of ethanol, take 1 part of 1.0 mm thick chrome-tanned pig skin in the prepared salt solution, and use a shaker at 45 ℃ for reaction 12 h, and then put the sample in a vacuum drying oven to dry, you can get nano-lanthanum nitrate-pigskin composite material.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了86%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了35%。再对该材料进行电镜扫描，得到如图2纳米硝酸镧–猪皮复合材料的扫描电镜图像。从图中可见，猪皮纤维上负载了大量硝酸镧纳米粒子，其分布较为致密，纳米粒子的粒径呈现两种不同的尺寸，但整体均在100 nm以下。扫描电镜的结果证明，硝酸镧通过本发明所述的方法已经成功地负载在猪皮中。The test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 86%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 35%. Then the material is scanned by electron microscope, and the scanning electron microscope image of the nano-lanthanum nitrate-pigskin composite material is obtained as shown in Figure 2. It can be seen from the figure that a large number of lanthanum nitrate nanoparticles are loaded on the pigskin fiber, and the distribution is relatively dense. The particle size of the nanoparticles presents two different sizes, but the whole is 100%. Below nm. Scanning electron microscopy results prove that lanthanum nitrate has been successfully loaded in pig skin by the method of the present invention.
实施例7Example 7
称取1.25份Sm(NO 3) 3·6H 2O溶于58.75份丙酮，取1份0.5 mm厚的铬鞣牛皮于该配制好的盐溶液中，在30 ℃下翻转振荡反应8 h，然后将样品置于阴凉通风处自然风干，即可得到纳米硝酸钐–牛皮复合材料。 Weigh 1.25 parts of Sm(NO 3 ) 3 ·6H 2 O dissolved in 58.75 parts of acetone, take 1 part of 0.5 mm thick chrome tanned cowhide in the prepared salt solution, invert and shake at 30 ℃ for 8 hours, then Place the sample in a cool and ventilated place to air dry, and then the nano-samarium nitrate-cowhide composite material can be obtained.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了72%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了21%。经检测，材料的透水气性为1418 g mm m – 2 d – 1 kPa – 1，说明所制备的复合材料具有优异的透水气性。 Inspection of the prepared composite material shows that the composite material has a shielding efficiency of 72% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The shielding efficiency of X-ray with 0.24 mm Cu reached 21%. After testing, the water vapor permeability of the material is 1418 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
实施例8Example 8
称取0.75份Gd(NO 3) 3·5H 2O溶于9.25份乙醇，取1份0.5 mm厚的铬鞣猪皮于该配制好的盐溶液中，在25 ℃下使用摇床振荡反应20 h，然后将样品冷冻干燥，即可得到纳米硝酸钆–猪皮复合材料。 Weigh 0.75 parts of Gd(NO 3 ) 3 ·5H 2 O dissolved in 9.25 parts of ethanol, take 1 part of 0.5 mm thick chrome-tanned pig skin in the prepared salt solution, and shake it on a shaker at 25 ℃ for 20 h, then freeze-dry the sample to obtain nano-gadolinium nitrate-pigskin composite material.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了63%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了24%。经检测，材料的抗张强度为19 MPa，可见所制备的复合材料具有优异的抗张强度。The test of the prepared composite material shows that the composite material has an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 63%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 24%. After testing, the tensile strength of the material is 19 MPa, which shows that the prepared composite material has excellent tensile strength.
实施例9Example 9
称取20份Na 2WO 4·2H 2O溶于20份去离子水，使用HCl将溶液pH调整为8.0，取1份0.8 mm厚的铬鞣牛皮于该配制好的盐溶液中，在40 ℃下翻转振荡反应6 h，然后将样品浸泡于过量乙醇中脱水，即可得到纳米钨酸钠–牛皮复合材料。 Weigh 20 parts of Na 2 WO 4 ·2H 2 O dissolved in 20 parts of deionized water, use HCl to adjust the pH of the solution to 8.0, take 1 part of 0.8 mm thick chrome tanned cowhide in the prepared salt solution, Invert and shake the reaction at ℃ for 6 h, and then soak the sample in excess ethanol for dehydration to obtain nano-sodium tungstate-cowhide composite material.
对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了99%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了42%。再对该材料及铅片进行X射线衍射，得到如图5所示的纳米钨酸钠–牛皮复合材料和铅片的X射线衍射图。从图中可见，铅片在某些角度会产生强烈的反射，而所制备的复合材料相比于铅片，在仪器所能测试的角度范围内没有明显的衍射峰，故显著降低了二次辐射的发生。经检测，材料的抗张强度为22 MPa、撕裂强度为69 N mm – 1、透水气性为1713 g mm m – 2 d – 1 kPa – 1，说明所制备的复合材料具有优异的机械性能及透水气性。 Inspection of the prepared composite material shows that the composite material has a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The X-ray shielding efficiency of 0.24 mm Cu reached 42%. X-ray diffraction was performed on the material and the lead flakes to obtain the X-ray diffraction pattern of the nano sodium tungstate-cowhide composite material and the lead flakes as shown in Figure 5. It can be seen from the figure that the lead sheet will produce strong reflections at certain angles. Compared with the lead sheet, the prepared composite material has no obvious diffraction peaks within the range of angles that the instrument can test, so the secondary is significantly reduced. The occurrence of radiation. After testing, the material has a tensile strength of 22 MPa, a tear strength of 69 N mm – 1 , and a water vapor permeability of 1713 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent mechanical properties And water vapor permeability.
实施例10Example 10
称取0.5份Pb(NO 3) 2溶于4.5份去离子水，使用NaOH将溶液pH调整为6.0，取1份0.5 mm厚的铬鞣羊皮于该配制好的盐溶液中，在50 ℃下使用摇床振荡反应24 h，然后将样品浸泡于过量乙醇中脱水，即可得到纳米硝酸铅–羊皮复合材料。 Weigh 0.5 parts of Pb(NO 3 ) 2 dissolved in 4.5 parts of deionized water, use NaOH to adjust the pH of the solution to 6.0, take 1 part of 0.5 mm thick chrome-tanned sheepskin in the prepared salt solution, and place it at 50 ℃ Use a shaker to oscillate the reaction for 24 hours, and then soak the sample in excess ethanol for dehydration to obtain nano-lead nitrate-sheepskin composite material.
对所制得的复合材料进行检测，得到如图7所示的纳米硝酸铅–羊皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图，从图中可见所制备的复合材料对不同能量段的X射线都有较强的屏蔽性能。尤其是对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了99%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了48%。经检测，材料的透水气性为1618 g mm m – 2 d – 1 kPa – 1，说明所制备的复合材料具有优异的透水气性。 The prepared composite material was tested, and the shielding performance graph of the nano-lead nitrate-sheep skin composite material to X-rays with average energy of 16, 33, 48, 65, 83 keV as shown in Figure 7 was obtained, which can be seen from the figure. The prepared composite material has strong shielding performance against X-rays in different energy ranges. In particular, the inspection of the prepared composite material shows that the composite material has a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The shielding efficiency of X-ray with a value of 0.24 mm Cu reaches 48%. After testing, the water and gas permeability of the material is 1618 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
实施例11Example 11
称取1份CsI溶于199份乙醇，取1份1.0 mm厚的铬鞣牛皮于该配制好的盐溶液中，在30 ℃下翻转振荡反应24 h，然后将样品置于真空干燥箱脱去乙醇，即可得到纳米碘化铯–牛皮复合材料。Weigh 1 part of CsI dissolved in 199 parts of ethanol, take 1 part of 1.0 mm thick chrome tanned cowhide in the prepared salt solution, invert and shake at 30 ℃ for 24 hours, then place the sample in a vacuum drying oven to remove Ethanol, you can get nano cesium iodide-cowhide composite material.
对所制得的复合材料进行检测，得到如图9所示的纳米碘化铯–牛皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图，从图中可见所制备的复合材料对不同能量段的X射线都有较强的屏蔽性能。尤其是对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了99%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了64%。再对该材料进行电镜扫描及元素面扫描，得到如图3纳米碘化铯–牛皮复合材料的扫描电镜图像及元素面扫描图像。由图可知，铯元素和碘元素的分布都和纤维结构走向相同，证明两种高Z元素都已经成功地负载在牛皮中。The prepared composite material was tested, and the shielding performance graph of the nano cesium iodide-cowhide composite material against X-rays with average energy of 16, 33, 48, 65, and 83 keV was obtained as shown in Figure 9. It can be seen that the prepared composite material has strong shielding performance against X-rays in different energy ranges. Especially for an average energy of 16 keV and a half-value layer of 0.32 The shielding efficiency of mm Al X-rays reached 99%, and the shielding efficiency of X-rays with an average energy of 48 keV and a half-value layer of 0.24 mm Cu reached 64%. Then, the material is scanned by electron microscope and element surface scanning, and the scanning electron microscope image and element surface scanning image of the nanometer cesium iodide-cowhide composite material are obtained as shown in Figure 3. It can be seen from the figure that the distribution of cesium and iodine is the same as the fiber structure, which proves that both high-Z elements have been successfully loaded in the cowhide.
实施例12Example 12
称取20份BiI 3溶于30份去离子水，使用HNO 3将溶液pH调整为7.0，取1份0.7 mm厚的铬鞣羊皮于该配制好的盐溶液中，在60 ℃下使用摇床振荡反应4 h，然后使用冷冻干燥除去皮革中的水分，即可得到纳米碘化铋–羊皮复合材料。 Weigh 20 parts of BiI 3 dissolved in 30 parts of deionized water, use HNO 3 to adjust the pH of the solution to 7.0, take 1 part of 0.7 mm thick chrome-tanned sheepskin in the prepared salt solution, and use a shaker at 60 ℃ After shaking for 4 hours, freeze-drying is used to remove the moisture in the leather, and the nano-bismuth iodide-sheepskin composite material can be obtained.
将得到的复合材料使用片皮机制成1mm厚和2mm厚，然后再分别对其进行检测，同时以铅片为对比，得到如图10所示的1 mm、2 mm厚的纳米碘化铋–羊皮复合材料与0.1 mm、0.25mm铅片对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图。从图中可见，1 mm厚的复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率均达到了100%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率均达到了85%；2 mm厚的复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率均达到了100%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率均达到了94%。制备的复合材料对不同能量段的X射线均有较强的屏蔽性能，其中1 mm厚的复合材料的X射线屏蔽性能已经超过了0.1 mm铅片，2 mm厚的复合材料的X射线屏蔽性能已经超过了0.25 mm铅片。经检测，材料的抗张强度为20 MPa、撕裂强度为65 N mm – 1、透水气性为1602 g mm m – 2 d – 1 kPa – 1，说明所制备的复合材料具有优异的机械性能及透水气性。 The obtained composite material was made into 1mm thick and 2mm thick using a sheeting machine, and then tested separately. At the same time, the lead sheet was used as a comparison to obtain 1 mm and 2 mm thick nano-bismuth iodide as shown in Figure 10. Shielding performance graph of sheepskin composite material and 0.1 mm, 0.25mm lead sheet against X-rays with average energy of 16, 33, 48, 65, 83 keV. It can be seen from the figure that the 1 mm thick composite material has a shielding efficiency of 100% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The average energy is 48 keV and a half-value layer is 0.24 mm. The shielding efficiency of Cu X-rays reached 85%; the shielding efficiency of 2 mm thick composite materials against X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al reached 100%, with an average energy of 48 The shielding efficiency of X-rays with keV and half-value layer of 0.24 mm Cu reached 94%. The prepared composite material has strong shielding performance against X-rays of different energy ranges. The X-ray shielding performance of the 1 mm thick composite material has exceeded the X-ray shielding performance of the 0.1 mm lead sheet and the 2 mm thick composite material. It has exceeded the 0.25 mm lead sheet. After testing, the tensile strength of the material is 20 MPa, the tearing strength is 65 N mm – 1 , the water vapor permeability is 1602 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent mechanical properties And water vapor permeability.
实施例13Example 13
称取2.5份Na 2WO 4·2H 2O溶于2.5份去离子水，使用NaOH将溶液pH调整为8.0，取1份1.5 mm厚的铬鞣猪皮于该配制好的盐溶液中，在10 ℃下使用超声辅助反应0.5 h，然后将样品置于过量乙醇中脱水。 Weigh 2.5 parts of Na 2 WO 4 ·2H 2 O dissolved in 2.5 parts of deionized water, use NaOH to adjust the pH of the solution to 8.0, take 1 part of 1.5 mm thick chrome-tanned pig skin in the prepared salt solution, Use ultrasound to assist the reaction at 10 ℃ for 0.5 h, and then place the sample in excess ethanol for dehydration.
称取10份Pb(NO 3) 2溶于90份去离子水，使用HNO 3将溶液pH调整为4.0，将上步中的样品置于该配制好的盐溶液中，在40 ℃下翻转振荡反应12 h，然后将样品置于60 ℃烘箱中干燥，即可得到纳米钨酸铅–猪皮复合材料。 Weigh 10 parts of Pb(NO 3 ) 2 and dissolve in 90 parts of deionized water, use HNO 3 to adjust the pH of the solution to 4.0, put the sample in the previous step in the prepared salt solution, and turn and shake at 40 ℃ After reacting for 12 hours, the sample is dried in an oven at 60 ℃ to obtain nano-lead tungstate-pigskin composite material.
对所制得的复合材料进行检测，得到如图8所示的纳米钨酸铅–猪皮复合材料对平均能量为16、33、48、65、83 keV的X射线的屏蔽性能图，从图中可见所制备的复合材料对不同能量段的X射线都有较强的屏蔽性能。尤其是对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了99%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了58%。经检测，材料的透水气性为1727 g mm m – 2 d – 1 kPa – 1，说明所制备的复合材料具有优异的透水气性。 The prepared composite material was tested, and the shielding performance graph of the nano-lead tungstate-pigskin composite material against X-rays with average energy of 16, 33, 48, 65, 83 keV was obtained as shown in Figure 8. It can be seen that the prepared composite material has strong shielding performance against X-rays in different energy ranges. In particular, the inspection of the prepared composite material shows that the composite material has a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The shielding efficiency of X-ray with a value layer of 0.24 mm Cu reaches 58%. After testing, the water vapor permeability of the material is 1727 g mm m – 2 d – 1 kPa – 1 , indicating that the prepared composite material has excellent water and gas permeability.
实施例14Example 14
称取7.5份Bi(NO 3) 3并加入142.5份去离子水，使用HNO 3将溶液pH调整为3.0，取1份1.5 mm厚的铬鞣牛皮于该配制好的盐溶液中，在20 ℃下使用摇床振荡反应1 h，然后将样品置于阴凉处使其自然风干。 Weigh 7.5 parts of Bi(NO 3 ) 3 and add 142.5 parts of deionized water, use HNO 3 to adjust the pH of the solution to 3.0, take 1 part of 1.5 mm thick chrome tanned cowhide in the prepared salt solution, and place it at 20 ℃ Use a shaker to shake the reaction for 1 h, then place the sample in a cool place to allow it to air dry naturally.
称取6份Na 2MoO 4·2H 2O溶于24份去离子水，使用NaOH将溶液pH调整为8.0，将上步中的样品置于该配制好的盐溶液中，在30 ℃下使用超声辅助润湿2 h，然后将样品置于过量丙酮中脱水，即可得到纳米钼酸铋–牛皮复合材料。 Weigh 6 parts of Na 2 MoO 4 ·2H 2 O dissolved in 24 parts of deionized water, use NaOH to adjust the pH of the solution to 8.0, put the sample in the previous step into the prepared salt solution, and use it at 30 ℃ Ultrasound assisted wetting for 2 h, and then put the sample in excess acetone for dehydration to obtain nano-bismuth molybdate-cowhide composite material.
对该材料进行电镜扫描及元素面扫描，得到如图4所示的纳米钼酸铋–牛皮复合材料的扫描电镜图像及元素面扫描图像。由图可知，铋元素和钼元素的分布都和纤维结构走向相同，证明两种高Z元素都已经成功地负载在皮革中。再对所制得的复合材料进行检测得知，该复合材料对平均能量为16 keV、半值层为0.32 mm Al的X射线的屏蔽效率达到了99%，对平均能量为48 keV、半值层为0.24 mm Cu的X射线的屏蔽效率达到了72%。经检测，材料的抗张强度为 22 MPa、撕裂强度为55 N mm – 1、透水气性为1680 g mm m – 2 d – 1 kPa – 1，可见所制备的复合材料具有优异的机械强度及透水气性。 The scanning electron microscopy and element surface scanning of the material were performed to obtain the scanning electron microscopy image and the element surface scanning image of the nano bismuth molybdate-cowhide composite material as shown in Figure 4. It can be seen from the figure that the distribution of bismuth and molybdenum is the same as the fiber structure, which proves that both high-Z elements have been successfully loaded in leather. The resultant composite material was tested and found that the composite material had a shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half-value layer of 0.32 mm Al. The shielding efficiency of X-rays with a layer of 0.24 mm Cu reached 72%. After testing, the tensile strength of the material is 22 MPa, the tearing strength is 55 N mm – 1 , and the water vapor permeability is 1680 g mm m – 2 d – 1 kPa – 1 , which shows that the prepared composite material has excellent mechanical strength And water vapor permeability.

Claims (10)

  1. 一种高Z元素–天然皮革复合X射线屏蔽材料，其特征在于，为高Z元素纳米粒子与天然皮革的复合材料，1 mm厚的该复合材料在对平均能量为60~100 keV的X射线进行屏蔽时，效率高达66%。A high-Z element-natural leather composite X-ray shielding material, which is characterized in that it is a composite material of high-Z element nanoparticles and natural leather. The composite material with a thickness of 1 mm can resist X-rays with an average energy of 60-100 keV. When shielded, the efficiency is as high as 66%.
  2. 根据权利要求1所述的复合X射线屏蔽材料，其特征在于，所述高Z元素为37≤原子序数≤92的元素中的至少一种。The composite X-ray shielding material according to claim 1, wherein the high-Z element is at least one of elements with 37≦atomic number≦92.
  3. 根据权利要求1或2所述的复合X射线屏蔽材料，其特征在于，所述天然皮革由牛皮、羊皮或猪皮鞣制而成。The composite X-ray shielding material according to claim 1 or 2, wherein the natural leather is tanned from cowhide, sheepskin or pigskin.
  4. 一种如权利要求1-3任意一项所述的高Z元素–天然皮革复合X射线屏蔽材料的制备方法，其特征在于，该制备方法包括：将天然皮革置于高Z元素的盐溶液中进行反应，反应完成后取出皮革并进行脱溶剂处理；再重复上述步骤0~5次，即得复合X射线屏蔽材料。A method for preparing a high-Z element-natural leather composite X-ray shielding material according to any one of claims 1 to 3, characterized in that the preparation method comprises: placing the natural leather in a high-Z element salt solution The reaction is carried out. After the reaction is completed, the leather is taken out and subjected to solvent removal treatment; the above steps are repeated 0 to 5 times to obtain the composite X-ray shielding material.
  5. 根据权利要求4所述的制备方法，其特征在于，所述高Z元素的盐溶液中的溶剂为水或有机溶剂，所述有机溶剂为乙醇或丙酮；所述脱溶剂处理的方法为自然风干、有机溶剂脱水、高温脱溶剂、冷冻干燥或减压脱溶剂。The preparation method according to claim 4, wherein the solvent in the salt solution of the high-Z element is water or an organic solvent, and the organic solvent is ethanol or acetone; and the solvent removal treatment method is natural air drying , Organic solvent dehydration, high temperature desolventization, freeze drying or reduced pressure desolvation.
  6. 根据权利要求4或5所述的制备方法，其特征在于，所述高Z元素的盐溶液的浓度为1~50 wt%、pH值为3~8。The preparation method according to claim 4 or 5, wherein the concentration of the salt solution of the high-Z element is 1-50 wt%, and the pH value is 3-8.
  7. 根据权利要求6所述的制备方法，其特征在于，所述高Z元素的盐溶液与天然皮革按5~200:1的质量比进行反应。The preparation method according to claim 6, wherein the high-Z element salt solution and natural leather are reacted at a mass ratio of 5 to 200:1.
  8. 根据权利要求7所述的制备方法，其特征在于，所述反应是在10~60 ℃条件下进行的。The preparation method according to claim 7, wherein the reaction is carried out at 10-60°C.
  9. 根据权利要求7或8所述的制备方法，其特征在于，每次反应的时长为0.5~24 h。The preparation method according to claim 7 or 8, wherein the duration of each reaction is 0.5-24 h.
  10. 根据权利要求9所述的制备方法，其特征在于，所述反应过程中，还会采用超声、摇床振荡或翻转振荡来加快反应速度。The preparation method according to claim 9, characterized in that, during the reaction process, ultrasound, shaker oscillation or overturning oscillation is also used to accelerate the reaction speed.
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