CN110218823B - high-Z element-natural leather composite X-ray shielding material and preparation method thereof - Google Patents
high-Z element-natural leather composite X-ray shielding material and preparation method thereof Download PDFInfo
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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
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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
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
Abstract
The invention discloses a preparation method of a high Z element-natural leather composite material, which comprises the steps of dipping leather produced by a conventional tanning process into a salt solution containing a high Z element, and combining a large number of active functional groups in the leather with high Z element ions to obtain a high Z element nano particle-natural leather composite X-ray shielding material. The method provided by the invention has the advantages of simple and controllable preparation process, rich material sources, low price, mild reaction conditions, no need of special processing equipment and easiness in industrial large-scale production. The high-Z element-natural leather composite material prepared by the method has small density and light weight, and when the high-Z element-natural leather composite material is applied to X-ray shielding, the material has excellent shielding performance and reduces secondary radiation. In addition, the material not only solves the defect of poor mechanical property of the traditional polymer shielding material, but also provides good wearing comfort.
Description
Technical Field
The invention belongs to the technical field of functional materials and preparation thereof, 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.
Background
With the development of nuclear physics, ionizing radiation is increasingly used in people's daily lives, such as medical imaging, radiotherapy, metal probing, and material characterization. Also, in nature and in industrial production, ionizing Radiation is often present 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, when a human body is exposed to ionizing radiation for a long time, DNA is damaged to different degrees, causing cell mutation, and further causing symptoms such as vomiting, diarrhea, cataract and cancer (Huley, Liujiali, Marong and. radiation dose and protection [ M ]. Beijing: electronics industry Press, 2015.), therefore, all kinds of ionizing radiation are listed as carcinogens by the International Agency for Research on cancers of the world health organization (International Agency for Research on IARC Monographs on the Evaluation of Carcinogenic Risks to Humans [ M ]. Lyon: WHO Press, 2012, 100D.).
Ionizing radiation refers to radiation that carries energy sufficient to free electrons from the nuclei of atoms, thereby ionizing atoms or molecules (Wangjianlong, who Shi is the basic course of radiation protection [ M)]Beijing, Qinghua university Press, 2012). Ionizing radiation can be divided into direct ionizing radiation and indirect ionizing radiation according to the nature of the radiation causing ionization, wherein the former mainly consists of He2+A constituting alpha ray and a beta ray composed of an electron or a positron. The range of alpha rays in the air is only 1 cm, and the harm to human bodies can be ignored; beta rays have a larger range in air than alpha rays, but have low energy and a small ionization effect on air, and can be simply shielded by shielding facilities or materials (Chenwangjin, Chenyanli, Caiejie. radiation and its safety protection technology [ M)]Beijing chemical industry Press, 2006). Indirect ionizing radiation mainly comprises X rays, gamma rays and neutron rays which are all neutral in electricity, so that the direct action with substances is weaker, but the indirect ionizing radiation can ionize and excite substance molecules when the indirect ionizing radiation reacts with the substances to form unstable free radicals with active chemical properties, so that serious harm is caused to human bodies, and the effective shielding of the indirect ionizing radiation directly relates to whether human beings can safely utilize the ionizing radiation.
X-rays are the most exposed indirect ionizing Radiation in people' S daily life, and act with substances mainly through the three ways of photoelectric effect, Compton scattering and Rayleigh scattering, and essentially mainly with nuclear electrons of atoms (Nambiar S, Yeow J T W. Polymer-Composite Materials for Radiation Protection [ J ]. ACS Applied Materials & Interfaces 2012, 4(11): 5717-5726.). The present theory holds that the attenuation effect of a substance on X-rays is proportional to the fourth power of the material density and atomic number (Lusic H, Grinstoff M W. X-ray-calculated Tomograph Contrast Agents [ J ]. Chemical Reviews, 2013, 113(3): 1641-1666.), and therefore, to shield X-rays, bulk materials composed of high-Z elements are mainly used.
Although the bulk material has good shielding performance for X-rays, the bulk material is extremely heavy and is only suitable for being used as radiation shielding of fixed occasions and cannot be used for protecting moving targets. Therefore, a large number of researchers have made Polymer-based nanocomposites from nano-oxides containing high-Z elements and Polymer materials through different processes and used them for X-ray Shielding (Kim Y, Park S, Seo Y. Enhanced X-ray Shielding adhesion of Polymer-Nonleaded metals by multi layer structure [ 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-. However, the polymer-based nanocomposite prepared at present still has the following problems: (1) due to poor compatibility, the synthetic polymer and the high-Z element oxide nanoparticles are not uniformly mixed; (2) the used high-Z element oxide nanoparticles have a fixed crystal form, can generate stronger secondary radiation at a specific angle, and can cause harm to other surrounding personnel; (3) the mechanical strength of the prepared composite material is not high, and can be reduced along with the increase of the loading capacity of the high-Z element nano particles; (4) the prepared composite material is lack of a pore structure, poor in water and air permeability and insufficient in wearability.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a light-weight low-scattering high-Z element-loaded natural leather-based composite X-ray shielding material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the composite X-ray shielding material is a composite material of high-Z element nano particles and natural leather, wherein the high-Z element is at least one of elements with an atomic number not less than 37 and not more than 92, and the natural leather is formed by tanning cow leather, sheep leather or pigskin. Through detection, when the composite material with the thickness of 1mm is used for shielding X-rays with the average energy of 60-100 keV, the efficiency is up to 66%.
Another object of the present invention is to provide a method for preparing the above natural leather-based composite material. In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the natural leather is used as a framework, and a large number of active functional groups on the natural leather are combined with high Z element ions, so that the natural leather-based composite material loaded with the high Z element nano particles is obtained. Specifically, the method comprises the following steps:
(1) preparing the high Z element salt into a solution with a certain concentration, and adjusting the pH value of the solution to a proper range.
(2) And (3) placing a proper amount of leather into the prepared solution, and reacting for a certain time at a fixed temperature.
(3) The leather is removed from the above solution and subjected to a desolventizing treatment.
(4) If necessary, the above steps (1) to (3) may be repeated to increase the high Z element loading.
The natural leather used in the method is leather produced by taking cow leather, sheep leather or pigskin as raw materials according to a conventional tanning process.
The high-Z element salt is a soluble salt of an element having an atomic number of 37 to 92.
The solvent used includes but is not limited to water or common organic solvents such as ethanol, acetone, etc.
The concentration of the used salt solution is 1-50 wt%, and the mass ratio of the salt solution to the leather is 5-200: 1.
The pH value of the reaction is 3-8.
The reaction temperature is 10-60 ℃.
The reaction time is 0.5-24 h.
The reaction means used include, but are not limited to, ultrasound assistance, shaking table shaking, tumbling shaking.
The desolventizing method used includes but is not limited to natural air drying, organic solvent dehydration, high temperature desolventizing, freeze drying, and desolventizing under reduced pressure.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method provided by the invention is characterized in that high-Z element salt is loaded in natural leather with a multi-level fiber structure for compounding, and the method utilizes active groups such as amino, carboxyl, hydroxyl, amide and the like in the natural leather to interact with high-Z nano particles so as to fix the high-Z nano particles in the natural leather, so that the method can effectively avoid the agglomeration of the nano particles. Compared with the traditional preparation method, the method can load the high-Z element nanoparticles more stably and in a high-dispersion manner.
(2) The method provided by the invention is that high Z element salt is dissolved in a proper solvent, then the solution is soaked in natural leather, and finally the solvent is removed to obtain the natural leather-based nano composite material. Because the salt solution is a homogeneous system, the salt solution can be more easily and uniformly permeated into the natural leather, so that the method can realize larger loading capacity and smaller particle size of the nano particles.
(3) The invention uses soluble high Z element salt to load the high Z element nano particles in the natural leather, so the high Z element can be easily loaded as long as the high Z element has corresponding soluble salt, therefore, the method has extremely strong universality and can be almost suitable for the loading of all high Z elements. In addition, the high Z element of the invention refers to an element with an atomic number Z being more than or equal to 37, and compared with the Z being more than or equal to 56 in the prior art, the high Z element has wider application range, lower cost and more universality.
(4) The composite material prepared by the invention can be applied to X-ray shielding, and because the high-Z element is loaded by dipping the corresponding salt solution into natural leather and then removing the solvent, the amorphous nano salt particles can be obtained by controlling the condition of removing the solvent, so that the problem that the shielding material prepared by a block shielding material or a nano oxide generates secondary radiation can be avoided, a target object is protected, and the influence on the surrounding environment is avoided.
(5) The composite material prepared by the invention fully utilizes the multi-level structure of the natural leather, and the X-rays and the high-Z element nano particles in the natural leather perform multiple actions to attenuate and absorb the X-rays. In addition, the density of the composite material prepared by the invention is 1.10 g cm–3The weight of the material is less than 10 percent of that of the traditional block material, the material is lighter, the material can be used for radiation shielding of fixed occasions and can also be used for protection of moving targets, and the application range is wider.
(6) The present invention uses natural leather with a natural multi-layered structure as a base material, and thus still has excellent mechanical properties at higher high Z elemental salt loadings. The prepared composite material with the thickness of 1.0 mm has the tensile strength of up to 25 MPa and the tearing strength of up to 70N mm–1Is more than 10 times of the macromolecule based composite material. Meanwhile, the water and air permeability of the composite material prepared by the invention is 1727 g mm m–2 d–1 kPa–1It is 100 times higher than common polymer-based composite material. Therefore, the composite material prepared by the invention has good wearability.
(7) The method provided by the invention has the advantages of simple preparation process, mild reaction conditions, no need of special processing equipment and easiness in industrial amplification production.
Drawings
Fig. 1 is a scanning electron microscope image of the nano silver nitrate-sheepskin composite material prepared in example 2.
Fig. 2 is a scanning electron microscope image of the nano lanthanum nitrate-pigskin composite material prepared in example 6.
Fig. 3 is a scanning electron microscope image and an element surface scanning image of the nano cesium iodide-cow leather composite material prepared in example 11.
Fig. 4 is a scanning electron microscope image and an element plane scanning image of the nano bismuth molybdate-cow leather composite material prepared in example 14.
Figure 5 is an X-ray diffraction pattern of the sodium tungstate nano-cow leather composite and lead sheet prepared in example 9.
Fig. 6 is a graph of the shielding performance of the nano potassium iodide-sheepskin composite material prepared in example 4 against X-rays with average energies of 16, 33, 48, 65 and 83 keV.
Fig. 7 is a graph of the shielding performance of the nano lead nitrate-sheepskin composite material prepared in example 10 against X-rays with average energy of 16, 33, 48, 65, 83 keV.
Fig. 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 energies of 16, 33, 48, 65 and 83 keV.
Fig. 9 is a graph showing the shielding performance of the nano cesium iodide-cow leather composite material prepared in example 11 against X-rays with average energies of 16, 33, 48, 65 and 83 keV. The prepared composite material has stronger shielding performance on X-rays in different energy sections.
FIG. 10 is a graph of the shielding performance of the nano bismuth iodide-sheepskin composite material of 1mm and 2mm thickness prepared in example 12 and 0.1 mm and 0.25mm lead plate on X-rays with average energy of 16, 33, 48, 65 and 83 keV.
Fig. 11 is a stress-strain image of the nano barium chloride-cow leather composite prepared in example 5.
Fig. 12 is a stress-elongation image of a nano strontium chloride-cow leather composite.
Detailed Description
The present invention is described in detail by the following embodiments, and it should be noted that the embodiments are only used for further illustration of the present invention, and should not be construed as limiting the scope of the present invention, and the modification and modification of the present invention by those skilled in the art are not essential to the above disclosure. The parts referred to in the following examples are all calculated by mass.
Example 1
Weighing 1 part of SrCl2·6H2Dissolving O in 15 parts of deionized water, adjusting the pH value of the solution to 3.0 by using HCl, taking 1 part of chrome tanning cow leather with the thickness of 1.0 mm, adding the chrome tanning cow leather into the prepared salt solution, carrying out ultrasonic-assisted reaction for 0.5 h at the temperature of 20 ℃, and then placing a sample in an oven at the temperature of 60 ℃ for drying to obtain the nano strontium chloride-cow leather composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 95 percent, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 36 percent. And detecting the tearing strength of the composite material to obtain a stress-elongation image of the nano strontium chloride-pigskin composite material shown in figure 12. It can be seen from the figure that the prepared composite material has excellent tear strength.
Example 2
Weighing 2 parts of AgNO3Dissolving in 198 parts of deionized water, adjusting the pH value of the solution to 4.0 by using HCl, taking 1 part of chrome tanned sheepskin with the thickness of 0.7 mm, placing the chrome tanned sheepskin into the prepared salt solution, carrying out turnover oscillation reaction for 1 h at the temperature of 35 ℃, and then soaking a sample in excessive acetone for dehydration to obtain the nano silver nitrate-sheepskin composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 68 percent, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 17 percent. And then scanning the material by an electron microscope to obtain a scanning electron microscope image of the nano silver nitrate-sheepskin composite material shown in figure 1. As can be seen from the figure, a large amount of silver nitrate nano particles are loaded on the sheepskin fiber, the distribution is dense, and the particle size of the nano particles is small. The scanning electron microscope results prove that the silver nitrate is successfully loaded in the sheepskin by the method.
Example 3
Weighing 36 parts of SnCl4Dissolving in 84 portions of acetone, and taking 1 portionChrome tanned pigskin with the thickness of 1.5 mm is put into the prepared salt solution, the shaking table is used for oscillation reaction for 2 hours at the temperature of 10 ℃, and then the sample is put into a vacuum drying oven for drying, thus obtaining the nano tin chloride-pigskin composite material.
The detection of the prepared composite material shows that the composite material has the shielding efficiency of 73% for X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al and 24% for X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu. The detection proves that the tear strength of the material is 53N mm–1Therefore, the prepared composite material has excellent tearing strength.
Example 4
Weighing 60 parts of KI, dissolving in 90 parts of deionized water, adjusting the pH value of the solution to 6.0 by using NaOH, putting 1 part of chrome tanned sheepskin with the thickness of 1.0 mm into the prepared salt solution, carrying out ultrasonic-assisted reaction for 3 hours at 15 ℃, and naturally air-drying a sample in a cool and ventilated place to obtain the nano potassium iodide-sheepskin composite material.
The prepared composite material is detected to obtain a shielding performance diagram of the nano potassium iodide-sheepskin composite material shown in figure 6 for X-rays with average energy of 16 keV, 33 keV, 48 keV, 65 keV and 83 keV, and the diagram shows that the prepared composite material has stronger shielding performance for X-rays with different energy sections. In particular, the shielding efficiency of 96% for X-rays with an average energy of 16 keV and a half value layer of 0.32 mm Al and 61% for X-rays with an average energy of 48 keV and a half value layer of 0.24 mm Cu are achieved. Through detection, the water and air permeability of the material is 1691 g mm m–2 d–1 kPa–1The prepared composite material has excellent water vapor permeability.
Example 5
Weighing 5 parts of BaCl2·6H2Dissolving O in 95 parts of deionized water, adjusting the pH value of the solution to 5.0 by using HCl, taking 1 part of chrome tanning cow leather with the thickness of 1.5 mm, placing the chrome tanning cow leather in the prepared salt solution, carrying out oscillation reaction for 4 hours at the temperature of 60 ℃ by using a shaking table, and then carrying out freeze drying on a sample to obtain the nano barium chloride-cow leather composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 70%, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 31%. And then the tensile strength is detected, and a stress-strain image of the nano barium chloride-cow leather composite material shown in fig. 11 is obtained. It can be seen from the figure that the prepared composite material has excellent tensile strength.
Example 6
Weighing 16 parts of La (NO)3)3·6H2Dissolving O in 64 parts of ethanol, taking 1 part of chrome tanned pigskin with the thickness of 1.0 mm, putting the chrome tanned pigskin into the prepared salt solution, carrying out oscillation reaction for 12 hours at the temperature of 45 ℃ by using a shaking table, and then putting a sample into a vacuum drying oven for drying to obtain the nano lanthanum nitrate-pigskin composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 86 percent, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 35 percent. And then scanning the material by an electron microscope to obtain a scanning electron microscope image of the nano lanthanum nitrate-pigskin composite material shown in figure 2. As can be seen from the figure, a large number of lanthanum nitrate nano particles are loaded on the pigskin fiber, the distribution is compact, the particle size of the nano particles is two different sizes, but the whole size is below 100 nm. The scanning electron microscope results prove that the lanthanum nitrate is successfully loaded in the pigskin by the method.
Example 7
Weighing 1.25 parts of Sm (NO)3)3·6H2Dissolving O in 58.75 parts of acetone, taking 1 part of chrome tanning cow leather with the thickness of 0.5 mm, placing the chrome tanning cow leather in the prepared salt solution, turning and oscillating the mixture at the temperature of 30 ℃ for reaction for 8 hours, and then placing a sample in a cool and ventilated place for natural air drying to obtain the nano samarium nitrate-cow leather composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 72 percent, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reachesThe shielding efficiency of the X-ray reaches 21 percent. The detection proves that the water and air permeability of the material is 1418 g mm m–2 d–1 kPa–1The prepared composite material has excellent water vapor permeability.
Example 8
Weighing 0.75 part of Gd (NO)3)3·5H2Dissolving O in 9.25 parts of ethanol, taking 1 part of chrome tanned pigskin with the thickness of 0.5 mm, putting the chrome tanned pigskin into the prepared salt solution, carrying out oscillation reaction for 20 hours at 25 ℃ by using a shaking table, and then freezing and drying a sample to obtain the nano gadolinium nitrate-pigskin composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 63 percent, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 24 percent. The detection shows that the tensile strength of the material is 19 MPa, and the prepared composite material has excellent tensile strength.
Example 9
Weighing 20 parts of Na2WO4·2H2Dissolving O in 20 parts of deionized water, adjusting the pH value of the solution to 8.0 by using HCl, taking 1 part of chrome tanning cow leather with the thickness of 0.8 mm, placing the chrome tanning cow leather in the prepared salt solution, carrying out turnover oscillation reaction for 6 hours at the temperature of 40 ℃, and then soaking a sample in excessive ethanol for dehydration to obtain the nano sodium tungstate-cow leather composite material.
The detection of the prepared composite material shows that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 99 percent, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 42 percent. And then carrying out X-ray diffraction on the material and the lead sheet to obtain an X-ray diffraction pattern of the nano sodium tungstate-cow leather composite material and the lead sheet shown in figure 5. As can be seen from the figure, the lead sheet can generate strong reflection at certain angles, and compared with the lead sheet, the prepared composite material has no obvious diffraction peak in the angle range which can be tested by an instrument, so that the occurrence of secondary radiation is obviously reduced. The detection proves that the tensile strength of the material is 22 MPa, and the tearing strength is 69N mm–1Is disclosedThe water vapor property is 1713 g mm m–2 d–1 kPa–1The prepared composite material has excellent mechanical property and water vapor permeability.
Example 10
Weighing 0.5 part of Pb (NO)3)2Dissolving in 4.5 parts of deionized water, adjusting the pH value of the solution to 6.0 by using NaOH, taking 1 part of chrome tanned sheepskin with the thickness of 0.5 mm, placing in the prepared salt solution, carrying out oscillation reaction for 24 hours at 50 ℃ by using a shaking table, and then soaking a sample in excessive ethanol for dehydration to obtain the nano lead nitrate-sheepskin composite material.
The prepared composite material is detected to obtain a shielding performance diagram of the nano lead nitrate-sheepskin composite material shown in figure 7 for X-rays with average energy of 16 keV, 33 keV, 48 keV, 65 keV and 83 keV, and the diagram shows that the prepared composite material has stronger shielding performance for X-rays with different energy sections. Particularly, the prepared composite material is detected, so that the shielding efficiency of the composite material on X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 99%, and the shielding efficiency on X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 48%. The detection proves that the water and air permeability of the material is 1618 g mm m–2 d–1 kPa–1The prepared composite material has excellent water vapor permeability.
Example 11
Weighing 1 part of CsI, dissolving in 199 parts of ethanol, taking 1 part of chrome tanned cowhide with the thickness of 1.0 mm, placing the chrome tanned cowhide in the prepared salt solution, turning and oscillating the mixture at the temperature of 30 ℃ for reaction for 24 hours, and then placing a sample in a vacuum drying oven to remove the ethanol, thus obtaining the nano cesium iodide-cowhide composite material.
The prepared composite material is detected to obtain a shielding performance graph of the nano cesium iodide-cow leather composite material shown in fig. 9 for X-rays with average energy of 16 keV, 33 keV, 48 keV, 65 keV and 83 keV, and the graph shows that the prepared composite material has stronger shielding performance for X-rays with different energy bands. In particular, the shielding efficiency of 99% for X-rays with an average energy of 16 keV and a half value layer of 0.32 mm Al and 64% for X-rays with an average energy of 48 keV and a half value layer of 0.24 mm Cu are achieved. And then carrying out electron microscope scanning and element surface scanning on the material to obtain a scanning electron microscope image and an element surface scanning image of the nano cesium iodide-cow leather composite material shown in the figure 3. As can be seen from the figure, the distribution of the cesium element and the iodine element is the same as the fiber structure trend, and the two high-Z elements are proved to be successfully loaded in the cowhide.
Example 12
Weighing 20 parts of BiI3Dissolved in 30 parts of deionized water and HNO was used3Adjusting the pH value of the solution to 7.0, putting 1 part of chrome tanned sheepskin with the thickness of 0.7 mm into the prepared salt solution, carrying out oscillation reaction for 4 hours at the temperature of 60 ℃ by using a shaking table, and then removing water in the leather by using freeze drying to obtain the nano bismuth iodide-sheepskin composite material.
The obtained composite material is made into a thickness of 1mm and a thickness of 2mm by using a flaking machine, then the thickness is detected respectively, and meanwhile, the lead sheets are used as comparison, so that a shielding performance graph of the nano bismuth iodide-sheepskin composite material with the thickness of 1mm and 2mm and the lead sheets with the average energy of 16 keV, 33 keV, 48 keV, 65 keV and 83 keV shown in the figure 10 is obtained. As can be seen from the figure, the shielding efficiency of the composite material with the thickness of 1mm on X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 100 percent, and the shielding efficiency on X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 85 percent; the shielding efficiency of the composite material with the thickness of 2mm on X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 100 percent, and the shielding efficiency on X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 94 percent. The prepared composite material has stronger shielding performance on X-rays in different energy sections, wherein the X-ray shielding performance of the composite material with the thickness of 1mm exceeds that of a 0.1 mm lead sheet, and the X-ray shielding performance of the composite material with the thickness of 2mm exceeds that of a 0.25mm lead sheet. The detection proves that the tensile strength of the material is 20 MPa, and the tearing strength is 65N mm–1The water and gas permeability is 1602 g mm m–2 d–1 kPa–1The prepared composite material has excellent mechanical property and water vapor permeability.
Example 13
Weighing 2.5 partsNa2WO4·2H2Dissolving O in 2.5 parts of deionized water, adjusting the pH value of the solution to 8.0 by using NaOH, putting 1 part of chrome tanned pigskin with the thickness of 1.5 mm into the prepared salt solution, carrying out ultrasonic-assisted reaction for 0.5 h at the temperature of 10 ℃, and then putting the sample into excessive ethanol for dehydration.
Weighing 10 parts of Pb (NO)3)2Dissolved in 90 parts of deionized water using HNO3Adjusting the pH value of the solution to 4.0, placing the sample in the step into the prepared salt solution, turning and oscillating the solution at 40 ℃ for reaction for 12 hours, and then placing the sample in a drying oven at 60 ℃ for drying to obtain the nano lead tungstate-pigskin composite material.
The prepared composite material is detected to obtain a shielding performance diagram of the nano lead tungstate-pigskin composite material shown in fig. 8 for X-rays with average energy of 16 keV, 33 keV, 48 keV, 65 keV and 83 keV, and the diagram shows that the prepared composite material has stronger shielding performance for X-rays with different energy sections. Particularly, the prepared composite material is detected, so that the shielding efficiency of the composite material on X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 99%, and the shielding efficiency on X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 58%. The detection proves that the water and air permeability of the material is 1727 g mm m–2 d–1 kPa–1The prepared composite material has excellent water vapor permeability.
Example 14
Weighing 7.5 parts of Bi (NO)3)3And 142.5 parts deionized water was added, using HNO3Adjusting the pH of the solution to 3.0, adding 1 part of chrome tanned cowhide with thickness of 1.5 mm into the prepared salt solution, oscillating and reacting at 20 deg.C for 1 h with a shaker, and naturally air drying the sample in shade.
Weighing 6 parts of Na2MoO4·2H2Dissolving O in 24 parts of deionized water, adjusting the pH value of the solution to 8.0 by using NaOH, placing the sample in the previous step into the prepared salt solution, wetting the sample for 2 hours at 30 ℃ by using ultrasonic assistance, and then placing the sample into excessive acetone for dehydration to obtain the nano bismuth molybdate-cow leather composite material.
Scanning the material by an electron microscope and an element surface to obtain a scanning electron microscope image and an element surface scanning image of the nano bismuth molybdate-cow leather composite material shown in fig. 4. As can be seen, the distribution of the bismuth element and the molybdenum element is the same as the fiber structure trend, which proves that the two high-Z elements are successfully loaded in the leather. Then, the prepared composite material is detected, so that the shielding efficiency of the composite material to X-rays with the average energy of 16 keV and the half value layer of 0.32 mm Al reaches 99%, and the shielding efficiency to X-rays with the average energy of 48 keV and the half value layer of 0.24 mm Cu reaches 72%. The detection proves that the tensile strength of the material is 22 MPa, and the tearing strength is 55N mm–1The water and air permeability is 1680 g mm m–2 d–1 kPa–1Therefore, the prepared composite material has excellent mechanical strength and water vapor permeability.
Claims (7)
1. A preparation method of a high-Z element-natural leather composite X-ray shielding material is characterized by comprising the following steps: placing natural leather in a salt solution of a high-Z element for reaction, taking out the leather after the reaction is finished, and performing desolventizing treatment; repeating the steps for 0-5 times to obtain the composite X-ray shielding material; wherein the high Z element is at least one of elements with an atomic number not less than 37 and not more than 92; the natural leather is selected from any one of chrome-tanned cow leather, chrome-tanned sheep leather or chrome-tanned pig leather.
2. The method according to claim 1, 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; the solvent removing method comprises natural air drying, organic solvent dehydration, high-temperature solvent removal, freeze drying or reduced pressure solvent removal.
3. The method according to claim 1 or 2, wherein the salt solution of the high-Z element has a concentration of 1 to 50 wt% and a pH of 3 to 8.
4. The preparation method according to claim 3, wherein the salt solution of the high Z element is reacted with the natural leather at a mass ratio of 5-200: 1.
5. The method according to claim 4, wherein the reaction is carried out at 10 to 60 ℃.
6. The method according to claim 4 or 5, wherein the reaction time is 0.5 to 24 hours.
7. The method of claim 6, wherein the reaction is further accelerated by using ultrasound, shaking table or tumbling.
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| PCT/CN2019/098976 WO2020252861A1 (en) | 2019-06-21 | 2019-08-02 | High-z-element-natural leather composite x-ray shielding material and preparation method therefor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624508A (en) * | 2009-07-28 | 2010-01-13 | 四川大学 | Method for preparing radar absorbing materials with hide glue fibril |
| CN105040163A (en) * | 2015-08-19 | 2015-11-11 | 四川大学 | Method for manufacturing radar wave absorption material with collagen fibers as template |
| CN105219895A (en) * | 2015-10-27 | 2016-01-06 | 四川大学 | A kind of leather with capability of electromagnetic shielding and preparation method thereof |
| CN106714537A (en) * | 2016-12-29 | 2017-05-24 | 四川大学 | Broadband electromagnetic wave shielding material and preparation method thereof |
| CN109022638A (en) * | 2018-06-11 | 2018-12-18 | 四川大学 | The low reflection of one kind, high-selenium corn electromagnetic shielding material and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| SU500735A1 (en) * | 1974-06-12 | 1977-03-05 | Means to protect leather materials from ionizing radiation | |
| JP2001242288A (en) * | 2000-02-29 | 2001-09-07 | Toshiba Corp | Radiation shielding material, and radiation shielding suit, radiation shield and radiation shielding equipment using it |
| CN108997732A (en) * | 2018-09-06 | 2018-12-14 | 含山县金中环装饰材料有限公司 | A kind of preparation method of permanent protective property rtificial leather |
| CN109461511B (en) * | 2018-10-24 | 2020-03-20 | 上海都浩医用新材料有限公司 | X-ray protective cloth and X-ray protective clothing |
| CN109887630B (en) * | 2019-04-15 | 2024-05-07 | 广州新莱福磁材有限公司 | Magnetic super-soft X/gamma ray protection film material with decoration or direct printing and preparation method thereof |
-
2019
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624508A (en) * | 2009-07-28 | 2010-01-13 | 四川大学 | Method for preparing radar absorbing materials with hide glue fibril |
| CN105040163A (en) * | 2015-08-19 | 2015-11-11 | 四川大学 | Method for manufacturing radar wave absorption material with collagen fibers as template |
| CN105219895A (en) * | 2015-10-27 | 2016-01-06 | 四川大学 | A kind of leather with capability of electromagnetic shielding and preparation method thereof |
| CN106714537A (en) * | 2016-12-29 | 2017-05-24 | 四川大学 | Broadband electromagnetic wave shielding material and preparation method thereof |
| CN109022638A (en) * | 2018-06-11 | 2018-12-18 | 四川大学 | The low reflection of one kind, high-selenium corn electromagnetic shielding material and preparation method thereof |
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