WO2022166171A1 - 一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法 - Google Patents

一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法 Download PDF

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WO2022166171A1
WO2022166171A1 PCT/CN2021/114460 CN2021114460W WO2022166171A1 WO 2022166171 A1 WO2022166171 A1 WO 2022166171A1 CN 2021114460 W CN2021114460 W CN 2021114460W WO 2022166171 A1 WO2022166171 A1 WO 2022166171A1
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core
shell structure
tungsten
gadolinium oxide
coating
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French (fr)
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姚理荣
夏勇
杨涛
孙通
潘刚伟
徐思峻
季涛
高强
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南通大学
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0061—Organic fillers or organic fibrous fillers, e.g. ground leather waste, wood bark, cork powder, vegetable flour; Other organic compounding ingredients; Post-treatment with organic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2209/00—Properties of the materials
    • D06N2209/16—Properties of the materials having other properties

Definitions

  • the invention relates to the field of preparation of radiation protection materials, in particular to a preparation method of a core-shell structure tungsten/gadolinium oxide PU coating fabric for X, gamma ray protection.
  • Radiation protection materials are mainly divided into two types: lead-containing materials and lead-free materials.
  • Lead is mainly based on lead.
  • the protective effect is excellent, it is toxic, has poor strength and has a large scattering of low-energy X-rays.
  • Lead-free materials mainly include composite materials made of rare earth elements and heavy metal compounds such as tin, tungsten, and bismuth, which have excellent protective effects and are lightweight and safe.
  • Micro-nano core-shell materials with special structures have attracted extensive attention in recent years.
  • Composite particles with different core-shell microstructures have unique physical and chemical properties, which also lead to their broad application prospects in many fields such as optics, electronics, catalysis, biology, and radiation.
  • the core-shell structure radiation protection material can synergistically protect, eliminate the weak protection area and effectively absorb the secondary radiation generated by radiation.
  • the preparation methods of core-shell structures mainly include template method, precipitation method, hydrothermal synthesis method, spray drying method, layer-by-layer self-assembly technology, etc. Li et al.
  • the purpose of the present invention is to provide a preparation method of a core-shell structure tungsten/gadolinium oxide PU coating fabric in order to overcome the above-mentioned defects in the prior art.
  • the invention provides a preparation method of a core-shell structure tungsten/gadolinium oxide PU coating fabric for X, ⁇ -ray protection, the method comprising the following steps:
  • step (2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution, stirring, filtering, and calcining at high temperature to obtain the core-shell structure W@Gd 2 O 3 powder.
  • step (3) adding the core-shell structure W@Gd 2 O 3 powder obtained in step (2) into dimethylacetamide to disperse, then adding a certain amount of polyurethane resin, stirring evenly, coating the fabric, and drying.
  • the concentration of the solution should be controlled at 1.5-2.5g/L.
  • the main reason is that when the DA concentration is lower than 1.5g/L, only a small amount of PDA particles are deposited on the surface of W.
  • the DA concentration is 1.5-2.5g/L, a PDA film is formed on the surface of the W powder.
  • the concentration of DA was higher than 2.5 g/L, larger PDA particles were formed by self-polymerization on the surface of W powder due to the high concentration of DA, which was not conducive to the subsequent adsorption of gadolinium ions.
  • tris buffer should be added to the system to adjust the pH value of the solution to 8.5, because dopamine can self-polymerize into polydopamine under weak alkaline and aerobic conditions. Polydopamine on the surface of different substances has extraordinary surface activity and adhesion, which can provide a platform for the secondary functionalization of materials.
  • step (1) needs to be stirred under an electric stirrer for 18-24h.
  • step (1) it is necessary to wash with water and ethanol for 2-3 times respectively.
  • step (1) the specific conditions for drying described in step (1) are not specifically limited, as long as the purpose of drying the sample can be achieved.
  • the concentration of the solution should be controlled at 0.3-0.5M/L. Because when the Gd + concentration is 0.02 M/L, the surface of W is coated with a small amount and sparse nano-dot-like Gd 2 O 3 particles. When the Gd + concentration increases to 0.1M/L, the Gd 2 O 3 nanoparticles on the surface of W become larger and larger, which is due to the increase of Gd + concentration, the Gd 2 O 3 nanoparticles combine with each other to form larger Gd 2 O 3 particles. When the Gd + concentration increased to 0.2 M/L, the Gd 2 O 3 nanoparticles on the W surface became larger and denser.
  • the Gd 2 O 3 nanoparticles on the W surface were combined with each other to form the core-shell structured W@Gd 2 O 3 .
  • the Gd2O3 nanoparticles on the W surface did not change much compared to when the Gd + concentration was 0.3M/L, which was due to the chelation of Gd + by the polydopamine on the W surface .
  • the synergy has reached saturation at Gd + concentration of 0.3M/L.
  • step (2) is not specifically limited, and only needs to be magnetically stirred for a certain period of time.
  • the high-temperature calcination in step (2) needs to be calcined in a muffle furnace at 800-1000° C. for 2-3 hours, and the heating temperature is 2-4° C./min.
  • the calcination in step (2) of the present invention is carried out in a protective gas, and the protective gas includes nitrogen or an inert gas, and the inert gas can be argon, helium, etc.
  • the protective gas includes nitrogen or an inert gas
  • the inert gas can be argon, helium, etc.
  • the invention does not make any special limitation on this.
  • the step (3) is added into dimethylacetamide and dispersed for 30-60min by ultrasonic dispersion.
  • the content of powder in the coating needs to be controlled to be 60wt%.
  • step (3) a small coating machine is used for coating.
  • step (3) is drying at 60-80° C. for 1-2 hours.
  • the preparation method of the core-shell structure tungsten/gadolinium oxide PU coating fabric of the present invention comprises the following steps:
  • step (2) adding the W@PDA obtained in step (1) into the gadolinium nitrate solution with a concentration of 0.3-0.5M/L, stirring magnetically for a certain period of time, filtering and separating, drying, and then the prepared sample was heated at 800-1000
  • the core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2-3 h (heating rate of 2-4 °C/min).
  • step (3) Add the core-shell structure W@Gd 2 O 3 powder obtained in step (2) into dimethylacetamide for ultrasonic dispersion for 30-60 min, and then add a certain amount of polyurethane resin glue to control the content of the powder in the coating to be 60wt %, use an electric mixer to stir for 2-3 hours, coat the fabric on a small coating machine, and finally dry it at 60-80°C for 1-2 hours.
  • the core-shell structure W@Gd 2 O 3 prepared by the above preferred technical solution can play a synergistic protective effect in radiation protection and eliminate the weak protection area. At the same time, the secondary radiation generated by the radiation is effectively absorbed.
  • the present invention at least has the following beneficial effects:
  • the present invention firstly utilizes that dopamine can self-polymerize into polydopamine under weak alkaline and aerobic conditions, and polydopamine has extraordinary adhesion on the surfaces of different substances, and can successfully coat tungsten to obtain W@PDA.
  • the surface of PDA contains a large number of polar groups such as phenolic hydroxyl groups and amine groups, which provide abundant active sites for complexing various metal ions, which can effectively chelate Gd + in gadolinium nitrate solution.
  • PDA forms a nitrogen-doped carbon layer attached to the surface of tungsten, and the W@PDA chelated with Gd + transforms into W@Gd 2 O 3 .
  • Example 1 is a scanning electron microscope image of the core-shell structure tungsten/gadolinium oxide powder prepared in Example 1.
  • the present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PU coating fabric for X, ⁇ -ray protection, the method comprising the following steps:
  • step (2) The W@PDA obtained in step (1) was added to a solution of gadolinium nitrate with a concentration of 0.3M/L, and after magnetic stirring for 2h, filtration and separation were performed, and dried at 80°C for 5h, and then the prepared sample was heated at 800°C.
  • the core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2 h (heating rate of 2 °C/min).
  • step (3) adding the core-shell structure W@Gd 2 O 3 powder obtained in step (2) into dimethylacetamide for ultrasonic dispersion for 30 min, and then adding a certain amount of polyurethane resin glue to control the content of the powder in the coating to be 60wt%, After stirring with an electric mixer for 2 hours, the fabric was coated on a small coating machine, and finally dried at 60 °C for 2 hours.
  • the W@Gd 2 O 3 powder prepared in this example was scanned by SEM, and the obtained photo is shown in Figure 1. It can be seen from the figure that a PDA film is formed on the surface of the W powder.
  • the present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PU coating fabric for X, ⁇ -ray protection, the method comprising the following steps:
  • step (2) The W@PDA obtained in step (1) was added to a gadolinium nitrate solution with a concentration of 0.35M/L, and after magnetic stirring for 3h, filtration and separation were carried out, and dried at 60°C for 8h, and then the prepared sample was heated at 900 °C.
  • the core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at high temperature under nitrogen for 2.5 h (heating rate of 3 °C/min).
  • step (3) adding the core-shell structure W@Gd 2 O 3 powder obtained in step (2) into dimethylacetamide for ultrasonic dispersion for 40 min, and then adding a certain amount of polyurethane resin glue to control the content of the powder in the coating to be 60wt%, After stirring with an electric mixer for 2.5 hours, the fabric was coated on a small coating machine, and finally dried at 70 °C for 1.5 hours.
  • the present embodiment provides a preparation method of a core-shell structure tungsten/gadolinium oxide PU coating fabric for X, ⁇ -ray protection, the method comprising the following steps:
  • step (2) The W@PDA obtained in step (1) was added to a gadolinium nitrate solution with a concentration of 0.4M/L, magnetically stirred for 2.5h, filtered and separated, dried at 70°C for 6h, and then the prepared sample was placed in The core-shell structure W@Gd 2 O 3 powder was finally obtained by calcining at 1000 °C under nitrogen for 3 h (the heating rate was 4 °C/min).
  • step (3) adding the core-shell structure W@Gd 2 O 3 powder obtained in step (2) into dimethylacetamide for ultrasonic dispersion for 50 min, then adding a certain amount of polyurethane resin glue, and controlling the content of the powder in the coating to be 60wt%, After stirring with an electric mixer for 3 hours, the fabric was coated on a small coating machine, and finally dried at 80 °C for 1 hour.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明涉及一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法，所述方法为：配置多巴胺盐溶液，加入缓冲液调节PH值，然后加入钨粉，搅拌，过滤，洗涤烘干后得到W@PDA；再将得到的W@PDA加入到硝酸钆溶液中，搅拌，过滤，经过高温煅烧得到核壳结构W@Gd 2O 3粉末；将W@Gd 2O 3粉末加入到二甲基乙酰胺中，再加入一定量聚氨酯树脂胶，搅拌均匀后对面料进行涂覆，烘干。本发明首先制备出W@PDA，是因为PDA在不同物质表面均具有非凡的黏附性，包覆钨之后，PDA表面还含有大量的酚羟基、胺基等极性基团，为络合Gd +提供了丰富的活性位点，高温煅烧后形成氮掺杂碳层。核壳结构相较于单一金属物理共混的方式，在辐射防护方面可以起到协同防护作用，消除防护弱区同时将辐射所产生的二次辐射进行有效吸收。PU树脂涂层织物服用性能与力学性能均较为优异，且W@Gd 2O 3粉末在PU树脂中分散性良好，使得该涂层面料最终的防护性能更为优异。

Description

一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法 技术领域
本发明涉及制备防辐射材料制备领域，尤其涉及一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法。
背景技术
核技术的发展给人们带来便利的同时也产生了很多辐射危害，轻便灵活且防护性能优良的辐射防护用纺织品是当前研究的热点。辐射防护材料主要分为有铅材料和无铅两种。有铅主要以铅为主，虽防护效果优良，但具有毒性，强度较差且对低能X射线散射较大。无铅材料主要包括稀土元素以及锡、钨、铋等重金属化合物制成的复合材料，防护效果优良且轻质安全。
近年来具有特殊结构的微纳米核壳材料引起了人们的广泛关注。不同核壳微观结构的复合粒子会具有独特物理化学性质，这也导致其在光学、电子、催化、生物、辐射等众多领域都具有广阔的应用前景。在防辐射方面，相较于单一金属物理共混的方式，核壳结构辐射防护材料可以协同防护，消除防护弱区同时将辐射所产生的二次辐射进行有效吸收。核壳结构的制备方法主要有模板法、沉淀法、水热合成法、喷雾干燥法、层层自组装技术等。Li等人以二氧化硅为模板采用均相沉淀法制备了壳层厚度可控的氧化钆空心球。然而这些方法都存在工序多、耗时长等缺点，因此有必要指定一种有效的、简单的方法来克服这些缺陷。贻贝分泌的黏附蛋白具有很强的黏附能力，受此启发美国西北大学Messer Smith课题组在2007年发现了多巴胺(DA)在模拟海水的弱碱条件下可以在任何材料表面氧化自聚合成聚多巴胺。其聚合条件简单可控且具有优良的粘附性、亲水性、稳定性、生物相容性。同时，聚多巴胺上存在大量的酚羟基、胺基活性集团，为金属离子的络合提供了丰富的活性位点。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种核壳结构钨/氧化钆PU涂层面料的制备方法。
本发明的目的可以通过以下技术方案来实现：
本发明提供了一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法，所述方法包括以下步骤：
(1)配置多巴胺盐溶液，加入缓冲液调节PH值，然后加入钨粉，搅拌，过滤，洗涤烘干后得到W@PDA；
(2)将步骤(1)得到的W@PDA加入到硝酸钆溶液中，搅拌，过滤，经过高温煅烧得到核壳结构W@Gd 2O 3粉末。
(3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末加入到二甲基乙酰胺中分散，再加入一 定量聚氨酯树脂，搅拌均匀后对面料进行涂覆，烘干。
根据本发明，步骤(1)所述的配置多巴胺盐溶液，溶液浓度应控制在1.5-2.5g/L。主要是因为当DA浓度为低于1.5g/L时，W的表面只沉积有少量的PDA颗粒，当DA浓度为1.5-2.5g/L时，在W粉的表面才形成了PDA薄膜。当DA的浓度高于2.5g/L时，由于DA浓度过高在W粉表面自聚合形成较大的PDA颗粒，又不利于后续对钆离子的吸附。
值得注意的是，在步骤(1)配置好多巴胺盐溶液后，要向体系中加入tris缓冲液调节溶液PH值为8.5，因为多巴胺在弱碱有氧的条件下可自聚合为聚多巴胺，在不同物质表面聚多巴胺均具有非凡的表面活性和黏附性，可以为材料的二次功能化提供平台。
进一步地，步骤(1)所述的搅拌，需在电动搅拌器下搅拌18-24h。
此外，对于步骤(1)所述的洗涤，需用水和乙醇分别洗涤2-3次。
还有，对于步骤(1)所述的烘干具体的条件不进行具体限定，只要能实现对试样的烘干目的即可。
根据本发明，步骤(2)所述的硝酸钆溶液，该溶液浓度应控制在0.3-0.5M/L。因为当Gd +浓度为0.02M/L时，W的表面包覆有少量且稀疏的纳米点状Gd 2O 3颗粒。当Gd +浓度增加到0.1M/L时，W表面的Gd 2O 3纳米颗粒变大增多，这是由于Gd +浓度的升高Gd 2O 3纳米颗粒互相结合形成更大的Gd 2O 3颗粒。当Gd +浓度增加到0.2M/L时，W表面的Gd 2O 3纳米颗粒变的更大且更为密集。随着Gd +浓度增加到0.3M/L，W表面的Gd 2O 3纳米颗粒相互结合形成核壳结构的W@Gd 2O 3。继续增加Gd +浓度到0.4M/L后，W表面的Gd 2O 3纳米颗粒相比于Gd +浓度为0.3M/L时没有太大变化，这是由于W表面的聚多巴胺对Gd +螯合作用在Gd +浓度为0.3M/L已经达到了饱和。
进一步地，步骤(2)所述的搅拌，无具体限定，只需磁力搅拌一定时间即可。
此外，步骤(2)所述的高温煅烧，需在马弗炉里800-1000℃条件下煅烧2-3h，升温温度为2-4℃/min。为避免在反应过程中生成杂质，本发明步骤(2)所述煅烧在保护性气体中进行，所述保护性气体包括氮气或惰性气体，所述惰性气体可以为氩气、氦气等，本发明对此不作特殊限定。
根据本发明，步骤(3)所述的加入到二甲基乙酰胺中分散为超声分散30-60min。
值得注意的是，对于步骤(3)所述的加入一定量聚氨酯树脂胶，需控制涂料中粉末的含量为60wt％。
进一步地，对于步骤(3)所述的涂覆为采用小型涂布机进行涂覆。
此外，对于步骤(3)所述的烘干为在60-80℃条件下干燥1-2h。
作为优选的技术方案，本发明所述的核壳结构钨/氧化钆PU涂层面料的制备方法包括以下步骤：
(1)配置1.5g/L-2.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节PH至8-9，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌18-24h后过滤分离，再分别用去离子水和乙醇洗涤2-3次后烘干，得到W@PDA；
(2)将步骤(1)得到的W@PDA加入到0.3-0.5M/L浓度的硝酸钆溶液中，磁力搅拌一定时间后，过滤分离，烘干，再将制得的样品在800-1000℃下通氮气高温煅烧2-3h(升温速率2-4℃/min)，最后得到核壳结构W@Gd 2O 3粉末。
(3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末加入到二甲基乙酰胺中超声分散30-60min，再加入一定量聚氨酯树脂胶，控制涂料中粉末的含量为60wt％，利用电动搅拌机搅拌 2-3h后，在小型涂布机上对面料进行涂覆，最后在60-80℃条件下干燥1-2h。
采用上述优选的技术方案制得的核壳结构W@Gd 2O 3，相比于钨和氧化钆共混粉末而言，核壳结构在辐射防护方面可以起到协同防护作用，消除防护弱区同时将辐射所产生的二次辐射进行有效吸收。
与现有技术方案相比，本发明至少具有以下有益效果：
本发明首先利用多巴胺在在弱碱有氧的条件下可自聚合为聚多巴胺，并且聚多巴胺在不同物质表面均具有非凡的黏附性，能够成功包覆钨，得到W@PDA。
PDA表面含有大量的酚羟基、胺基等极性基团，为络合各种金属离子提供了丰富的活性位点，能够有效地和硝酸钆溶液中的Gd +进行螯合。经过高温煅烧后PDA形成氮掺杂碳层附着在钨表面，而与Gd +发生螯的W@PDA转变成W@Gd 2O 3。
附图说明
图1为实施例1制得的核壳结构钨/氧化钆粉末的扫描电镜图。
具体实施方式
为更好地说明本发明，便于理解本发明的技术方案，本发明的典型但非限制性的实施例如下：
实施例1
本实施例提供了一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法，所述方法包括以下步骤为：
(1)配置2g/L浓度的多巴胺盐溶液，加入tris缓冲液调节溶液PH值为8.5，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌24h后过滤分离，再分别用去离子水和乙醇洗涤2次后，在80℃下烘干5h，得到W@PDA；
(2)将步骤(1)得到的W@PDA加入到0.3M/L浓度的硝酸钆溶液中，磁力搅拌2h后，过滤分离，在80℃下烘干5h，再将制得的样品在800℃下通氮气高温煅烧2h(升温速率2℃/min)，最后得到核壳结构W@Gd 2O 3粉末。
(3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末加入到二甲基乙酰胺中超声分散30min，再加入一定量聚氨酯树脂胶，控制涂料中粉末的含量为60wt％，利用电动搅拌机搅拌2h后，在小型涂布机上对面料进行涂覆，最后在60℃条件下干燥2h。
对本实施例制备得到的W@Gd 2O 3粉末进行了SEM扫描，所得照片如图1所示，由图中可以看出，在W粉的表面形成了PDA薄膜。
实施例2
本实施例提供了一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法，所述方法包括以下步骤为：
(1)配置1.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节溶液PH值为8，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌20h后过滤分离，再分别用去离子水和乙醇洗涤3次后，在60℃下烘干8h，得到W@PDA；
(2)将步骤(1)得到的W@PDA加入到0.35M/L浓度的硝酸钆溶液中，磁力搅拌3h后，过滤分离，在60℃下烘干8h，再将制得的样品在900℃下通氮气高温煅烧2.5h(升温速率3℃/min)，最后得到核壳结构W@Gd 2O 3粉末。
(3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末加入到二甲基乙酰胺中超声分散40min，再加入一定量聚氨酯树脂胶，控制涂料中粉末的含量为60wt％，利用电动搅拌机搅拌2.5h后，在小型涂布机上对面料进行涂覆，最后在70℃条件下干燥1.5h。
实施例3
本实施例提供了一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法，所述方法包括以下步骤为：
(1)配置2.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节溶液PH值为9，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌18h后过滤分离，再分别用去离子水和乙醇洗涤2次后，在70℃下烘干6h，得到W@PDA；
(2)将步骤(1)得到的W@PDA加入到0.4M/L浓度的硝酸钆溶液中，磁力搅拌2.5h后，过滤分离，在70℃下烘干6h，再将制得的样品在1000℃下通氮气高温煅烧3h(升温速率4℃/min)，最后得到核壳结构W@Gd 2O 3粉末。
(3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末加入到二甲基乙酰胺中超声分散50min，再加入一定量聚氨酯树脂胶，控制涂料中粉末的含量为60wt％，利用电动搅拌机搅拌3h后，在小型涂布机上对面料进行涂覆，最后在80℃条件下干燥1h。
上述对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改，并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此，本发明不限于上述实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (15)

  1. 一种X，γ射线防护用核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，所述方法包括以下步骤：
    (1)配置多巴胺盐溶液，加入缓冲液调节PH值，然后加入钨粉，搅拌，过滤，洗涤烘干后得到W@PDA：
    (2)将步骤(1)得到的W@PDA加入到硝酸钆溶液中，搅拌，过滤，经过高温煅烧得到核壳结构W@Gd 2O 3粉末；
    (3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末后加入到二甲基乙酰胺中分散，再加入一定量聚氨酯树脂胶，搅拌均匀后对面料进行涂覆，烘干。
  2. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(1)所述加入缓冲液调节PH值，所述缓冲液为tris，所述PH值为8-9。
  3. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(1)所述钨粉为用乙醇清洗过的钨粉。
  4. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(1)所述搅拌为电动搅拌器搅拌18-24h。
  5. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(1)所述洗涤为用去离子水和乙醇分别清洗2-3次。
  6. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(1)所述多巴胺盐溶液浓度为1.5g/L-2.5g/L。
  7. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(2)所述高温煅烧温度为800-1000℃，时间为2-3h，升温速率为2-4℃/min。
  8. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(2)所述煅烧在保护性气体中进行，所述保护性气体为氮气或惰性气体。
  9. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(2)所述硝酸钆溶液浓度为0.3-0.5M/L。
  10. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(3)所述加入到二甲基乙酰胺中分散需利用超声分散30-60min。
  11. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(3)所述加入一定量聚氨酯树脂胶，需控制涂料中粉末的含量为60wt％。
  12. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(3)所述搅拌为机械搅拌2-3h。
  13. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(3)所述涂覆为采用小型涂布机进行涂覆。
  14. 如权利要求1所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，在步骤(3)所述烘干为60-80℃条件下干燥1-2h。
  15. 如权利要求1-13任一项所述的核壳结构钨/氧化钆PU涂层面料的制备方法，其特征在于，所述方法包括以下步骤：
    (1)配置1.5g/L-2.5g/L浓度的多巴胺盐溶液，加入tris缓冲液调节PH至8-9，然后加入用乙醇清洗干净的钨粉，利用电动搅拌器搅拌18-24h后过滤分离，再分别用去离子水和乙醇洗涤2-3次后烘干，得到W@PDA：
    (2)将步骤(1)得到的W@PDA加入到0.3-0.5M/L浓度的硝酸钆溶液中，磁力搅拌一定时间后，过滤分离，烘干，再将制得的样品在800-1000℃下通氮气高温煅烧2-3h(升温速率2-4℃/min)，最后得到核壳结构W@Gd 2O 3粉末；
    (3)将步骤(2)得到的核壳结构W@Gd 2O 3粉末加入到二甲基乙酰胺中超声分散30-60min，再加入一定量聚氨酯树脂胶，控制涂料中粉末的含量为60wt％，利用电动搅拌机搅拌2-3h后，在小型涂布机上对面料进行涂覆，最后在60-80℃条件下干燥1-2h。
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