WO2023029564A1 - 三明治结构的碳/磁电磁波吸收材料及其制备方法 - Google Patents
三明治结构的碳/磁电磁波吸收材料及其制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 239000011358 absorbing material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001690 polydopamine Polymers 0.000 claims abstract description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 12
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 31
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000872 buffer Substances 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical group [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005054 agglomeration Methods 0.000 claims description 5
- 230000002776 aggregation Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- 229960002089 ferrous chloride Drugs 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 13
- 238000003763 carbonization Methods 0.000 abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910021577 Iron(II) chloride Inorganic materials 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229960003638 dopamine Drugs 0.000 description 3
- 238000009396 hybridization Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- CDRCPXYWYPYVPY-UHFFFAOYSA-N iron(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+2].[Fe+2].[Fe+2] CDRCPXYWYPYVPY-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0088—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a plurality of shielding layers; combining different shielding material structure
Definitions
- the application belongs to the technical field of electromagnetic materials, and in particular relates to a sandwich-structured carbon/magnetic electromagnetic wave absorbing material and a preparation method thereof.
- Electromagnetic pollution has become the fifth largest public hazard after wastewater, waste gas, solid waste and noise. Relevant reports indicate that electromagnetic pollution will replace noise pollution in this century and become one of the five major physical pollutions. At present, using electromagnetic wave absorbing materials to weaken or eliminate electromagnetic wave pollution is an effective method.
- ferrite or carbon materials are commonly used as electromagnetic wave absorbing materials in the market.
- Fe3iron tetroxide, carbonyl iron and magnetic electromagnetic wave absorbing materials are heavy in weight, and the prepared materials are thick and heavy, which limits their application range.
- carbon-based electromagnetic wave absorbing materials have the advantages of light weight, adjustable frequency range, and good compatibility with the organic/inorganic phase interface of the matrix.
- Graphite powder, carbon black, carbon nanotubes, chopped carbon fibers and activated carbon fibers have been reported as carbon-based electromagnetic wave protection functional fillers.
- the main factor determining the absorbing characteristics of carbon materials is electrical resistance, but its high conductivity makes it easy to reflect electromagnetic waves and affect the absorption efficiency.
- Electromagnetic wave absorbing materials are also improved by means of dielectric loss materials, a layer of magnetic loss materials, etc.
- the existing technology proposes a method for preparing electromagnetic wave absorbing materials with a sandwich structure, but there are still certain defects in the preparation process. It is not an obvious multi-layer structure, but a hybrid material, and the number of layers cannot be freely controlled. Self-regulated electromagnetic wave absorption performance.
- each exemplary embodiment of the present application provides a carbon/magnetic electromagnetic wave absorbing material with a sandwich structure and a preparation method thereof.
- the micro-flaky particles with multi-layer structures such as carbon layers and magnetic layers formed by bit hybridization can effectively absorb electromagnetic waves and have very broad application prospects.
- a carbon/magnetic electromagnetic wave absorbing material with a sandwich structure comprising a first composite layer, the first composite layer including a first inner layer, a first middle layer and a first outer layer, wherein the The first inner layer is ferroferric oxide, the first middle layer is a carbon layer, and the first outer layer is nano ferric oxide particles.
- the absorbing material further comprises a second composite layer, the second composite layer includes a second inner layer of iron tetraoxide, a second middle layer of carbon, and a nanometer layer of iron tetraoxide.
- the second outer layer of the particle is not limited to a second composite layer, the second composite layer includes a second inner layer of iron tetraoxide, a second middle layer of carbon, and a nanometer layer of iron tetraoxide.
- the present application provides a method for preparing a sandwich structure carbon/magnetic electromagnetic wave absorbing material, which includes the following steps, (1) by dissolving iron salt in diethylene glycol, preparing a mass fraction of 8 % to 10% metal salt solution S1; (2) by adding a buffering agent to the solution S1, stirring and dissolving, and standing for 5 minutes to prepare a solution S2; (3) by transferring the S2 solution to an autoclave , pass through the protective gas, keep at 200°C for 8 hours, shake once every 30 minutes to prevent the agglomeration of particles, and obtain ferric oxide, then take out the ferric oxide, wash and dry with deionized water , obtain flaky ferric oxide; (4) prepare solution S3 by configuring the dopamine hydrochloride of 1g/L to 2g/L and adjusting the pH to 8.5; (5) prepare the flaky ferric oxide by step (3) Iron ferric oxide is put into the solution S3, wherein the mass fraction of the sheet-shaped ferric iron tetro
- the iron salt is selected from ferric sulfate and ferric chloride.
- the sandwich structure carbon/magnetic electromagnetic wave absorbing material includes a first combined layer, the first combined layer includes a first inner layer, a first middle layer and a first outer layer, and the first and other The inner layer is iron ferric oxide, the first middle layer is a carbon layer, and the first outer layer is nano ferric oxide particles.
- the buffer is citric acid-sodium citrate.
- the protective gas is nitrogen.
- steps (4)-(7) are repeated to prepare an electromagnetic wave absorbing material with multiple combined layers.
- the sandwich-structured carbon/magnetic electromagnetic wave absorbing material prepared by cross-hybridization of ferroferric oxide and carbon in this application can significantly improve the electromagnetic wave absorbing performance of the material, has both dielectric loss and magnetic loss properties, and is light in weight. It can be used as an electromagnetic wave absorber and combined with textiles, polymer adhesives, etc. to prepare light and soft electromagnetic wave absorbing composite materials, and has very broad application prospects.
- Fig. 1 is the SEM picture of the carbon-magnetic electromagnetic wave absorbing material of the sandwich structure prepared by the present application;
- Fig. 2 is the carbon-magnetic electromagnetic wave absorbing material electromagnetic wave absorption performance figure of the sandwich structure that the embodiment 1 of the present application makes;
- Fig. 3 is the carbon-magnetic electromagnetic wave absorbing material electromagnetic wave absorption performance figure of the sandwich structure that the embodiment 2 of the present application makes;
- Fig. 4 is a diagram of the electromagnetic wave absorption performance of the sandwich-structured carbon-magnetic electromagnetic wave absorbing material prepared in Example 3 of the present application.
- step 3 transfer the solution prepared in step 2 to a stainless steel autoclave lined with Teflon, keep it at 200°C for 8 hours, feed nitrogen to protect ferric oxide from oxidation during the reaction, and simultaneously Vibrate once in 30 minutes to prevent the agglomeration of particles; then take it out and wash it with deionized water and dry it to obtain flake ferric oxide;
- Dopamine hydrochloride of 1g/L is configured, and the pH of the solution is adjusted to 8.5 by using a citric acid-sodium citrate buffer;
- step 5 Place the material prepared in step 5 into a nitrogen atmosphere at 450°C for carbonization treatment for 1 hour, and then take it out;
- the prepared material is ferroferric oxide as the inner layer, the middle layer is a carbon layer, and the outermost layer is nanometer ferric oxide particles, the conductivity is 0.2S/cm, and the special sandwich structure has certain electromagnetic wave absorption performance, as shown in Figure 2 below.
- step 3 transfer the solution prepared in step 2 to a stainless steel autoclave lined with Teflon, keep it at 200°C for 8 hours, feed nitrogen to protect ferric oxide from oxidation during the reaction, and simultaneously Vibrate once in 30 minutes to prevent the agglomeration of particles; then take it out and wash it with deionized water and dry it to obtain flake ferric oxide;
- step 5 Place the material prepared in step 5 into a nitrogen atmosphere at 600°C for carbonization treatment for 1 hour, and then take it out;
- the prepared material is ferroferric oxide as the inner layer, the middle layer is carbon layer, the outermost layer is nanometer ferric oxide particles, the conductivity is 0.8S/cm, and the special sandwich structure has good electromagnetic wave Absorption performance, controlling the carbonization temperature of dopamine can effectively improve the electromagnetic wave absorption performance of the material, as shown in Figure 3 below.
- step 3 transfer the solution prepared in step 2 to a stainless steel autoclave lined with Teflon, keep it at 200°C for 8 hours, feed nitrogen to protect ferric oxide from oxidation during the reaction, and simultaneously Vibrate once in 30 minutes to prevent the agglomeration of particles; then take it out and wash it with deionized water and dry it to obtain flake ferric oxide;
- step 5 Place the material prepared in step 5 into a nitrogen atmosphere at 600°C for carbonization treatment for 1 hour, and then take it out;
- the prepared material is ferroferric oxide as the inner layer, and the outer layer is alternately loaded with carbon layer and nanometer ferric oxide particle layer.
- the conductivity is 0.85S/cm.
- the multi-layer special sandwich structure has excellent electromagnetic wave absorption Performance, we found that the electromagnetic wave absorption performance of the material becomes stronger, the minimum loss reaches -19dB, and the bandwidth of the effective loss ( ⁇ -10dB) in the 2-18GHz band reaches 12GHz, as shown in Figure 4 below.
- the coating, carbonization and other preparation processes involved in this application generate a carbon layer in situ on the surface of the flake ferric oxide, so that the product structure is more stable, and the carbonization rate of dopamine can be controlled by the carbonization temperature.
- the preparation process controls the number of layers in order to achieve the maximum absorption performance under different electromagnetic wave frequency bands.
- the dispersion of various materials prepared by it is not stable, and the stability is not good.
- this patent is loaded layer by layer, and the thickness of each layer is controllable.
- the prepared material has stable performance.
- the carbon layer has a great influence on the performance of the material.
- This patent uses dopamine coating and carbonization technology to prepare carbon layers with different conductivity to control the electromagnetic wave impedance matching and coordinated electromagnetic wave loss of the material as a whole.
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- Physics & Mathematics (AREA)
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- Engineering & Computer Science (AREA)
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- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Hard Magnetic Materials (AREA)
Abstract
本申请公开了一种三明治结构的碳/磁电磁波吸收材料及其制备方法，其利用铁盐制备片状四氧化三铁；将5-10g片状四氧化三铁包覆聚多巴胺获得片状材料，再将包覆聚多巴胺的片状材料置入450-600℃氮气气氛中碳化处理1小时得到材料，加入到100ml蒸馏水中，然后加入摩尔比为2:1的氯化铁和氯化亚铁共混物5g，搅拌溶解后逐渐滴入8ml氨水，在50℃水浴中反应1小时，洗净即可。三明治结构碳/磁电磁波吸收材料，结构为四氧化三铁为内层，中间层为碳层，最外层为纳米四氧化三铁颗粒，可以明显的改善材料的电磁波吸收性能，兼具介电损耗和磁损耗性能，而且质量轻，具有非常广阔的应用前景。
Description
相关申请
本申请要求于2021年9月6日提交中国专利局、申请号为202111038277X、申请名称为“一种三明治结构的碳/磁电磁波吸收材料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
本申请属于电磁材料技术领域，具体涉及一种三明治结构的碳/磁电磁波吸收材料及其制备方法。
随着电子、电气技术的迅速发展，电磁能利用范围不断扩大，随之而来的就是电磁辐射污染。电磁污染问题已成为继废水、废气、固体废弃物和噪音之后的第5大公害，有关报道表明本世纪电磁污染将取代噪声污染而成为主要的5大物理污染之一。目前，利用电磁波吸收材料来减弱或消除电磁波污染是一种有效的方法。
目前市场上普遍使用铁氧体或者碳材料作为电磁波吸收材料。四氧化三铁、羰基铁以及磁性电磁波吸收材料质量重，所制备的材料厚重，限制了其应用的范围。另一方面，碳基电磁波吸收材料具有重量轻、频率范围可调、与基体的有机/无机相界面相容性好的优点。石墨粉、炭黑、碳纳米管、短切碳纤维和活性碳纤维作为碳基电磁波防护功能填料均已有研究报道。但是，碳材料决定其吸波特性的主要因素是电阻，但是其电导率较高，容易反射电磁波，影响吸收效率。为此，许多研究者在碳材料上负载磁性粒子，包括石墨粉镀镍、碳纳米管镀镍、以及负载纳米铁氧体粒子等方式来提高材料的电磁波吸收性能，另外也有通过涂覆一层介电损耗材料、一层磁损耗材料等方式也改善电磁波吸收材料。现有技术提出了制备三明治结构的电磁波吸收材料的方法，但是在制备工艺上还存在着一定的缺陷，不是明显的多层结构，而是混杂材料，不能自由的进行层数的控制，从而不能自主调控电磁波吸收性能。
发明内容
为了克服现有技术中电磁波吸收材料产品质量重、成型困难、电磁波损耗机制单一等问题，本申请各示例性实施例提供了一种三明治结构的碳/磁电磁波吸收材料及其制 备方法，通过原位杂化方式形成碳层、磁层等多层结构的微米片状颗粒，可以针对电磁波进行有效的吸收，具有非常广阔的应用前景。
本申请提供的技术方案：一种三明治结构的碳/磁电磁波吸收材料，包括第一组合层，所述第一组合层包括第一内层、第一中间层和第一外层，其中，所述第一内层为四氧化三铁，所述第一中间层为碳层，所述第一外层为纳米四氧化三铁颗粒。
在一实施例中，所述吸收材料还包含第二组合层，所述第二组合层包括为四氧化三铁的第二内层、为碳层的第二中间层以及为纳米四氧化三铁颗粒的第二外层。
作为本申请的另一方面，本申请提供一种三明治结构碳/磁电磁波吸收材料的制备方法，其包括以下步骤，(1)通过将铁盐溶解到二乙二醇中，制备质量分数为8％至10％金属盐溶液S1；(2)通过向所述溶液S1中加入缓冲剂，并搅拌溶解后静置5分钟，制备溶液S2；(3)通过将所述S2溶液转移至高压釜中，通入保护气体，在200℃下保持8小时，每隔30min进行震动1次来防止颗粒的团聚，得到四氧化三铁，然后取出所述四氧化三铁，并用去离子水洗净烘干，得到片状四氧化三铁；(4)通过配置1g/L至2g/L的盐酸多巴胺并调节pH至8.5，制备溶液S3；(5)通过将步骤(3)制备的所述片状四氧化三铁放入所述溶液S3中，其中所述片状四氧化三铁的质量分数为9％至11％，然后在30℃水浴中震荡反应10至24小时，得到包覆聚多巴胺的片状材料；(6)将所述包覆聚多巴胺的片状材料置入450℃至600℃的氮气气氛中碳化处理1小时得到材料S4；(7)将每10g的所述材料S4加入到100ml蒸馏水中，然后加入摩尔比为2:1的氯化铁和氯化亚铁共混物5g搅拌溶解后，逐渐滴入8ml氨水，在50℃水浴中反应1小时，洗净以得到所述三明治结构碳/磁电磁波吸收材料。
在一实施例中，所述铁盐选自硫酸铁、氯化铁。
在一实施例中，所述三明治结构碳/磁电磁波吸收材料，包括第一组合层，所述第一组合层包括第一内层、第一中间层以及第一外层，所述第一其内层为四氧化三铁，所述第一中间层为碳层，所述第一外层为纳米四氧化三铁颗粒。
在一实施例中，所述缓冲剂为柠檬酸-柠檬酸钠。
在一实施例中，所述保护气体为氮气。
在一实施例中，重复步骤(4)-(7)，以制备具有多个组合层的电磁波吸收材料。
本申请的有益效果如下：
本申请以四氧化三铁和炭交叉杂化成型制备的三明治结构的片状碳/磁电磁波吸收材料可以明显的改善材料的电磁波吸收性能，兼具介电损耗和磁损耗性能，而且质量轻，可以作为电磁波吸收剂与纺织品、高分子粘合剂等复合制备轻质且柔软的电磁波吸收复合材料，具有非常广阔的应用前景。
图1为本申请制备的三明治结构的碳-磁电磁波吸收材料的SEM图片；
图2为本申请实施例1制得的三明治结构的碳-磁电磁波吸收材料电磁波吸收性能图；
图3为本申请实施例2制得的三明治结构的碳-磁电磁波吸收材料电磁波吸收性能图；
图4为本申请实施例3制得的三明治结构的碳-磁电磁波吸收材料电磁波吸收性能图。
下面结合附图对本申请作更进一步的说明。
实施例1：
(1)将2g无水氯化铁溶解到20ml二乙二醇中，制备金属盐溶液；
(2)将2g柠檬酸-柠檬酸钠缓冲剂(pH＝10)加入到步骤1溶液中，搅拌溶解后静置5分钟，制备溶液；
(3)将步骤2制备的溶液转移至内衬为特氟龙的不锈钢高压釜中，在200℃下保持8小时，在反应过程中通入氮气保护四氧化三铁不被氧化，同时每隔30min进行震动1次来防止颗粒的团聚；然后取出用去离子水洗净烘干，得到片状四氧化三铁；
(4)配置1g/L的盐酸多巴胺，利用柠檬酸-柠檬酸钠缓冲剂将溶液pH调节至8.5；
(5)将5g片状四氧化三铁放入50ml的步骤4制备的溶液中，然后在30℃水浴中震荡反应10小时，得到包覆聚多巴胺的片状材料，聚多巴胺厚度为5nm；
(6)将步骤5制备的材料置入450℃氮气气氛中碳化处理1小时，然后取出；
(7)将10g步骤6制备的材料加入到100ml蒸馏水中，然后加入摩尔比为2:1的氯化铁和氯化亚铁共混物5g，搅拌溶解后逐渐滴入8ml氨水，在50℃水浴中反应1小时，然后洗净备用；
(8)所制备的材料为四氧化三铁为内层，中间层为碳层，最外层为纳米四氧化三铁颗粒，电导率为0.2S/cm，特殊的三明治结构具有一定的电磁波吸收性能，如下图2 所示。
实施例2：
(1)将10g无水氯化铁溶解到80ml二乙二醇中，制备金属盐溶液；
(2)将5g柠檬酸-柠檬酸钠缓冲剂(pH＝10)加入到步骤1溶液中，搅拌溶解后静置5分钟，制备溶液；
(3)将步骤2制备的溶液转移至内衬为特氟龙的不锈钢高压釜中，在200℃下保持8小时，在反应过程中通入氮气保护四氧化三铁不被氧化，同时每隔30min进行震动1次来防止颗粒的团聚；然后取出用去离子水洗净烘干，得到片状四氧化三铁；
(4)配置2g/L的盐酸多巴胺，利用柠檬酸-柠檬酸钠缓冲剂将溶液pH调节至8.5；
(5)将10g片状四氧化三铁放入80ml的步骤4制备的溶液中，然后在30℃水浴中震荡反应24小时，得到包覆聚多巴胺的片状材料，聚多巴胺厚度为10nm；
(6)将步骤5制备的材料置入600℃氮气气氛中碳化处理1小时，然后取出；
(7)将10g步骤6制备的材料加入到100ml蒸馏水中，然后加入摩尔比为2:1的氯化铁和氯化亚铁共混物5g，搅拌溶解后逐渐滴入8ml氨水，在50℃水浴中反应1小时，然后洗净备用；
(8)所制备的材料为四氧化三铁为内层，中间层为碳层，最外层为纳米四氧化三铁颗粒，电导率为0.8S/cm，特殊的三明治结构具有很好的电磁波吸收性能，控制好多巴胺的碳化温度，可以有效的提高材料的电磁波吸收性能，如下图3所示。
实施例3：
(1)将10g无水氯化铁溶解到80ml二乙二醇中，制备金属盐溶液；
(2)将柠檬酸-柠檬酸钠5g缓冲剂(pH＝10)加入到步骤1溶液中，搅拌溶解后静置5分钟，制备溶液；
(3)将步骤2制备的溶液转移至内衬为特氟龙的不锈钢高压釜中，在200℃下保持8小时，在反应过程中通入氮气保护四氧化三铁不被氧化，同时每隔30min进行震动1次来防止颗粒的团聚；然后取出用去离子水洗净烘干，得到片状四氧化三铁；
(4)配置2g/L的盐酸多巴胺，利用柠檬酸-柠檬酸钠缓冲剂将溶液pH调节至8.5；
(5)将10g片状四氧化三铁放入80ml的步骤4制备的溶液中，然后在30℃水浴中 震荡反应24小时，得到包覆聚多巴胺的片状材料，聚多巴胺厚度为10nm；
(6)将步骤5制备的材料置入600℃氮气气氛中碳化处理1小时，然后取出；
(7)将10g步骤6制备的材料加入到100ml蒸馏水中，然后加入摩尔比为2:1的氯化铁和氯化亚铁共混物5g，搅拌溶解后逐渐滴入8ml氨水，在50℃水浴中反应1小时，然后洗净备用；
(8)重复4-7步骤1次，再次进行聚多巴胺的包覆、碳化及最外层四氧化三铁的负载；
(9)所制备的材料为四氧化三铁为内层，外面为碳层、纳米四氧化三铁颗粒层交替负载，电导率为0.85S/cm，多层的特殊三明治结构具有优异的电磁波吸收性能，我们发现材料的电磁波吸收性能变强，最低损耗达到了-19dB，在2-18GHz波段范围有效损耗(＜-10dB)的频宽达到了12GHz，如下图4所示。
本申请所涉及的包覆、碳化等制备工艺，通过在片状四氧化三铁表面进行原位生成碳层，所生产的产品结构更加稳定,通过碳化温度来控制多巴胺的碳化率，同时可以通过制备工艺进行层数的控制，以便达到不同电磁波频段下最大吸收性能。相比于其他技术进行多种材料的共混及杂化，其制备的各种材料分散规律不定，稳定性不佳，而本专利是一层一层的进行负载，每层的厚度可控，制备出的材料性能稳定。碳层对材料性能影响较大，本专利利用多巴胺包覆及碳化技术进行不同导电率碳层的制备，来控制材料整体的电磁波阻抗匹配及协同电磁波损耗。
以上所述仅是本申请的优选实施方式，应当指出：对于本技术领域的普通技术人员来说，在不脱离本申请原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本申请的保护范围。
Claims (8)
- 一种三明治结构的碳/磁电磁波吸收材料，其中，所述三明治结构碳/磁电磁波吸收材料，包括第一组合层，所述第一组合层包括第一内层、第一中间层和第一外层，其中，所述第一内层为四氧化三铁，所述第一中间层为碳层，所述第一外层为纳米四氧化三铁颗粒。
- 如权利要求1所述的电磁波吸收材料，其中，所述吸收材料还包含第二组合层，所述第二组合层包括为四氧化三铁的第二内层、为碳层的第二中间层以及为纳米四氧化三铁颗粒的第二外层。
- 一种三明治结构碳/磁电磁波吸收材料的制备方法，包括：(1)通过将铁盐溶解到二乙二醇中，制备得到质量分数为8％至10％金属盐溶液S1；(2)通过向所述溶液S1中加入缓冲剂，并搅拌溶解后静置5分钟，制备得到溶液S2；(3)通过将所述溶液S2转移至高压釜中，通入保护气体，在200℃下保持8小时，每隔30min进行震动1次来防止颗粒的团聚，得到四氧化三铁，然后取出所述四氧化三铁，并用去离子水洗净烘干，得到片状四氧化三铁；(4)通过配置1g/L至2g/L的盐酸多巴胺并调节pH至8.5，制备得到溶液S3；(5)通过将步骤(3)制备的所述片状四氧化三铁放入所述溶液S3中，其中所述片状四氧化三铁的质量分数为9％至11％，然后在30℃水浴中震荡反应10至24小时，得到包覆聚多巴胺的片状材料；(6)将所述包覆聚多巴胺的片状材料置入450℃至600℃的氮气气氛中碳化处理1小时得到材料S4；(7)将每10g的所述材料S4加入到100ml蒸馏水中，然后加入摩尔比为2:1的氯化铁和氯化亚铁共混物5g搅拌溶解后，逐渐滴入8ml氨水，在50℃水浴中反应1小时，洗净以得到所述三明治结构碳/磁电磁波吸收材料。
- 如权利要求3所述的方法，其中，步骤(1)中所述铁盐选自硫酸铁、氯化铁。
- 如权利要求3所述的方法，其中，步骤(7)得到的所述三明治结构碳/磁电磁波吸收材料包括第一组合层，所述第一组合层包括第一内层、第一中间层以及第一外层，所述第一内层为四氧化三铁，所述第一中间层为碳层，所述第一外层为纳米四氧化三铁颗粒。
- 如权利要求3所述的方法，其中，所述缓冲剂为柠檬酸-柠檬酸钠。
- 如权利要求3所述的方法，其中，所述保护气体为氮气。
- 如权利要求5所述的方法，其中，重复步骤(4)-(7)，以制备具有多个组合层的电磁波吸收材料。
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