摘要
微米螺旋碳纤维(CMC)不仅具有普通碳纤维的高强度、低密度、耐高温、化学性质稳定等优点,而且其独特的螺线管大空腔的结构,有望用作新型雷达吸波材料。
本论文采用多种方法对微米螺旋碳纤维材料进行了磁性修饰,并深入研究了其电磁吸波性能。论文中另一部分工作围绕形貌不同于微米螺旋碳纤维的新型弹簧状微纳米螺旋碳纤维的制备、结构及性能进行了系统的研究,并对其生成机理进行了初步的探讨。主要内容如下:
1.论文首先对相关领域的研究工作进行总结。基于电磁基本方程、电磁参数以及电磁波平面阻抗匹配理论,在综述螺旋碳纤维、铁氧体、铁碳复合材料研究现状的基础上,提出本论文的研究内容及要解决的主要科学问题。
2.采用化学气相沉积法,合成了规则的弹簧状微纳米螺旋碳纤维。系统研究了催化剂种类、助剂噻吩的用量、反应温度、反应气组成及流量等各种实验条件对产物结构的影响;在此基础上,优化了实验条件并得到形貌均一的微纳米螺旋碳纤维。基于气-液-固-固生长机理,论文从实验上对螺旋碳纤维形成进行了研究,结果表明弹簧状微纳米螺旋碳纤维与CMC具有相同的生成机理。
3.选用共沉淀、高聚物保护液相合成方法和溶胶凝-胶法制备了多种形貌的铁氧体,首次用所合成的多种形貌的纳米级铁氧体和铁颗粒对活化后的微米螺旋碳纤维进行了修饰和填充,并用优化了的修饰方法和填充工艺,得到了电磁性能兼备的纳米铁氧体和纳米铁颗粒填充的螺旋碳纤维复合材料,并对其性能进行了详细研究。
4.利用反胶束法制备的明胶包覆草酸亚铁颗粒作为前躯体,通过高温下氢气还原,制备了核壳式碳包铁复合微球,对其性能研究表明,这是一种具有优良电磁性能的复合材料。
5.论文首次针对微米螺旋碳纤维的粒径和样品的添加比例对复合结构的电磁参数和吸波性能的影响进行了系统研究,模拟了相关添加比例的反射率曲线,为螺旋碳纤维作为雷达吸波材料的应用提供了有价值的参考数据。
Due to the excellent physical and chemical properties, as well as the novel structure, the carbon micro-coils (CMC) have the promise of being used as an efficacious material for radar absorption. In this dissertation, the spring-like carbon fibers having distinct morphologies from the carbon micro-coils were successfully synthesized. Furthermore, the as-synthesized CMC were modified with nanometer ferrite and ferric grain. The electromagnetic properties of this new kind of composite material were investigated in detail.
At first, the relevant researches about the helical carbon fibers were summarized. From the basic electromagnetic equations, electromagnetic parameters, and electromagnetic wave impedance matching theory to the spiral of carbon fiber, ferrite and iron-carbon composite materials, the contents of their research were reviewed in this paper, respectively.
Secondly, the regular spring-like carbon fibers were fabricated by a catalytic pyrolysis method with acetylene as a carbon resource, Fe as a catalyst and thiophene as a promoter. The dependence of the products’structures on the preparation conditions, including the catalyst, additive thiophene, reaction temperature as well as gas composition and flow rate, etc. was explored. By optimizing experimental parameters, the uniform spring-like carbon fibers were obtained. It was demonstrated that the growth of the spring-like carbon fibers might be attributed to the process of gas-liquid-solid-solid, similar to the growth mechanism of CMC.
The nano-sized ferrites and ferric particles with various morphologies were prepared by co-precipitation and liquid synthesis with polymer protection. The as-prepared nanoparticles were employed to fill and modify the CMCs through an optimized process. The electromagnetic properties of the synthesized iron-carbon composites were studied. It is indicated that the present composites own excellent electric as well as magnetic properties, and were expected to achieve better impedance matching.
The gelatin-coated ferrous oxalate particles were fabricated as precursors by reverse micelles method. The precursors were subsequently reduced by hydrogen at a high temperature. As a result, the carbon-coated iron core-shell composite microspheres were obtained. The electromagnetic properties of the core-shell structure were characterized.
It was found that the electromagnetic properties of the CMCs were strongly depended on the size of the CMC grain as well as th ratio of the CMC to matrices. These data could be utilized to design the coat for radar absorption in the further.
引文
1刘顺华,刘军民,董星龙等.电磁波屏蔽和吸波材料.北京,化学工业出版社,2007.
2刑丽英等.隐身材料.北京,化学工业出版社,2004.
3康青.新型微波吸收材料.北京,科学出版社,2006.
4 Yang S, Chen X, Motojima S. Diamond & Related Materials, 2004,13:2152– 2155
5 Yang S, Chen X, Motojima S, etc. Carbon, 2005,43:827–834
6 Chen X, Yang S, Motojima S. Materials Letters, 2005,59:854– 858
7 Bajpai V, Dai L, Ohashi T. J. Am. Chem. Soc. 2004, 126:5070-5071
8李文治,解思深,钱露茜等.高技术通讯,1997,1:19-21
9元岛栖二.高科技纤维与应用, 1998,23(264):52-53
10吴明在,姚连增,姜国伟等.无机材料学报, 2003,18(1):115-120
11陈程雯,蔡云,林敬东等.厦门大学学报(自然科学版), 2003,42 (1):130-132
12陈一匡,徐鸿辉,熊琪等.汕头大学学报(自然科学版), 2003,18(2):30-34
13赵东林,沈曾民.无机材料学报,2003,18(5):1057-1062
14彭峰,姜靖雯,黄碧纯等.无机化学学报, 2003, 19(11):1160-1162
15郭定和,郑朝丹,范湘军.湖北大学学报(自然科学版), 2004,26(1):31-34
16郭定和,郑朝丹,范湘军.功能材料与器件学报,2004, 10(1):49-53
17陆梅,郭新勇,力虎林等.高等学校化学学报,2004,25(8):1541-1544
18郭定和,范湘军.武汉大学学报(理学版), 2004,50(5):559- 562
19于立岩,张乾,崔作林.高等学校化学学报, 2005,26(1):5- 8
20 Yang S, Chen X, Motojima S,etc.Carbon, 2005,43:916–922
21 Qin Y, Zhang Z, Cui Z. Letters to the Editor / Carbon, 2003,41:3063– 3074
22 Yang S, Chen X, Motojima S,etc. Carbon, 2005,43:827–834
23 Xie J, Sharma P K, Varadan V V,etc. Materials Chemistry and physics, 2002,76:217-223
24 Mukhopadhyay K, Ram K, Lal D,etc. Letters to the Editor / Carbon, 2005,43 :2397–2429
25 Chen X, Yang S, Motojima S,etc. Diamond and Related Materials, 2003,12 : 1836–1840
26 Chen X, Yang S, Motojima S. Materials Letters, 2005,59:854– 858
27 Pan L, Hayashida T, Harada A, etc. Physica B, 2002,323:350–351
28 Motojima S, Kawaguchi M, Nozaki K, etc. Appl. Phys. Lett. 1990,56(4), 321-323
29 Yang S, Chen X, Motojima S, etc. Carbon, 2005,43:916–922
30 Yang S, Chen X, Motojima S, etc. Carbon, 2005,43 :827–834
31 Chen X, Yang S, Motojima S. Materials Letters, 2005,59:854– 858
32 Bai J B. Materials Letters, 2003,57:2629– 2633
33 Yang S, Chen X, Motojima S, etc. Carbon, 2005,43 :827–834
34 Chen X, Yang S, Motojima S,etc. Diamond and Related Materials, 2003,12 : 1836–1840
35 Lu M, Li H. J. Phys. Chem. B, 2004, 108: 6186-6192
36 Yang S, Chen X, Motojima S, etc. Carbon, 2005,43 :827–834
37 Chen X, Yang S, Motojima S,etc. Diamond and Related Materials, 2003,12 : 1836–1840
38 Motojima S, Yang S, Chen X. Materials Research Bulletin, 2000,35:203–209
39 Motojima S, In-Hwang W, Chen X. Materials Research Bulletin, 2000,35:1517–1524
40 Motojima S, In-Hwang W. J. Mater. Sci., 2001,36 :673– 677
41 Motojima S, Yang S, Chen X. J. Mater. Sci., 1999,34: 5989– 5994
42 Yang S, Ueshima N, Motojima S. Materials Science and Engineering A, 2003,346:29-33
43 Motojima S, Suzuki T, Noda Y, etc. Chemical Physics Letters, 2003,378:111-116
44 Chen X, Motojima S, Iwanaga H. Carbon, 1999,37:1825-1831
45 Motojima S, Chen X, Yang S, etc. Diamond & Related Materials, 2004,13:1989–1992
46 Kaneto K, Tsuruta M, Motojima S. Synthetic Metals, 1999,103:2578-2579
47赵东林,沈曾民.无机材料学报,2003,18(5):1057-1062
48沈曾民,戈敏,赵东林.新型炭材料,2005,20(4):289-293
49 Xie G, Wang Z, Cui Z,etc. Letters to the Editor /Carbon, 2005,43:3181–3194
50 Du J, Sun C, Bai S, etc. J. Mater. Res., 17(5):1232-1236
51 Motojima S, Noda Y, Hoshiya S, etc. J. Appl. Phys., 2003,94( 4):2325-2330
52 Motojima S, Hoshiya S, Hishikawa Y. Letters to the Editor / Carbon, 2003,41:2653– 2689
53 Pan L, Hayashida T, Zhang M,etc. Jpn. J. Appl. Phys., 2001, 40,pt.2(3b):L235-L237
54 Pan L, Konishi Y, Tanaka H, etc. Jpn. J. Appl. Phys. 2005,44(4a):1652-1654
55 Fujiia M, Matsui M, Motojima S etc. Journal of Crystal Growth, 2002,237–239:1937–1941
56磁性材料.北京:科学出版社,克雷克:特贝尔:北京冶金研究所<<磁性材料>>翻译组.
57车仁超,李永清,陈朝辉等.钴铁氧体微粉的化学法制备工艺及其吸波性能.宇航材料工艺,1999(6):46-48
58车仁超,李永清,陈朝辉等.钴铁氧体微粉的化学法制备工艺及其磁特性研究.功能材料,1999,30(6):615-616
59葛秀涛,冯剑,侯长平等. YFe1-y CoyO3半导体气敏材料的制备和性能研究.无机材料学报,2002,17(3):526-530
60邵海成,戴红莲,黄健等.化学共沉淀法合成CoFe204纳米颗粒及其磁性能.硅酸盐学报, 2005,33(8)
61姜玉敏,刘辉,魏雨.纳米铁酸钴的液相催化制备.河北师范大学学报(自然科学版),2005,29(6):591-594
62朱伟长,周安娜,晋传贵,姚万斌,冒爱琴.铁酸钴纳米晶体的制备及机理.化工冶金, 2000,21(1):68-71
63王静,邓彤,冯亚萍,戴玉杰.钴基铁酸盐的室温合成和表征.光谱学和光谱分析,2005,25(8):1366—1370
64 Sol-gel法制备纳米晶镍锌钴铁氧体/二氧化硅复合颗粒的研究.徐小玉等.材料导报.2005(19):189-192
65肖利,方正,李元高,张全茹,王少芬.溶胶-凝胶法制备纳米级CoFe2O4尖晶石.材料导报.2004(18专辑):147-149
66于洪浩,高文元,孙俊才.复掺杂钴铁酸盐的制备及性能.电池,2005,35(3):185-187
67午丽娟,沈国柱,徐政,蔡瑞琦.铁氧体及碳纤维填充水泥基复合材料吸波性能.建筑材料学报,2006,9(5):603-607
68刘莹莹,褚莹,王元鸿. AHOT/异辛烷反胶束体系制备铁酸钴纳米粒子.分子科学学报, 2006,22 (1)
69魏雨,郑学忠,刘晓林等.均分散针状a-Fe203的制备.应用化学, 1996,13(1):86-88
70李龙土,桂治轮,岳振星,周济,齐西伟.溶胶凝胶自燃烧法合成Mn0.6Cu0.2Zn0.2O(Fe2O3)0.98纳米晶铁氧体及其磁性能研究.硅酸盐学报,2003(02)
71杨毅,李凤生,谈玲华.纳米a-Fe2O3的制备及其催化高氯酸铵热分解.兵工学报, 2004,25(1)
72葛秀涛,冯剑,侯长平等. YFe1一y Coy O3半导体气敏材料的制备和性能研究.无机材料学报, 2002,17(3)
73车仁超,李永清,陈朝辉等.钴铁氧体微粉的化学法制备工艺及其吸波性能.宇航材料工艺,1999(6):46-48
74刘飚,官建国,王琦等.核壳型铁钴复合材料的制备及其微波吸收性.功能材料,2005年第1期(36)卷:133-135
75 Jiu Rong Liua, Masahiro Itoha, Jianzhuang Jiangb, Ken-ichi Machida.Electromagnetic wave absorption properties of e-Fe3N/Y2O3 nanocomposites derived from Y2Fe17 intermetallic compound. Journal of Magnetism and Magnetic Materials, 2004 (277): 251–256
76午丽娟,沈国柱,徐政,蔡瑞琦.铁氧体及碳纤维填充水泥基复合材料吸波性能.建筑材料学报,2006,9(5): 603-607
77沈国柱,徐政,蔡瑞琦.短切碳纤维一铁氧体填充的复合材料吸波性能.同济大学学报(自然科学版),2006, 34(7):933-936
78沈国柱,徐政,蔡瑞琦.基于铁氧体和碳纤维的双层复合材料吸波性能研究.玻璃钢/复合材料,2007(1):19-23
79王海.雷达吸波材料的研究现状和发展方向[J].上海航天,1999 (1):55-59
80方亮,龚荣州,宫建国.雷达吸波材料的现状与展望[J].武汉工业大学学报,1999,21(6):21-24
81赵振声,张秀成,聂彦,何华辉.多晶铁纤维吸波材料的微波磁性研究.磁性材料及器件,2000年2月Vol31 No1:18-21
82周敏,杨觉明,周建军.吸波材料研究进展.西安工业学院学报,2000年12月第20卷第4期:296-302
83刘俊能,邢丽英.雷达吸波涂料研究进展[J],航空制造工程,1996,120[12):6
84雷中兴,刘菁,李轩科等. CVD法制备的碳包覆(Fe,Co)纳米粒子的结构及电磁特性.磁性材料及器件,2003,34(4):4-6
85 Ok Ja Yoon, Sung Min Kang , Soung Min Moon, etc. Deposition of iron nanoparticles onto multiwalled carbon nanotubes by helicon plasma- enhanced, chemical vapor deposition. Journal of Non-Crystalline Solids ,2007 (353): 1208–1211
86 Z.H. Wang, C.J. Choi, B.K. Kim, etc. C haracterization and magnetic properties of carbon-coated cobalt nanocapsules synthesized by the chemical vaporcondensation process. Carbon ,2003 (41): 1751–1758
87 Z.H. Wang, Z.D. Zhanga, C.J. Choib, etc. Structure and magnetic properties of Fe(C) and Co(C) nanocapsules prepared by chemical vapor condensation. Journal of Alloys and Compounds, 2003 (361): 289–293
88 Satoshi Tomita , Masahiro Hikita , Minoru Fujii,etc. A new and simple method for thin graphitic coating of magnetic-metal nanoparticles.Chemical Physics Letters. 2000(316):361–364
89 Hisato Tokoro , Shigeo Fujii, Takeo Oku.Iron nanoparticles coated with graphite nanolayers and carbon nanotubes. Diamond and Related Materials 2004 (13): 1270–1273
90 Hisato Tokoroa, Shigeo Fujiia, Takeo Oku.Magnetic fine particles of Fe and Co encapsulated bycarbon layers. Journal of Magnetism and Magnetic Materials , 2005 (290–291) :141–144
91 M. Inagaki, Y. Okada, H. Miura, H. Konno. Preparation of carbon-coated transition metal particles from mixtures of metal oxide and polyvinylchloride. Carbon , 1999 (37) :329–334
92 Nicholas A. D. Burke, Harald D. H. Stover, and Francis P. Dawson. Magnetic Nanocomposites: Preparation and Characterization of Polymer-Coated Iron Nanoparticles. Chem. Mater. 2002( 14): 4752-4761
93 Sung-Soo Kima, Seon-Tae Kima, Joon-Mo Ahn,etc. Magnetic and microwave absorbing properties of Co–Fe thin films plated on hollow ceramic microspheres of low density. Journal of Magnetism and Magnetic Materials, 2004 (271) :39–45
94 F.Z. Kong, X.B. Zhang, W.Q. Xiong, etc. Continuous Ni-layer on multiwall carbon nanotubes by an electroless plating method. Surface and Coatings Technology 2002 (155): 33–36
95 Susumu Arai, Morinobu Endo, Shinji Hashizume, etc. Nickel-coated carbon nanofibers prepared by electroless deposition. Electrochemistry Communications 2004 (6) :1029–1031
96 Zhi Yang, Hui Xu, Meng-Ke Li, etc.Preparation and properties of Ni/P/single-walled carbon nanotubes composite coatings by means of electroless plating. Thin Solid Films 2004 (466) :86– 91
97 Controlled growth of Ni particles on carbon nanotubes for fabrication of carbon nanotubes. Huaping Liu, Guoan Cheng, Ruiting Zheng, etc. Journal of Molecular Catalysis A: Chemical 225 (2005) 233–237
98 Zhongbing Huang and Fangqiong Tang.Preparation, structure, and magnetic properties of polystyrene coated by Fe3O4 nanoparticles. Journal of Colloid and Interface Science2004 (275): 142–147
99 X. C. Sun, X. L. Dong.Magnetic properties and microstructure of carbon encapsulated Ni nanoparticles and pure Ni nanoparticles coated NiO layer. Material research bulletin.2002(37): 991-1002
100 C.P. Chen, T.H. Chang, T.F. Wang. Synthesis of magnetic nano-composite particles. Ceramics International 2001 (27): 925–930
101 Preparation of carbon-coated magnetic iron nanoparticles from composite rods made from coal and iron powders. Jieshan Qiua, Yongfeng Li, Yunpeng Wang, etc. Fuel Processing Technology. 2004 (86): 267– 274
102 Zhifei Wang, Pengfen Xiao, Nongyue He.Synthesis and characteristics of carbon encapsulatedmagnetic nanoparticles produced by a hydrothermal reaction. Carbon, 2006 (44) :3277–3284
103 X. G. Li, S. Takahashi, K. Watanabe. Hybridization and Characteristics of Fe and Fe-Co Nanoparticles with Polymer Particles. Nano Letters, 2001, 1(9):475-480
104 Junping Huo, Huaihe Song, Xiaohong Chen. Preparation of carbon-encapsulated iron nanoparticles by co-carbonization of aromatic heavy oil and ferrocene. Carbon. 2004 (42): 3177–3182
105 Yanwen Ma, Zheng Hu, Kaifu Huo,etc. A practical route to the production of carbon nanocages. Carbon 2005 (43): 1667–1672
106 Luiz Claudio de Santa Mariaa, Marcia C.A.M. Leite, Marcos A.S. Costa, etc.Characterization of magnetic microspheres based on network styrene and divinylbenzene copolymers. Materials Letters 2004 (58): 3001– 3006
107 Y. Yang, B.S. Zhang, W.D. Xu, etc. Preparation and electromagnetic characteristics of a novel iron-coated carbon fiber. Journal of Alloys and Compounds 2004 (365): 300–302
108雷中兴,刘菁,李轩科等. CVD法制备的碳包覆(Fe,Co)纳米粒子的结构及电磁特性.磁性材料及器件. 2003,34(4):4-6
109 X. Shen, R.Z. Gong, Y. Nie, J.H. Nie. Preparation and electromagnetic performance of coating of multiwall carbon nanotubes with iron nanogranule. Journal of Magnetism and Magnetic Materials 2005 (288): 397–402
110 S. Yang, X. Chen, S. Motojima. Morphology of the growth tip of carbon microcoils/nanocoils. Diamond & Related Materials,2004 (13):2152– 2155
111 Shaoming Yang, Xiuqin Chen, Seiji Motojima, Masaki Ichihara. Morphology and microstructure of spring-like carbon micro-coils/nano-coils prepared by catalytic pyrolysis of acetylene using Fe-containing alloy catalysts. Carbon, 2005 (43) :827–834
112 Lujun Pana, Taichi Hayashida, Akio Harada, Yoshikazu Nakayama. Effects of iron and indium tin oxide on the growth of carbontubule nanocoils. Physica B , 2002 (323) :350–351
113 J.B. Bai. Growth of nanotube/nanofibre coils by CVD on an alumina substrate. Materials Letters, 2003 (57):2629– 2633
114 Vardhan Bajpai, Liming Dai, and Toshiyuki Ohashi. Large-Scale Synthesis of Perpendicularly Aligned Helical Carbon Nanotubes. J. AM. CHEM. SOC,2004(126): 5070-5071
115 Yong Qin , Zhikun Zhang, Zuolin Cui.Helical carbon nanofibers prepared by pyrolysis of acetylene with a catalyst derived from the decomposition of copper tartrate. Carbon, 2003 (41): 3063- 3074
116于立岩,张乾,崔作林.螺旋纳米碳纤维的制备与表征.高等学校化学学报,2005(1): 5-8
117 Guangwen Xie , Zhaobo Wang, Zuolin Cui, Yulong Shi. Ni–Fe–Co–P coatings on coiled carbon nano.bers. Carbon, 2005 (43): 3181–3194
118赵东林,沈曾民.螺旋形手征碳纤维的微波介电特性.无机材料学报,2003,18(5): 1057-1062
119 Chen,X.;Saito,T.;Kusunoki,M.;Motojima,S.J.Mater.Res.,1999,14:4329
120 Du,J.H.;Su,G.;Bai,S.;Sun。C.;Cheng,H.M.Sci.Chin.f, 2001,44(4):377
121李文军,徐海涛,郭燕川,陈丽娟.碳微线圈的气-液-固-固生长机理.物理化学学报,2006,22(6),768-770
122 Motojima,S.;Asakura。S.;1wanaga,H.Carbon,1996, 34(3):289
123葛秀涛,冯剑,侯长平等. YFe1-y CoyO3半导体气敏材料的制备和性能研究.无机材料学报,2002,17(3):526-530
124 Z.B Huang,Y.Q Zhang, F.Q Tang.Solution-Phase Syntheses of Single-Crystalline Magenetic Nanowires with High Aspect Ratio and Uniformity. Chem. Comm. 2005,(3),342-344
125 Kazuyoshi Shibagaki, Seiji Motojima, Yasuhiro Umemoto, etc. Outermost surface microstructure of as-grown, heat-treated and partially oxidized carbon microcoils. Carbon 39 (2001) 1337–1342
126 Shibagaki K, Motojima S. Carbon 2000;36(5):2087–93.
127 Shibagaki K, Motojima S. Carbon 2001;39(3):411–7.
128 Shafi K, Gedanken A, Goldfarb R, Felner I. Sonochemical preparation of nanosized amorphous Fe-Ni Alloys. J. Appl. Phys., 1997, 81: 6901-6905
129黄婉霞等.PZT/Ni—Zn铁氧体复合材料电磁特性研究.功能材料,1996;27(5):431
130 Meixiang Wan et al. Composite of polyaniline containing iron oxides with nanometer size. Synthetic Metals, 1996;78:27-31
131 Meixiang Wan et al. Synthesis and electrical-magnetic properties of polyaniline composites. J.of Polym. Sci.:Part A:PloymChem1998;36:2799-2805
132 Yanwen Ma, Zheng Hu, Kaifu Huo et al. A practical route to the production of carbon nanocages. Carbon 43 (2005) 1667–1672
133 Satoshi Tomita , Masahiro Hikita , Minoru Fujii et al. A new and simple method for thin graphitic coating of magnetic-metal nanoparticles. Chemical Physics Letters. 2000, 316,361–364
134雷中兴,刘静,李轩科等,CVD法制备的碳包覆(Fe,Co)纳米粒子的结构及电磁特性.磁性材料及器件, 2003, 34(4),4-6
135郑兰香,彭国新.超细四氧化三铁微粒的制备.精细化工,1995, 12(6),11-14
136孙瑞雪,史京京,郭燕川,陈丽娟.明胶微球粒径控制的研究.高分子学报,2008(8),762-767
137廖邵彬,伊光俊,周丽年.微波吸收材料电磁参数的控制.宇航材料工艺,1989,(4-5):39