碳纳米管表面化学镀Co的研究
摘要
碳纳米管的发现,引起了全世界众多科学家的广泛关注,其优异的力学性能、电学性能、独特的微观结构,极大的长径比和比表面积,在众多领域有潜在的巨大应用价值然而,碳纳米管本身存在着许多缺陷,分散性也比较差,特别是碳纳米管的表面结构往往影响电学、力学和光学等诸多性能。因此,改善碳纳米管表面结构、增强碳纳米管与基体的湿润性和碳纳米管如何在基体中均匀分散度的研究引起了人们浓厚的兴趣。本研究采用化学镀工艺在碳纳米管表面包覆钴金属层,可改善碳纳米管表面结构和性能,以增强碳纳米管和金属、陶瓷和高分子等基体材料界面结合力,是扩大碳纳米管应用领域和有效利用碳纳米管优异性能的主要方法之一。
本研究选用CVD法制备的多壁碳纳米管作为施镀对象,对施镀前的碳纳米管进行微波、NaOH、浓硝酸提纯处理,再将提纯后的碳纳米管在SnCl_2溶液中进行敏化,在PdCl_2溶液中进行活化处理,最后在进行化学镀。在碳纳米管表面包覆得到了较为连续的钴镀层。并利用红外光谱(IR)、透射电镜(TEM)、X射线衍射(XRD)及能谱(EDS)等现代分析手段,对碳纳米管包覆体系的微观结构进行了研究。
结果表明,对碳纳米管进行微波处理,可消除非晶碳改善碳纳米管结晶度;然后将微波处理过的碳纳米管用NaOH溶液进一步提纯,除去碳纳米管中的由于CVD法制备过程中所使用的催化剂载体硅藻土中的主要成份SiO_2等杂质;再将经NaOH溶液处理后的碳纳米管用浓HNO_3处理,进一步提纯并改善其表面性能、接枝官能团。经红外光谱检测显示,经过浓硝酸处理后,在碳纳米管表面接枝了大量的官能团:羰基(＞C=O)、羟基(—OH)、羧基(—COOH)等官能团。然后采用超声的方法对提纯后的碳纳米管在SnCl_2溶液中进行敏化,在PdCl_2溶液中进行活化处理。使碳纳米管表面产生活化点,尽可能多的活化点将有利于金属钴在碳纳米管表面沉积,并能获得连续的金属钴镀层,从而提高化学镀的质量。化学镀在恒温和搅拌下进行,并对配方、温度、pH值、时间等方面进行调整,在碳纳米管表面获得完整、均匀、致密的金属钴包覆层。通过TEM、EDS及XRD等分析表明,采用正交试验方案7,即施镀条件为:施镀温度为45℃、pH值为10、主盐为硫酸钴(CoSO_4·7H_2 O)25g、还原剂为次亚磷酸钠(NaH_2PO_2·2H_2O)30g、稳定剂为硝酸铅(Pb(NO_3)_2)4.5×10~(-2)g、络合剂为柠檬酸三铵((NH_4)_3C_6H_5O_7)24g。通过此方案,能将金属钴镀层连续的包覆在碳纳米管的表面,并获得均匀、连续的镀层。
The discovery of carbon nanotubes has given rise to many scientists widely attention around the world,which exhibit excellent mechanical properties、electrical properties、the unique micro-structure、high aspect ratio and high specific surface area,,carbon nanotubes(CNT) have many potential applications in various fields.However,carbon nanotubes which have many defects and relatively poor dispersion,in particular,the structure of carbon nanotubes on the surface tend to affect the electrical/mechanical and optical performance and so on.As a result,improve the surface structure of carbon nanotubes、strengthen the humid of carbon nanotubes and medium、how to disperse the carbon nanotubes in medium and so on,this researchs have given rise to people' s interest.This study used Electroless plating process coating cobalt metal layer on the surface of carbon nanotube,the carbon nanotubes with cobalt metal layer can improve the structure and properties of carbon nanotubes, to enhance the carbon nanotubes and metal、ceramics、polymers、such as the medium material bonding interface,which is the main methods to expansion of carbon nanotube' s Application and use of carbon nanotube' s excellent capability.
This study prepared multi-walled carbon nanotubes as a target plating which produced by CVD,a series of purify treatment brfore the Electroless plating, microwave、NaOH、nitric acid,and then used the purification' s carbon nanotubes in the SnCl_2 solution to carry out sensitization,in the PdCl_2 solution to carry out activation.the next to Electroless plating.A series of cobalt deposits was coated On the surface of carbon nanotubes.And use of infrared spectroscopy(IR).transmission electron microscopy(TEM).spectroscopy(EDS).X-ray diffraction(XRD) analysis and other modern means to studied the micro-structure of carbon nanotubes coated.
The results showed:Microwave processing of carbon nanotubes can elimination of amorphous carbon nanotubes to improve the crystallinity;and then used NaOH solution to proceed further purification,except the main components of impurities,such as SiO_2 which bring by prepared carbon nanotubes by CVD process used in the catalyst support,and then treated with carbon nanotubes concentrated by HNO_3,further purification and improve it' s performance on the surface、graft functional groups,infrared spectroscopy showed that after dealing with concentrated nitric acid,a large number of functional groups graft ed on the surface of carbon nanotubes:carbonyl(>C=O),hydroxyl(-OH),carboxyl(-COOH),and so on.And then with the purification of carbon nanotubes carry out sensitization in the SnCl_2 solution and carry out activation in PdCl_2 solution using ultrasound method.So that the surface of carbon nanotubes can be activated,As much as possible' s activated will be beneficial that cobalt metal coats carbon nanotubes on the surface,and can obtain a row of cobalt metal coating,to improve the quality of electroless plating. Electroless plating was operated under the constant temperature and mixing,and adjust many factors:compound、temperature、pH valve、time and so on,and obtained a complete、uniform、dense coating of cobalt metal on the surface of carbon nanotubes.Through TEM.EDS and XRD analysis showed that orthogonal program 7, plating conditions are as follows:at the temperature is 45℃and pH is 10,with the (COSO_4·7H_2O 25g)as the main salt and(NaH_2PO_2·7H_2O 30g) as the reducer, (Pb(NO_3)_2 4.5×10~(-2)g) as the stabilizer and((NH_4)_3C_6H_5O_724g) as the complexing agent.With this program,A series of cobalt metal coated on the carbon nanotube' s surface,and obtained uniform.continuous coating.
本研究选用CVD法制备的多壁碳纳米管作为施镀对象,对施镀前的碳纳米管进行微波、NaOH、浓硝酸提纯处理,再将提纯后的碳纳米管在SnCl_2溶液中进行敏化,在PdCl_2溶液中进行活化处理,最后在进行化学镀。在碳纳米管表面包覆得到了较为连续的钴镀层。并利用红外光谱(IR)、透射电镜(TEM)、X射线衍射(XRD)及能谱(EDS)等现代分析手段,对碳纳米管包覆体系的微观结构进行了研究。
结果表明,对碳纳米管进行微波处理,可消除非晶碳改善碳纳米管结晶度;然后将微波处理过的碳纳米管用NaOH溶液进一步提纯,除去碳纳米管中的由于CVD法制备过程中所使用的催化剂载体硅藻土中的主要成份SiO_2等杂质;再将经NaOH溶液处理后的碳纳米管用浓HNO_3处理,进一步提纯并改善其表面性能、接枝官能团。经红外光谱检测显示,经过浓硝酸处理后,在碳纳米管表面接枝了大量的官能团:羰基(＞C=O)、羟基(—OH)、羧基(—COOH)等官能团。然后采用超声的方法对提纯后的碳纳米管在SnCl_2溶液中进行敏化,在PdCl_2溶液中进行活化处理。使碳纳米管表面产生活化点,尽可能多的活化点将有利于金属钴在碳纳米管表面沉积,并能获得连续的金属钴镀层,从而提高化学镀的质量。化学镀在恒温和搅拌下进行,并对配方、温度、pH值、时间等方面进行调整,在碳纳米管表面获得完整、均匀、致密的金属钴包覆层。通过TEM、EDS及XRD等分析表明,采用正交试验方案7,即施镀条件为:施镀温度为45℃、pH值为10、主盐为硫酸钴(CoSO_4·7H_2 O)25g、还原剂为次亚磷酸钠(NaH_2PO_2·2H_2O)30g、稳定剂为硝酸铅(Pb(NO_3)_2)4.5×10~(-2)g、络合剂为柠檬酸三铵((NH_4)_3C_6H_5O_7)24g。通过此方案,能将金属钴镀层连续的包覆在碳纳米管的表面,并获得均匀、连续的镀层。
The discovery of carbon nanotubes has given rise to many scientists widely attention around the world,which exhibit excellent mechanical properties、electrical properties、the unique micro-structure、high aspect ratio and high specific surface area,,carbon nanotubes(CNT) have many potential applications in various fields.However,carbon nanotubes which have many defects and relatively poor dispersion,in particular,the structure of carbon nanotubes on the surface tend to affect the electrical/mechanical and optical performance and so on.As a result,improve the surface structure of carbon nanotubes、strengthen the humid of carbon nanotubes and medium、how to disperse the carbon nanotubes in medium and so on,this researchs have given rise to people' s interest.This study used Electroless plating process coating cobalt metal layer on the surface of carbon nanotube,the carbon nanotubes with cobalt metal layer can improve the structure and properties of carbon nanotubes, to enhance the carbon nanotubes and metal、ceramics、polymers、such as the medium material bonding interface,which is the main methods to expansion of carbon nanotube' s Application and use of carbon nanotube' s excellent capability.
This study prepared multi-walled carbon nanotubes as a target plating which produced by CVD,a series of purify treatment brfore the Electroless plating, microwave、NaOH、nitric acid,and then used the purification' s carbon nanotubes in the SnCl_2 solution to carry out sensitization,in the PdCl_2 solution to carry out activation.the next to Electroless plating.A series of cobalt deposits was coated On the surface of carbon nanotubes.And use of infrared spectroscopy(IR).transmission electron microscopy(TEM).spectroscopy(EDS).X-ray diffraction(XRD) analysis and other modern means to studied the micro-structure of carbon nanotubes coated.
The results showed:Microwave processing of carbon nanotubes can elimination of amorphous carbon nanotubes to improve the crystallinity;and then used NaOH solution to proceed further purification,except the main components of impurities,such as SiO_2 which bring by prepared carbon nanotubes by CVD process used in the catalyst support,and then treated with carbon nanotubes concentrated by HNO_3,further purification and improve it' s performance on the surface、graft functional groups,infrared spectroscopy showed that after dealing with concentrated nitric acid,a large number of functional groups graft ed on the surface of carbon nanotubes:carbonyl(>C=O),hydroxyl(-OH),carboxyl(-COOH),and so on.And then with the purification of carbon nanotubes carry out sensitization in the SnCl_2 solution and carry out activation in PdCl_2 solution using ultrasound method.So that the surface of carbon nanotubes can be activated,As much as possible' s activated will be beneficial that cobalt metal coats carbon nanotubes on the surface,and can obtain a row of cobalt metal coating,to improve the quality of electroless plating. Electroless plating was operated under the constant temperature and mixing,and adjust many factors:compound、temperature、pH valve、time and so on,and obtained a complete、uniform、dense coating of cobalt metal on the surface of carbon nanotubes.Through TEM.EDS and XRD analysis showed that orthogonal program 7, plating conditions are as follows:at the temperature is 45℃and pH is 10,with the (COSO_4·7H_2O 25g)as the main salt and(NaH_2PO_2·7H_2O 30g) as the reducer, (Pb(NO_3)_2 4.5×10~(-2)g) as the stabilizer and((NH_4)_3C_6H_5O_724g) as the complexing agent.With this program,A series of cobalt metal coated on the carbon nanotube' s surface,and obtained uniform.continuous coating.
引文
[1].Kroto H.W.,Heath J.R.,O'Brien S.C.,et al.:C60:buckminsterfullerene[J].Nature(London),1985,318(6042),162-163
[2].Kratschmer W,Lamb L D,Frostiropoulous K & Huffman D R,Solid C60:a new form of carbon[J].Nature,1990,347:354-358
[3].S.Iijima.HelicalMicrotubesofGraphiticCabon[J].Nature 354,56-58(1991)
[4]T.w.Ebbesen,P.M.Ajayan.Large scale synthesis of carbon nanotubes[J].Nature,1992,358:220-222.
[5]S.Iijima,T.Ichihashi.Single shell carbon nanotubes of lnm diameter[J].Nature,1993,363:603-605
[6]D.S.Bethune,C H Kiang,M.S Devries,etal.Cobalt catalyzed growth of carbon Nanotubes with single atomic layer walls[J].Nature,1993,363:605-605.
[7]徐明君.碳纳米管力学性能的研究进展及应用[J].北京工商业大学学报,2005,4(23):32-35.
[8]Ishigami M,Cumings J,Zettl A,et al[J].Chemical Physics Letters,2000,319:457
[9]Andreas Thess,Roland Lee,Pavel Nikolaev,et al.Crystalline ropes of metallic carbon nanotubes[J].Science,1996,273:483.
[10]Cheng HM,Li F,Sun X,et al[J].Chemical Physics Letters,1998,289:602.
[11]Jourent C,Bernier p[J].Appl phys A.1998,67:1
[12]S Iijima,T Ichihashi[J].Nature.1997,386:377
[13]Ajayan PM,Zhou O.in:Dresselhaus MS,Dresselhaus G,Avouris Ph,ed,Carbon Nanotubes [J].Springer.2001.391
[14]Britto PJ,Santhanam KSV,Ajayan PM[J].Bioelectrochemistry and Bioenergetics.1996,41:121
[15]Britto PJ,Santhanam KSV,Rubio A,et al[J].Adv Mater.1999,11:154
[16]Che G,Lakshmi BB,Fisher ER,et al[J].Nature.1998,393:346
[17]Planeix JM,Coustel N,Coq BB,et al[J].Am Chem Soc.1994,116:7935
[18]Y.Zhang,Nathan W.Franklin,Robert J.Chen,et al[J].Metal coating on suspended carbon nanotubes and its implication to metal-tube interaction[J].Chemical Physics Letters 331(2000) 35-41.
[19]Hamada N,Sawada SI,Oshiyama A.[J].Phsy Rev Lett.1992,68:1579
[20]Mintmire JW,Dunlap BI,White CT[J].Phys Rev Lett.1992,68:631
[21]Saito R,Fujita M,Dresselhaus G,Dresselhaus MS[J].Appl Phys Lett.1992,60:2204
[22]Appenzeller J,Martel R,Avouris P,et al[J].Appl Phys Lett.2001,86:2416
[23]Collins PG,Zettl A,Bando H,et al[J].Science.1997,278:100
[24]Tans SJ,Devoret MH,Dai HJ,et al[J].Nature.1997,386:474
[25]Baughman RH,Cui C,Zakhidov AA,et al[J].Science.1999,284:1340
[26]Ebbesen T W,Hiura H,Biher M E.Decoration of carbon nanotubes[J].Adv Mater,1996,8(2):155.
[27]Li Q Q,Fan S H,Han W Q.Coating of carbon nanotube with nickel by electroless plating method[J].Jpn J Appl Phys,1997,236(4B):L501-L503.
[28]Li J,Moskovits M,Haslett T L.Nanoscale electroless metal deposition in aligned carbon nanotubes[J].Chem Mater,1998,10(7):1963-1967.
[29]王正元,贾志杰,张增民等.用红外光谱研究硝酸处理对多壁碳纳米管表面羧基的影响[J].炭素技术,1999,5:14-16.
[30]陈小华,颜永红,张高明等.Ni-Co合金包覆碳纳米管的研究[J].微细加工技术,1999(2):17-22.
[31]Chen Xiaohua,Xia Jintong,Peng Jingcui,et al.Carbon-nanotube metal-matrix composites prepared by electroless plating[J],composites Science and technology,2000,60:301-306.
[32]陈小华,张高明,李宏健等.碳纳米管的化学镀银及SEM研究[J].湖南大学学报(自然科学版),1999,26(6):14-18.
[33]陈小华,王健雄,邓福铭等.碳纳米管的化学镀镍研究[J].新型炭材料,2000,15(4):39-44.
[34]易国军,陈小华,蒋文忠等.碳纳米管的表面改性与镍的包覆[J].中国有色金属学报,2004,14(3):479-484.
[35]Ang L.M,Hor Tsa,Xu Gq,et al.Electroless plating of metals onto carbon nanotubes activated by a single-step activation method[J].Chem Mater,1999,11(8):2115-2118.
[36]Ang L.M,Hor Tsa,Xu Gq.Decoration of activated carbon nanotubes with copper and nickel[J].Carbon,2000,38(3):363-372.
[37]Zong-Jian Liu,Zhude Xu,Zhong-Yong Yuan,Weixiang Chen,Wuzong Zhou and Lian-Mao Peng.A simple method for coating carbon nanotubes with CoB amorphous alloy[J].Materials Letters.Volume 57,Issue 7,January 2003:1339-1344
[38]沈曾民,赵东林.镀镍碳纳米管的微波吸收性能研究[J].新型炭材料,2001,16(1):1-3.
[39]曹茂盛.雷达波隐身材料若干基础问题研究[D].北京:清华大学,2003.
[40]曹茂盛,高正娟,朱静.CNTs/Polyester复合材料的微波吸收特性研究[J].材料工程,2003(2):34-36.
[41]陈玉金,曹茂盛,李辰砂.碳纳米管的表面镀镍钴研究[J].中国表面工程,2003,16(2):29-32.
[42]陈玉成,邱成军等.碳纳米管化学复合镀锢镍[J].中国表面工程,2003(2):29-32.
[43]Kong F Z,Zhang X B,Xiong W Q.Continuous Ni-layer on multiwall carbon nanotubes by an electro 1 ess plating method[J].Surface and Coatings Technology,2002,155:33-36.
[44]孔凡志,张效彬,熊文庆等.用于复合材料增强体的多壁纳米碳管化学镀镍[J].复合材料学报,2002,19(5):71-74.
[45]毕韶丹.化学镀Ni-Co-P合金的工艺控制因素[J]表面技术.2004(4):46-47
[46]凤仪,袁海龙等.碳纳米管的化学镀银[J],功能材料,2004,3(35):317-319.
[47]田永毅,李明等.石墨与碳纳米管的化学镀Co-P合金[J],重庆工业高等专科学校学报,2004,19(5):5-7.
[48]王莉萍,吴玉程,李云等.化学镀Co-B合金(1)[J],电镀与精饰,2004,26(6):1-5.
[49]袁海龙,凤仪等.碳纳米管的化学镀铜[J],中国有色金属学报,2004,14(4):665-669.
[50]陈慧敏,闵娜,李四年等.碳纳米管表面化学镀Ni的研究[J],湖北工学院学报,2004,19(1):30-32.
[51]Feng Wang,Susumu Arai,Morinobu Endo.The preparation of multi-walled carbon nanotubes with a Ni-P coating by an electroless deposition process[J]Carbon,43(2005):1716-1721
[52]刘华平,程国安,彭宜斌等.碳纳米管负载Ni催化剂制备碳纳米管的研究[J].北京师范大学学报(自然科学版),2005,41(1):38-42.
[53]沈翔,龚荣洲,邱静,雷中兴。碳纳米管的化学镀铁钴和电磁参数研究[J].华中科技大学学报(自然科学版)2006(6):99-101.
[54]王银春,王育人,于泳等.一种新型的碳纤维和碳纳米管化学镀镍工艺[J].中国表面工程,2005.(4):45-48.
[55]袁定胜,陈俊智,陈子伦等.碳纳米管复合材料表面化学镀Ni-P合金[J].材料保护,2006,7:29-30.
[56]胡小晔,吴玉程,刘家琴等.碳纳米管预处理及化学复合镀研究现状[J].电镀与涂料,2006,4:46-49.
[57]张会平,江中浩,刘先黎等.玻璃表面化学镀纳米铜膜[J],吉林大学学报(工学版),2007,37(1):11-16.
[58]胡光辉,吴辉煌,杨防祖.碳纳米管表面的无钯活化化学镀镍研究[J].电化学,2006(1):25-28
[59]X.H.Chen,C.S.Chen,H.N.Xiao,F.Q.Cheng,G.Zhang,G.J.Yi Corrosion behavior of carbon nanotubes-Ni composite coating[J].Surface & Coatings Technology 2005,191:351-356.
[60]Pddmakar D.Kichambare,Dali Qian,Elizabeth C.Dickey,Craig A.Grimes Thin film metallic catalyst coatings for the growth of multiwalled carbon nanotubes by pyrolysis of xylene.Carbon 2002,40:1903-1909.
[61]Marc Bockrath,J.Hone,A.Zeal,and Paul L.McEuen Chemical doping of individual semiconducting carbon-nanotube ropes[J].Physical Review B 2000,61,16.
[62]E.T.Mickelson,C.B.Huffman,A.G.Rinzler Fluorination of single-wall carbon nanotubes [J].Chemical Physics Letters 1998,296:188-194
[63]Y.Chen and R.C.Haddon S.Fang,A.M.Rao,and P.C.Eklund Chemical attachment of organic functional groups to single-walled carbon nanotube material[J].Materials Research Society,1998,13,9
[64]A.Koshio,M.Yudasaka,M.Zhang,and S.Iijima.A Simple Way to Chemically React Single-Wall Carbon Nanotubes with Organic Materials Using Ultrasonication[J].NANO LETTERS,2001,7:361-363.
[65]张声峰,石英光纤表面金属化[M].成都,电子科技大学,1999.
[66]黄承德,张宏祥等.合金电沉积的发展[J].材料保护,1997,30(5).
[67]T.Qiu,X.L.Wu,G.S.Huang,G.G.Siu,Individual alumina nanotubes coaxially wrapping carbon nanotubes and nanowires[J].Thin Solid Films 2005,478:56-60.
[68]Y.Zhang,Nathan W.Franklin,Robert J.Chen,Hongjie Dai Metal coating on suspended carbon nanotubes and its implication to metal-tube interaction[J].Chemical Physics Letters,2000,331:35-41.
[69]X.Shen,R.Z.Gong,Y.Nie,J.Nie Preparation and electromagnetic performance of coating of multiwall carbon nanotubes with iron nanogranule[J].Science 2005,288:397-402.
[70]Yingjiu Zhang,Qi Zhang,Yubao Li,Nanglin Wang,Jing Zhu Coating of carbon nanotubes with tungsten by physical vapor deposition[J].Solid State Communications,2000,115:51-55.
[71]Ajayan P M,O Stephan,C Colliex,et al.Aligned carbon nanotube composite[J].Science,1994,265(16):1212-1214
[72]Dujardin E,Ebbesen T W,Hiura H.Capillarity and wetting of carbon nanotubes[J].Science,1994,265(18):1850-1851
[73]Robert C.CRC Handbook of Physics and Chemistry[M].Florda:CRC Press,1988.
[74]吴瑾光.近代傅里叶变换红外光谱技术及应用[M].科技文献出版社,1994
[75]Ajayan PM,lijima S.Capillarity-induced filling of carbon nanotubes[J].Nature,1993,361:333.
[76]Tsang SC,Harris PJF,Green MLH.Thinning and opening of carbon nanotubes by oxidation using carbon dioxide[J].Nature,1993,362:520-522.
[77]Zhou O,Fieming RM,Murphy DW,et al.Defects in carbon nanostructures[J].Science,1994,263:174
78]钱苗根.材料表面技术及其应用手册[M].机械工业出版社,1998
[80]Stefanik P,Sebo P.Journal of Materials[J].Science Letters,1993,12:1083-1085.
[2].Kratschmer W,Lamb L D,Frostiropoulous K & Huffman D R,Solid C60:a new form of carbon[J].Nature,1990,347:354-358
[3].S.Iijima.HelicalMicrotubesofGraphiticCabon[J].Nature 354,56-58(1991)
[4]T.w.Ebbesen,P.M.Ajayan.Large scale synthesis of carbon nanotubes[J].Nature,1992,358:220-222.
[5]S.Iijima,T.Ichihashi.Single shell carbon nanotubes of lnm diameter[J].Nature,1993,363:603-605
[6]D.S.Bethune,C H Kiang,M.S Devries,etal.Cobalt catalyzed growth of carbon Nanotubes with single atomic layer walls[J].Nature,1993,363:605-605.
[7]徐明君.碳纳米管力学性能的研究进展及应用[J].北京工商业大学学报,2005,4(23):32-35.
[8]Ishigami M,Cumings J,Zettl A,et al[J].Chemical Physics Letters,2000,319:457
[9]Andreas Thess,Roland Lee,Pavel Nikolaev,et al.Crystalline ropes of metallic carbon nanotubes[J].Science,1996,273:483.
[10]Cheng HM,Li F,Sun X,et al[J].Chemical Physics Letters,1998,289:602.
[11]Jourent C,Bernier p[J].Appl phys A.1998,67:1
[12]S Iijima,T Ichihashi[J].Nature.1997,386:377
[13]Ajayan PM,Zhou O.in:Dresselhaus MS,Dresselhaus G,Avouris Ph,ed,Carbon Nanotubes [J].Springer.2001.391
[14]Britto PJ,Santhanam KSV,Ajayan PM[J].Bioelectrochemistry and Bioenergetics.1996,41:121
[15]Britto PJ,Santhanam KSV,Rubio A,et al[J].Adv Mater.1999,11:154
[16]Che G,Lakshmi BB,Fisher ER,et al[J].Nature.1998,393:346
[17]Planeix JM,Coustel N,Coq BB,et al[J].Am Chem Soc.1994,116:7935
[18]Y.Zhang,Nathan W.Franklin,Robert J.Chen,et al[J].Metal coating on suspended carbon nanotubes and its implication to metal-tube interaction[J].Chemical Physics Letters 331(2000) 35-41.
[19]Hamada N,Sawada SI,Oshiyama A.[J].Phsy Rev Lett.1992,68:1579
[20]Mintmire JW,Dunlap BI,White CT[J].Phys Rev Lett.1992,68:631
[21]Saito R,Fujita M,Dresselhaus G,Dresselhaus MS[J].Appl Phys Lett.1992,60:2204
[22]Appenzeller J,Martel R,Avouris P,et al[J].Appl Phys Lett.2001,86:2416
[23]Collins PG,Zettl A,Bando H,et al[J].Science.1997,278:100
[24]Tans SJ,Devoret MH,Dai HJ,et al[J].Nature.1997,386:474
[25]Baughman RH,Cui C,Zakhidov AA,et al[J].Science.1999,284:1340
[26]Ebbesen T W,Hiura H,Biher M E.Decoration of carbon nanotubes[J].Adv Mater,1996,8(2):155.
[27]Li Q Q,Fan S H,Han W Q.Coating of carbon nanotube with nickel by electroless plating method[J].Jpn J Appl Phys,1997,236(4B):L501-L503.
[28]Li J,Moskovits M,Haslett T L.Nanoscale electroless metal deposition in aligned carbon nanotubes[J].Chem Mater,1998,10(7):1963-1967.
[29]王正元,贾志杰,张增民等.用红外光谱研究硝酸处理对多壁碳纳米管表面羧基的影响[J].炭素技术,1999,5:14-16.
[30]陈小华,颜永红,张高明等.Ni-Co合金包覆碳纳米管的研究[J].微细加工技术,1999(2):17-22.
[31]Chen Xiaohua,Xia Jintong,Peng Jingcui,et al.Carbon-nanotube metal-matrix composites prepared by electroless plating[J],composites Science and technology,2000,60:301-306.
[32]陈小华,张高明,李宏健等.碳纳米管的化学镀银及SEM研究[J].湖南大学学报(自然科学版),1999,26(6):14-18.
[33]陈小华,王健雄,邓福铭等.碳纳米管的化学镀镍研究[J].新型炭材料,2000,15(4):39-44.
[34]易国军,陈小华,蒋文忠等.碳纳米管的表面改性与镍的包覆[J].中国有色金属学报,2004,14(3):479-484.
[35]Ang L.M,Hor Tsa,Xu Gq,et al.Electroless plating of metals onto carbon nanotubes activated by a single-step activation method[J].Chem Mater,1999,11(8):2115-2118.
[36]Ang L.M,Hor Tsa,Xu Gq.Decoration of activated carbon nanotubes with copper and nickel[J].Carbon,2000,38(3):363-372.
[37]Zong-Jian Liu,Zhude Xu,Zhong-Yong Yuan,Weixiang Chen,Wuzong Zhou and Lian-Mao Peng.A simple method for coating carbon nanotubes with CoB amorphous alloy[J].Materials Letters.Volume 57,Issue 7,January 2003:1339-1344
[38]沈曾民,赵东林.镀镍碳纳米管的微波吸收性能研究[J].新型炭材料,2001,16(1):1-3.
[39]曹茂盛.雷达波隐身材料若干基础问题研究[D].北京:清华大学,2003.
[40]曹茂盛,高正娟,朱静.CNTs/Polyester复合材料的微波吸收特性研究[J].材料工程,2003(2):34-36.
[41]陈玉金,曹茂盛,李辰砂.碳纳米管的表面镀镍钴研究[J].中国表面工程,2003,16(2):29-32.
[42]陈玉成,邱成军等.碳纳米管化学复合镀锢镍[J].中国表面工程,2003(2):29-32.
[43]Kong F Z,Zhang X B,Xiong W Q.Continuous Ni-layer on multiwall carbon nanotubes by an electro 1 ess plating method[J].Surface and Coatings Technology,2002,155:33-36.
[44]孔凡志,张效彬,熊文庆等.用于复合材料增强体的多壁纳米碳管化学镀镍[J].复合材料学报,2002,19(5):71-74.
[45]毕韶丹.化学镀Ni-Co-P合金的工艺控制因素[J]表面技术.2004(4):46-47
[46]凤仪,袁海龙等.碳纳米管的化学镀银[J],功能材料,2004,3(35):317-319.
[47]田永毅,李明等.石墨与碳纳米管的化学镀Co-P合金[J],重庆工业高等专科学校学报,2004,19(5):5-7.
[48]王莉萍,吴玉程,李云等.化学镀Co-B合金(1)[J],电镀与精饰,2004,26(6):1-5.
[49]袁海龙,凤仪等.碳纳米管的化学镀铜[J],中国有色金属学报,2004,14(4):665-669.
[50]陈慧敏,闵娜,李四年等.碳纳米管表面化学镀Ni的研究[J],湖北工学院学报,2004,19(1):30-32.
[51]Feng Wang,Susumu Arai,Morinobu Endo.The preparation of multi-walled carbon nanotubes with a Ni-P coating by an electroless deposition process[J]Carbon,43(2005):1716-1721
[52]刘华平,程国安,彭宜斌等.碳纳米管负载Ni催化剂制备碳纳米管的研究[J].北京师范大学学报(自然科学版),2005,41(1):38-42.
[53]沈翔,龚荣洲,邱静,雷中兴。碳纳米管的化学镀铁钴和电磁参数研究[J].华中科技大学学报(自然科学版)2006(6):99-101.
[54]王银春,王育人,于泳等.一种新型的碳纤维和碳纳米管化学镀镍工艺[J].中国表面工程,2005.(4):45-48.
[55]袁定胜,陈俊智,陈子伦等.碳纳米管复合材料表面化学镀Ni-P合金[J].材料保护,2006,7:29-30.
[56]胡小晔,吴玉程,刘家琴等.碳纳米管预处理及化学复合镀研究现状[J].电镀与涂料,2006,4:46-49.
[57]张会平,江中浩,刘先黎等.玻璃表面化学镀纳米铜膜[J],吉林大学学报(工学版),2007,37(1):11-16.
[58]胡光辉,吴辉煌,杨防祖.碳纳米管表面的无钯活化化学镀镍研究[J].电化学,2006(1):25-28
[59]X.H.Chen,C.S.Chen,H.N.Xiao,F.Q.Cheng,G.Zhang,G.J.Yi Corrosion behavior of carbon nanotubes-Ni composite coating[J].Surface & Coatings Technology 2005,191:351-356.
[60]Pddmakar D.Kichambare,Dali Qian,Elizabeth C.Dickey,Craig A.Grimes Thin film metallic catalyst coatings for the growth of multiwalled carbon nanotubes by pyrolysis of xylene.Carbon 2002,40:1903-1909.
[61]Marc Bockrath,J.Hone,A.Zeal,and Paul L.McEuen Chemical doping of individual semiconducting carbon-nanotube ropes[J].Physical Review B 2000,61,16.
[62]E.T.Mickelson,C.B.Huffman,A.G.Rinzler Fluorination of single-wall carbon nanotubes [J].Chemical Physics Letters 1998,296:188-194
[63]Y.Chen and R.C.Haddon S.Fang,A.M.Rao,and P.C.Eklund Chemical attachment of organic functional groups to single-walled carbon nanotube material[J].Materials Research Society,1998,13,9
[64]A.Koshio,M.Yudasaka,M.Zhang,and S.Iijima.A Simple Way to Chemically React Single-Wall Carbon Nanotubes with Organic Materials Using Ultrasonication[J].NANO LETTERS,2001,7:361-363.
[65]张声峰,石英光纤表面金属化[M].成都,电子科技大学,1999.
[66]黄承德,张宏祥等.合金电沉积的发展[J].材料保护,1997,30(5).
[67]T.Qiu,X.L.Wu,G.S.Huang,G.G.Siu,Individual alumina nanotubes coaxially wrapping carbon nanotubes and nanowires[J].Thin Solid Films 2005,478:56-60.
[68]Y.Zhang,Nathan W.Franklin,Robert J.Chen,Hongjie Dai Metal coating on suspended carbon nanotubes and its implication to metal-tube interaction[J].Chemical Physics Letters,2000,331:35-41.
[69]X.Shen,R.Z.Gong,Y.Nie,J.Nie Preparation and electromagnetic performance of coating of multiwall carbon nanotubes with iron nanogranule[J].Science 2005,288:397-402.
[70]Yingjiu Zhang,Qi Zhang,Yubao Li,Nanglin Wang,Jing Zhu Coating of carbon nanotubes with tungsten by physical vapor deposition[J].Solid State Communications,2000,115:51-55.
[71]Ajayan P M,O Stephan,C Colliex,et al.Aligned carbon nanotube composite[J].Science,1994,265(16):1212-1214
[72]Dujardin E,Ebbesen T W,Hiura H.Capillarity and wetting of carbon nanotubes[J].Science,1994,265(18):1850-1851
[73]Robert C.CRC Handbook of Physics and Chemistry[M].Florda:CRC Press,1988.
[74]吴瑾光.近代傅里叶变换红外光谱技术及应用[M].科技文献出版社,1994
[75]Ajayan PM,lijima S.Capillarity-induced filling of carbon nanotubes[J].Nature,1993,361:333.
[76]Tsang SC,Harris PJF,Green MLH.Thinning and opening of carbon nanotubes by oxidation using carbon dioxide[J].Nature,1993,362:520-522.
[77]Zhou O,Fieming RM,Murphy DW,et al.Defects in carbon nanostructures[J].Science,1994,263:174
78]钱苗根.材料表面技术及其应用手册[M].机械工业出版社,1998
[80]Stefanik P,Sebo P.Journal of Materials[J].Science Letters,1993,12:1083-1085.