摘要
海洋贻贝类黏性蛋白的发现,为材料表面改性提供了一种新方法。本论文主要利用多巴胺自聚合引入酚羟基和含氮官能团等功能基团,实现对玻璃纤维和针状硅酸盐纳米纤维的表面改性。然后,利用多巴胺辅助化学镀或聚多巴胺直接氧化还原方法制备镀银玻璃纤维和银/针状硅酸盐纳米纤维复合材料,从而实现在微纳米纤维上实现金属化。主要工作如下:
(1)本论文提出了一种高效、环保的方法制备高导电镀银玻璃纤维。在有氧潮湿碱性条件下,将玻璃纤维放入配好的多巴胺溶液中,多巴胺就会氧化自聚合从而在玻璃纤维表面形成聚多巴胺层。含有酚羟基和含氮官能团的聚多巴胺既是银粒子和玻璃纤维的连接剂,又是将Ag+还原为单质银的还原剂。利用化学镀方法,在外加还原剂葡萄糖的作用下制备的镀银玻璃纤维,用X射线光电子能谱(XPS),X射线衍射(XRD),扫描电镜(SEM)和四探针分别表征玻璃纤维的表面元素组成,物相组成,表面形貌和电阻率。结果表明,金属态的银粒子致密均匀的沉积在玻璃纤维表面。通过改变硝酸银和多巴胺浓度可以得到银的质量分数为9.5-24%的镀银玻璃纤维,且镀银玻璃纤维的电阻率最低为1.0mΩ cm。
(2)由微米级过渡到纳米级,本论文还研究了多巴胺改性针状硅酸盐纳米纤维,并利用聚多巴胺还原银离子制备银/针状硅酸盐纳米复合材料。一方面研究了多巴胺浓度和聚合时间对改性纳米纤维的影响,另一方面研究了外加还原剂,pH,温度和络合剂对银/纳米纤维复合材料的影响。用X射线光电子能谱(XPS)和傅立叶红外光谱(FTIR)对改性前后针状硅酸盐的表面元素组成和官能团进行表征,扫描电镜(SEM)观察改性纳米纤维的表面形貌,高分辨透射电镜(HRTEM)研究纳米纤维的微观形貌和微观结构,X射线衍射(XRD)表征纳米纤维的物相组成。结果表明当pH为8.5,反应温度为60℃时,单质纳米银粒子粒径为2.15nm且粒径分布均匀。
本论文用多巴胺对无机纤维材料进行表面改性,并在此基础上采用化学镀、氧化还原法实现微米/纳米材料表面金属化,金属与材料表面具有牢固的结合力,为材料表面金属化提供一个新思路、新方法。
The techniques to modify substrate surfaces are significant for manyindustrial and research applications. In this work,dopamine was used tomodification of glass fiber (GF) and fibrillar silicate nanofiber (FS) viadopamine self-polymerization to polydopamine (PDA) on the materialsurfaces. What’s more, silver-plating glass fiber and Ag/fibrillar silicatenanofiber were synthesized by PDA-assisting electroless plating or PDAoxidation reduction directly. The details of the work are as follows:
(1) Highly conductive silver-coated GF was fabricated in an efficientand environment-friendly way. When the GF powder was immersed indopamine solution, an adherent self-polymerized PDA layer was formedon the GF surface. PDA acts as both a linker between GF and silvernanoparticles and a reducing agent for reducing silver ions to metallicsilver. The silver nanoparticles can be chemically bound to the catecholand amine functional groups in PDA by electroless plating using glucoseas reducing agent. Chemical and physical characterizations of thesilver-coated GF were carried out by using X-ray photoelectronspectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Four-point probe was used to study the electricalresistivity of the silver-coated glass fibers. The results indicated that thesilver coated on the GF surface was compact, uniform, continuous, and ina metallic crystal state. The silver content could be well controlled from9.5to24wt.%by adjusting the reduction conditions. The electricalresistivity of the silver-coated glass fibers could be as low as1.0mΩ cm.
(2) The transition from micron to nanometer, in this work, a novelmethod was developed for the preparation of silver/FS nanocomposite, inwhich dopamine acts as both modification agent and reducing agent. Onthe one hand, the effects of dopamine concentration and polymerizationtime on the modified FS nanofiber were studied. On the other hand, theeffects of extra-reducing agent, pH, temperature and complexing agenton the Ag/FS nanocomposites were also studied. The surface elementalcomposition and functional groups of FS before and after dopaminemodification were characterized by using X-ray photoelectronspectroscopy (XPS) and fourier transform infrared spectrometer (FTIR),surface morphology of samples were characterized by scanning electronmicroscopy (SEM), microscopic morphology and structure of Ag/FS wasdetected by transmission electron microscope (TEM) or high resolutiontransmission electron microscope (HRTEM), phase composition ofsample was characterized by X-ray diffraction (XRD). The resultindicated that metal silver nanoparticles with mean diameter of2.15nm and narrow particle size distribution deposited on the FS, when the pH is8.5, temperature is60℃.
In conclusion, this paper shows that dopamine is a versatile methodto functionalize the surface of inorganic materials, and the combination ofthe following electroless plating technique and redox method couldprepare surface metalized composites good adhesion between the metalwith the substrate.
引文
[1] Yongjun Hu, Haiyan Zhang, Feng Li, Xiaoling Cheng, Tianli Chen, Investigation intoelectrical conductivity and electromagnetic interference shielding effectiveness of siliconerubber filled with Ag-coated cenosphere particles [J]. Polymer testing,2010,29,609-612.
[2] Ki Yeon Park, Sang Eui Lee, Chun Gon Kim, Jae Hung Han, Application of MWNT-addedglass fabric/epoxy composites to electromagnetic wave shielding enclosures [J]. Compositestructures,2007,81,401-406.
[3] Chiyuan Huang, Wenwei Mo, Ming Lih Roan, Studies on the influence of double-layerelectroless metal deposition on the electromagnetic interference shielding effectiveness ofcarbon fiber/ABS composites [J]. Surface and coatings technology,2004,184,163-169.
[4] Mohammed H. Al-Saleh, Genaro A. Gelves, Uttandaraman Sundararaj, Coppernanowire/polystyrene nanocomposites: lower percolation threshold and higher EMIshielding [J]. Composites: part A,2011,42,92-97.
[5] B.R. Kim, H.K. Lee, S.H. Park, H.K. Kim, Electromagnetic interference shieldingcharacteristics and shielding effectiveness of polyaniline-coated films [J]. Thin solid films,2011,519,3492-3496.
[6] Yong Huang, Shanyong Chen, Junhong Liu. Progress of Application of electricallyconductive fillers used in conductive rubber[J]. Yunnan chemical technology,2009,36(5),47-51.
[7] Yiyan He, Xueyan Wu, Shiguo Du. Status que and development of conductive fillers inconductive composite plastics[J]. Plastics science and technology,2004,161(3),50-53.
[8] Yao Sun, Hada Bao, Zhaoxia Guo, Jian Yu. Modeling of the electical percolation of mixedcarbon fillers in polymer-based composites[J]. Macromolecules,2009,42,459-463.
[9] Jee Hyun Moon, Kyung Hwan Kim, Hyung Wook Choi, Sang Wha Lee, Sang Joon Park,Electroless silver coating of rod-like glass particles[J]. Ultramicroscopy,2008,108,1307-1310.
[10] Yongjun Hu, Haiyan Zhang, Feng Li, Xiaoling Cheng, Tianli Chen, Investigation intoelectrical conductivity and electromagnetic interference shieding effectiveness of siliconerubber filled with Ag-coated cenosphere particles[J]. Polymer testing,2010,29,609-612.
[11] G. Jiang, M. Gilbert, D.J. Hitt, G.D. Wilcox, K. Balasubramanian, Preparation of nickelcoated mica as a conductive filler[J]. Composites: part A,2002,33,745-751.
[12] Wencai Wang, Ainv Zhang, Li Liu, Ming Tian, Liqun Zhang, Dopamine-Induced SurfaceFunctionalization for the Preparation of Al-Ag Bimetallic Microspheres[J]. Journal of theelectrochemical society,2011,158(4),1-6.
[13] Yilong Wang, Jianguo Guan, Hanmei Shao, Qiaoxin Zhang, Junyuan Duan, Bin Sun,Preparation and properties of silver-coated glass microsphere core-shell particles onelectromagnetic shieding materials[J]. Journal of the Chinese Ceramic Society,2008,36(3),301-305.
[14] Liang Tongxiang, Guo Wenli, Yan Yinghui, Tang Chunhe, Electroless plating of silver ongraphite powders and the study of its conductive adhesive[J]. International journal ofadhesion and adhesives,2007,28,55-58.
[15] Haihui Zhou, Qiang Yu, Qiling Peng, Hua Wng, Jinhua Chen, Yafei Kuang, Catalyticgraphitization of carbon fibers with electrodeposited Ni-B alloy coating[J]. Materialschemistry and physics,2008,110,434-439.
[16] Jeong Hoon Byeon, Jang-Woo Kim, Novel electroless copper deposition on carbon fiberswith environmentally friendly processes[J]. Journal of colloid and interface science,2010,348,649-653.
[17] J. Akesson, S. Seal, S. Shukla, Z. Rahman, Copper-plating process control by SEM[J].Advanced material process,2002,160,33-35.
[18] H.X. Guo, Z.P. Qin, J. Wei, C.X. Qin, A novel activation for electroless plating onpreparing Ni-PS microspheres[J]. Surface coating technology,2005,200,2531-2538.
[19] Ph. Hasler, Th. Allmendinger, Morphological effects on electrodeposited Pd-Ag films dueto the electroplating conditions[J]. Surface and coating technology,1993,58(3),185-192.
[20] Wan Fu Lien, Po-chen huang, Shi-chang Tseng, Chia-hsiang Cheng, Shih-ming Lai,Electroless silver plating on tetraethoxy silane-bridged fiber glass[J], Applied surfacescience,2012,258,2246-2254.
[21] Jee Hyun Moon, Kyung Hwan Kim, Hyung Wook Choi, Sang Wha Lee, Sang Joon Park,Electroless silver coating of rod-like glass particles[J]. Ultramicroscopy,2008,108,1307-1310.
[22] Gordon Nangmenyi, Zhongren Yue, Sharifeh Mehrabi, Eric Mintz, James Economy,Synthesis and characterization of silver-nanoparticle-impregnated fiberglass and utility inwater disinfection[J]. Nanotechnology,2009,20,495705-495715.
[23] Yinxiang Liu, Suhua Jiang, Yongming Huang, Ultrasonic-assisted electroless deposition ofAg on PET fabric with low silver content for EMI shielding[J]. Surface and coatingstechnology,2010,204,2829-2833.
[24] Fern M. Lelly, James H. Johnston, Colored and functional silver nanoparticle-wool fibercomposites[J]. Applied materials and interfaces,2011,3,1083-1092.
[25] Soo Jin Park, Byung Joo Kim, A study on NO removal of activated carbon fibers withdeposited silver nanoparticles[J], Journal of colloid and interface science,2005,282,124-127.
[26] Kang Pyo So, Chandan Biswas, Seong Chu Lim, Kay Hyeok An, Young Hee Lee,Electroplating formation of Al-C covalent bonds on multiwalled carbon nanotubes[J].Synthetic Metals,2011,161,208-212.
[27] Omayma Abdel Gawad, M.H. Abou Tabl, Z. Abdel Hamid, S.F. Mostafa, Electroplating ofchromium and Cr-carbide coating for carbon fiber[J]. Surface and coating technology,2006,201,1357-1362.
[28] Lei Wang, Fang He, Yizao Wan, Facile synthesis electromagnetic wave absorptionproperties of magnetic carbon fiber coated with Fe-Co alloy by electroplating[J]. Journal ofalloys and compounds,2011,509,4726-4730.
[29] Toshiki Tsubota, Shunsuke Tanii, Toshihito Ishida, Masanori Nagata, YasumichiMatsumoto, Composite electroplating of Ni and surface-modified diamond particles withsilane coupling regent[J]. Diamond and related materials,2005,14,608-612.
[30] M.J. Shapiro, W.J. Lackey, J.A. Hanigofsky, D.N. Hill, W.B. Carter, E.K. Barefield,Chemical vapor deposition of silver films for superconducting wire applications[J]. Journalof alloys and compounds,1992,187(2),331-349.
[31] C.N. He, N.Q. Zhao, C.S. Shi, S.Z. Song, Optimization of the chemical vapor depositionprocess for fabrication of carbon nanotube/Al composite powders[J]. Materials researchbulletin,2010,45,1182-1188.
[32] Haipeng Li, Naiqin Zhao, Yuan Liu, Chunyong Liang, Xiwen Du, Jiajun Li, Fabricationand properties of carbon nanotubes reinforced Fe/hydroxyapatite composites by in situchemical vapor deposition[J]. Composites: part A,2008,39,1128-1132.
[33] Nafiseh Sharifi, Nima Taghavinia, Silver nanoislands on glass fibers using heat segregationmethod[J]. Materials chemistry and phsics,2009,113,63-66.
[34] Chaohe Xu, Jing Sun, Lian Gao, Large scale synthesis of nickel oxide/multiwalled carbonnanotube composites by direct thermal decomposition and their lithium storageproperties[J]. Journal of power sources,2011,196,5138-5142.
[35] Jong Hwa Sohn, Long Quoc Pham, Hyun Suk Kang, Ji Hyun Park, Byung Cheol Lee,Young Soo Kang, Preparation of conducting silver paste with Ag nanoparticles prepared bye-beam irradiation [J]. Radiation physics and chemistry,2010,79,1149-1153.
[36] E. Trave, F. Gonella, P. Calvelli, E. Cattaruzza, P. Canton, D. Cristofori, A. Quaranta, G.Pellegrini, Laser beam irradiation of silver doped silicate glasses [J]. Nuclear instrumentsand methods in physics research B,2010,268,3177-3182.
[37] Yeong Joon Kim, Gyoujin Cho, Jae Hee Song, Ag+concentration effect on the shape of Aunanomaterials under proton beam irradiation [J]. Nuclear instruments and methods inphysics research B,2007,254,73-77.
[38] Neil P. Dasgupta, Hee Joon Jung, Orlando Trejo, Matthew T. Mccdowell, Aaron Hryciw,Mark Brongersma, Robert Sinclair, Fritz B. Prinz, Atomic layer deposition of lead sulfidequantum dots on nanowire surfaces [J]. Nano letters,2011,11,934-940.
[39] Alessandro La Torre, Maria del Carmen Gimenez-Lopez, Michael W. Fay, Graham A.Rance, William A. Solomonsz, Thomas W. Chamberlain, Paul D. Brown, Andrei N.Khlobystov, Assembly, growth, catalytic activity of gold nanoparticles in hollow carbonnanofibers [J]. ACS NANO,2012,6(3),2000-2007.
[40] Kyler J. Carroll, Daniel M. Hudgins, Steven Spurgeon, Kennneth M. Kemner, BhoopeshMishra, Maxim I. Boyanov, Lester W. BrownⅢ, M itra L. Taheri, Everett E. Carpenter,One-pot aqueous synthesis of Fe and Ag core/shell nanoparticles [J]. Chemistry ofmaterials,2010,22,6291-6296.
[41] Shuzhuo Zhang, Weihai Ni, Xiaoshan Kou, Man Hau Yeung, Lingdong Sun, JianfangWang, Chunhua Yan, Formation of gold and silver nanoparticle arrays and thin shells onmesostructured silica nanofibers[J]. Advanced functional materials,2007,17,3258-3266.
[42] Yi Lin, Kent A. Watson, Michael J. Fallbach, Sayata Ghose, Joseph G. Smith, Donavon M.Delozier, Wei Cao, Roy E. Crooks, John W. Connell, Rapid, solventless, bulk preparationof metal nanoparticle-decorated carbon nanotubes [J]. ACS NANO,2009,3(4),871-884.
[43] Shuzhuo Zhang, Weihai Ni, Xiaoshan Kou, Man Hau Yeung, Lingdong Sun, JianfangWang, Chunhua Yan, Formation of gold and silver nanoparticles arrays and thin shells onmesostructured silica nanofibers [J]. Advanced functional materials,2007,17,3258-3266.
[44] Manthiriyappan Sureshkumar, Dessy Yovita Siswanto, Chengkang Lee, Magneticantimicrobial nanocomposite based on bacterial cellulose and silver nanoparticles [J].Journal of materials chemistry,2010,20,6948-6955.
[45] Fern M. Kelly, James H. Johnston, Colored and functional silver nanoparticle-wool fibercomposites [J]. Applied materials and interfaces,2011,3,1083-1092.
[46] Kaushik Mallick, Mike J. Witcomb, Andy Dinsmore, Mike S. Scurrell, Fabrication of ametal nanoparticles and polymer nanofibers composite material by an in situ chemicalsynthetic route [J]. Langmuir,2005,21,7964-7967.
[47] Daniel Gottlieb, Stephen A. Morin, Song Jin, Ronald T. Raines, Self-assembledcollagen-like peptide fibers as templates for metallic nanowires [J]. Journal of materialchemistry,2008,18,3865-3870.
[48] Mieke C. vander Leeden, Are conformational changes, induced by osmotic pressurevariation, the underlying mechanism of controlling the adhesive activity of mussel adhesiveproteins [J], Langmuir,2005,21,11373-11379.
[49] Haeshin Lee, Shara M. Dellatore, William M. Miller, Phillip B. Messersmith,Mussel-Inspired Surface Chemistry for Multifunctional Coatings[J]. Science,2007,318,426-430.
[50] Haeshin Lee, Bruce P. Lee, Phillip B. Messersmith, A reversible wet/dry adhesive inspiredby mussels and geckos[J]. Nature,2007,448,338-342.
[51] Li Qun Xu, Wen Jing Yang, Koon-Gee Neoh, En-Tang Kang, Guo Dong Fu,Dopamine-induced reduction and functionalization of Graphene Oxide Nanosheets[J],Macromolecules,2010,43,8336-8339.
[52] Qiang Wei, Fulong Zhang, Jie Li, Beijia Li, Changsheng Zhao, Oxidant-induced dopaminepolymerization for multifunctional coatings[J]. Polymer Chemistry,2010,1,1430-1433.
[53] Fei Yu, Shougang Chen, Yan Chen, Houmin Li, Lejiao Yang, Yuanyuan Chen, YanshengYin, Experimental and theoretical analysis of polymerization reaction process on thepolydopamine membranes and its corrosion protection properties for304Stainless Steel[J].Journal of molecular structure,2010,982,152-161.
[54] Lian Hong, John D. Simon, Current Understanding of the Binding Sites, Capacity, Affinity,and Biological Significance of Metals in Melanin[J]. Journal of physical and chemical B,2007,111,7938-7947.
[55] Bruno Szpoganicz, Shirley Gidanian, Philip Kong, Patrick Farmer, Metal binding bymelanins: studies of colloidal dihydroxyindole-melanin, and its complexation by CuⅡ()and Zn(Ⅱ) ions[J]. Journal of inorganic biochemistry,2002,89,45-53.
[56] B. Fei, B. Qian, Z.Y. Yang, R.H. Wang, W.C. Liu, C.L. Mak, John H. Xin, Coating carbonnanotubes by spontaneous oxidative polymerization of dopamine[J]. Carbon,2008,46(13),1795-1797.
[57] Y. Liao, Y.Q. Wang, X.X. Feng, W.C. Wang, F.J. Xu, L.Q. Zhang, Antibacterial surfacesthrough dopamine functionalization and silver nanoparticle immobilization[J]. Materialschemistry and physics,2010,121,534-540.
[58] Xiaolong Wang, Qian Ye, Tingting Gao, Jianxi Liu, Feng Zhou, Self-assembly of catecholicmacroinitiator on various substrates and surface-initiated polymerization[J]. Langmuir,2012,28,2574-2581.
[59] Wencai Wang, Yi Jiang, Shipeng Wen, Li Liu, Liqun Zhang, Preparation andcharacterization of polystyrene/Ag core-shell microspheres-a bio-inspired polydopamineapproach[J]. Journal of colloid and interface science,2012,368,241-249.
[60] Wencai Wang, Yi Jiang, Yuan Liao, Ming Tian, Hua Zou, Liqun Zhang, Fabrication ofsilver-coated silica microspheres through mussel-inspired surface functionalization[J].Journal of colloid and interface science,2011,358,567-574.
[61] Wencai Wang, Ainv Zhang, Li Liu, Ming Tian, Liqun Zhang, Dopamine-induced surfacefunctionalization for the preparation of Al-Ag bimetallic microspheres[J]. Journal of theelectrochemical society,2011,158,228-233.
[62] Yuan Liao, Yaqin Wang, Xiaoxia Feng, Wencai Wang, Fujian Xu, Liqun Zhang,Antibacterial sufaces through dopamine functionalization and silver nanoparticleimmobilization [J]. Materials chemistry and physics,2010,121,534-540.
[63] Bin Fei, Baitai Qian, Zongyue Yang, Ronghua Wang, W. C. Liu, C. L. Mak, John H. Xin,Coating carbon nanotubes by spontaneous polymerization of dopamine [J]. Carbon,2008,46,1792-1797.
[64] Kvar C. L. Black, Zhongqiang Liu, Phillip B. Messersmith, Catechol redox inducedformation of metal core-polymer shell nanoparticles [J]. Chemistry materials,2011,23,1130-1135.
[65] Jasmine A. Jacob, Harbir S. Mahal, Nandita Biswas, Tulsi Mukherjee, Sudhir Kapoor, Roleof rhenol derivatives in the formation of silver nanoparticles[J]. Langmuir,2008,24,528-533.
[66] J.D.S. Newman, G.J. Blanchard. Formation of gold nanoparticles using amine reducingagents[J]. Langmuir,2006,22,5882-5887.
[67] S. Tamil Selvan, Joachim P. Spatz, Harm-Anton Klok, Martin Moller, Gold-polypyrrolecore-shell particles in diblock copolymer micelles[J]. Advanced material,1998,10,132-134.
[68] Yingchun Fu, Penghao Li, Qingji Xie, Xiahong Xu, Lihong Lei, Chan Chen, Can Zou,Wenfeng Peng, Shouzhuo Yao, One-pot preparation of polymer-enzyme-metallicnanoparticle composite films for high-performance biosensing of glucose and galactose[J].Advaced functional material,2009,19,1784-1791.
[69] Weichun Ye, Haiyuan Hu, Hong Zhang, Feng Zhou, Weimin Liu, Multi-walled carbonnanotube supported Pd and Pt nanoparticles with high solution affinity for effectiveelectrocatalysis[J]. Applied surface science,2010,256,6723-6728.
[70] Kvar C.L. Black, Zhongqiang Liu, Phillip B. Messersmith, Catechol redox inducedformation of metal core-polymer shell nanoparticles[J]. Chemistry material,2011,23,1130-1135.
[71] Fern M. Kelly, James H. Johnston, Colored and functional silver nanoparticle-wool fibercomposites[J]. Application material interfaces,2011,3,1083-1092.
[72] Yushan Liu, Peng Liu, Zhixing Su, Core-shell attapulgite@polyaniline composite particlesvia in situ oxidative polymerization [J]. Synthetic metals,2007,157,585-591.
[73] Yushan Liu, Peng Liu, Zhixing Su, Fashen Li, Fusheng Wen, Attapulgite-Fe3O4magneticnanoparticles via coprecipitation technique [J]. Applied surface science,2008,255,2020-2025.
[74] Ray L. Frost, Efrain Mendelovici, Modification of fibrous silicates surfaces with organicderivatives: an infrared spectroscopic study [J]. Journal of colloid and interface science,2006,294,47-52.
[75]卢健体,李芝华,曹鼎,无钯活化化学镀银玻璃纤维的制备[J].稀有金属材料与工程,2010,39,27-30。
[76]李芝华,曹鼎,孙健,化学镀银玻璃纤维[J].稀有金属材料与工程,2009,38(4),748-752。