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2011 | OriginalPaper | Buchkapitel

6. Nanomaterials

verfasst von : Bradley D. Fahlman

Erschienen in: Materials Chemistry

Verlag: Springer Netherlands

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Abstract

Nanotechnology is more than a passing fad. The synthesis of nanoscale materials is used to fine-tune the properties of any existing solid-state material, or design an entirely new material from the bottom-up to afford a desired set of properties. This chapter begins by discussing the increasingly relevant topic of nanotoxicity for various classes of nanomaterials. Structures, properties, applications and synthetic techniques for a variety of nanomaterials are described throughout this chapter, citing many precedents from the scientific literature.

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Vorheriges Kapitel Polymeric Materials

Nächstes Kapitel Materials Characterization

Note: a sampling of some intriguing applications that are already possible using nanomaterials include: self-cleaning fabrics (via TiO₂ nanoparticles), automobile clearcoats that prevent scratches (PPG nanoparticle-based coatings), car wash solutions that prevent dirt from adhering to a painted surface, bandages that kill bacteria, drug-release agents and time-release biocidal coatings, and tennis balls that bounce twice as long as conventional balls.

Only U.S.-based institutes/centers are listed here; for a more comprehensive list of worldwide nanotechnology efforts, see http://sunsite.nus.sg/MEMEX/nanolink.html, a comprehensive listing of nanorelated websites hosted by the University of Singapore.

Now available online at: http://e-drexler.com/p/06/00/EOC_Cover.html

By 2014, commercial products that incorporate nanomaterials will be worth an estimated $6 trillion, with an estimated annual global market of $2 billion. For instance, see: (a) Holman, M. W.; Lackner, D. I. The Nanotech Report, 4th ed., Lux Research: New Yorki, 2006. (b) Thayer, A. M. Chem. Eng. News 2007, 85, 29.

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One of the most recent sources of nanotoxicity data is from the European Union Scientific Committee on Emerging and Newly Identified Health Risks (SCENIHR), Risk Assessment of Products of Nanotechnologies, Jan. 19, 2009. May be accessed online at:

http://ec.europa.eu/health/ph_risk/committees/04_scenihr/docs/scenihr_o_023.pdf. The main website of the SCENIHR, that houses other reports, such as the dangers associated with nanomaterials for cosmetics applications, may be found at: http://ec.europa.eu/health/ph_risk/committees/04_scenihr/04_scenihr_en.htm

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Shown from left to right are (a) Pd nanoclusters supported on hydroxyapatite: Mori, K.; Hara, T.; Mizugaki, T.; Ebitani, K.; Kaneda, K. J. Am. Chem. Soc. 2004, 126, 10657. (b) Copper nanoclusters: Williams, G. L.; Vohs, J. K.; Brege, J. J.; Fahlman, B. D. J. Chem. Ed. 2005, 82, 771.

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Current areal densities of the highest-capacity magnetic storage hard drives are >400 Gb.in², corresponding to bit areas <1500 nm², with the dimensions of one bit equal to ca. 80 nm x 20 nm; each bit is comprised of 50–100 grains with an average diameter of <10 nm. However, the use of nanomaterials with much smaller dimensions are predicted to yield bit cells with dimensions as small as 6 nm x 6 nm, corresponding to an astounding 15–20 Tb.in²!

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Ferrofluids are a class of important ternary ferrite spinels are of the formula MFe₂O₄ (M = Co, Mn, Ni), synthesized as nano-sized particulates dispersed in a solvent. These solutions have applications that span electronic devices (e.g., forming seals around spinning drive shafts in computer hard drives; heat conduction in speaker tweeters) to medicine (hyperthermia-based cancer treatment – i.e., directing nanoparticles to a cancerous area and raising their temperature via an external magnetic field). For a review of ferrofluids, see: Odenbach, S. J. Phys.: Condens. Matter 2004, 16, R1135.

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For examples of nanoparticles grown via the polyol route, see: (a) Elkins, K. E.; Chaubey, G. S.; Nandwana, V.; Liu, J. P. J. Nano Res. 2008, 1, 23. (b) Wiley, B.; Herricks, T.; Sun, Y.; Xia, Y. Nano Lett. 2004, 4, 2057, and references therein.

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Sun, S.; Zeng, H. J. Am. Chem. Soc. 2002, 124, 8204. Other examples of solution-phase growth of oxide, and other compound 0-D nanostructures (including quantum dots) are: (a) Strable, E.; Bulte, J. W. M.; Moskowitz, B.; Vivekanandan, K.; Allen, M.; Douglas, T.Chem. Mater. 2001, 13, 2201. (b) Frankamp, B. L.; Boal, A. K.; Tuominen, M. T.; Rotello, V. M. J. Am. Chem. Soc. 2005, 127, 9731. (c) Lemon, B. I.; Crooks, R. M. J. Am. Chem. Soc. 2000, 122, 12886. (d) Hanus, L. H.; Sooklal, K.; Murphy, C. J.; Ploehn, H. J. Langmuir 2000, 16, 2621.

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It should be noted that in addition to solution-phase methods, quantum dots are frequently synthesized using molecular-beam epitaxy or other vapor-phase technique. For example, see: Wang, X. Y.; Ma, W. Q.; Zhang, J. Y.; Salamo, G. J.; Xiao, M.; Shih, C. K. Nano Lett. 2005, 5, 1873, and references therein.

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For a detailed discussion of the mechanistic steps, see: Besson, C.; Finney, E. E.; Finke, R. G. J. Am. Chem. Soc. 2005, 127, 8179, and references therein.

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For a thorough recent review on nanostructural growth via coprecipitation of multiple species (and ways to synthesize/stabilize 0D nanostructures), consult: Cushing, B. L.; Kolesnichenko, V. L.; O’Connor, C. J. Chem. Rev. 2004, 104, 3893.

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Finke, R. G. in Metal Nanoparticles: Synthesis, Characterization, and Applications, Feldheim, D. L.; Foss, C. A. eds., Dekker: New York, 2002. Crooks and coworkers determined that a closed-shell metallic nanocluster of Au₅₅ has a diameter of 1.2 nm: Kim, Y.-G.; Oh, S.-K.; Crooks, R. M. Chem. Mater. 2004, 16, 167.

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Adamantyl groups were used on the periphery of the dendrimers since they strongly interact with cyclodextrins. For example, see: Rekharsky, M. V.; Inoue, Y. Chem. Rev. 1998, 98, 1880–1901.

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(a) The SEM image (low-resolution and high-resolution) of 9, 10-antraquinone nanorods is reproduced with permission from (copyright 2004 American Chemical Society): Liu, H.; Li, Y.; Xiao, S.; Li, H.; Jiang, L.; Zhu, D.; Xiang, B.; Chen, Y.; Yu, D. J. Phys. Chem. B 2004, 108, 7744. (b) The SEM image of GaP–GaAs nanowires is reproduced with permission from (copyright 2006 American Chemical Society): Verheijen, M. A.; Immink, G.; de Smet, T.; Borgstrom, M. T.; Bakkers, E. P. A. M. J. Am. Chem. Soc. 2006, 128, 1353. (c) The SEM image of carbon nanotubes is reproduced with permission from (copyright 2001 American Chemical Society): Chiang, I. W.; Brinson, B. E.; Smalley, R. E.; Margrave, J. L.; Hauge, R. H. J. Phys. Chem. B 2001, 105, 1157. (d) The SEM image of TiO₂ nanofibers is reproduced with permission from (copyright 2006 American Chemical Society): Ostermann, R.; Li, D.; Yin, Y.; McCann, J. T.; Xia, Y. Nano Lett. 2006, 6, 1297.

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(a) The HRTEM image of V₂O₅ nanorods on TiO₂ nanofibers is reproduced with permission from Frankamp, B. L.; Boal, A. K.; Tuominen, M. T.; Rotello, V. M. J. Am. Chem. Soc. 2005, 127, 9731. (b) The HRTEM image of GaP–GaAs nanowires is reproduced with permission from reference 54b. (c) The HRTEM image of multiwall carbon nanotubes is reproduced with permission from (copyright 2004 American Chemical Society): Lee, D. C.; Mikulec, F. V.; Korgel, B. A. J. Am. Chem. Soc. 2004, 126, 4951.

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(a) Iijima, S. Nature 1991, 354, 56 (first report of MWNTs). (b)Iijima, S. Nature 1993, 363, 603 (SWNT co-precedent). (c) Bethune, D. S.; Kiang, C. H.; Devries, M. S.; Gorman, G.; Savoy, R.; Vazquez, J.; Beyers, R. Nature 1993, 363, 605 (SWNT co-precedent).

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The term graphene designates a single layer of carbon atoms packed into hexagonal units. Though this structure is used to describe properties of many carbonaceous materials (e.g., CNTs, graphite, fullerenes, etc.), this planar structure is thermodynamically unstable relative to curved structures such as fullerenes, nanotubes, and other structures found in carbon soot. As such, the isolation of single graphene sheets has first been reported only recently through exfoliation from a high purity graphite crystal: Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306, 666.

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For a nice review of carbon nanotube properties and applications, see: (a) Collins, P. G.; Avouris, P. Scientific American 2000, 283, 62. (b) Milne, W. I.; Mann, M.; Dijon, J.; Bachmann, P.; McLaughlin, J.; Robertson, J.; Teo, K. B. K.; Lewalter, A.; de Souza, M.; Boggild, P.; Briggs, A.; Mogensen, K. B.; Gabriel, J. -C. P.; Roche, S.; Baptist, R. eNano Newsletter, Sept. 2008 (no. 13), available online at http://www.phantomsnet.net

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For extensive reviews of molecular electronics see: (a) Tour, J. M. Molecular Electronics: Commercial Insights, Chemistry, Devices, Architecture and Programming; World Scientific: River Edge, NJ, 2003. (b) Tour, J. M.; James, D. K. in Handbook of Nanoscience, Engineering and Technology; Goddard, W. A., III; Brenner, D. W.; Lyshevski, S. E.; Iafrate, G. J. eds.,; RC: New York, 2003; pp. 4.1–4.28. (c) Tour, J. M. Acc. Chem. Res. 2000, 33, 791.

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Note: field emission results from the tunneling of electrons from a metal tip into a vacuum, under an applied strong electric field (Chap. 7 will have more details on this phenomenon, and how it is exploited for high-resolution electron microscopy).

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(a) Avouris, P. Acc. Chem. Res. 2002, 35, 1026. (b) Wind, S. J.; Appenzeller, J.; Martel, R.; Derycke, V.; Avouris, P. Appl Phys. Lett. 2002, 80, 3817. A recent strategy for the bottom-up design of CNT interconnects: Li, J.; Ye, Q.; Cassel, A.; Ng, H. T.; Stevens, R.; Han, J.; Meyyappan, M. Appl. Phys. Lett. 2003, 82, 2491.

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Yakabson, B. I. Appl. Phys. Lett. 1998, 72, 918.

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Note: micro-Raman spectroscopy has shown that during tension, only the outer layers of MWNTs are loaded, whereas during compression, the load is transferred to all layers.

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Salvetat, J.-P.; Briggs, G. A. D.; Bonard, J.-M.; Basca, R. R.; Kulik, A. J.; Stöckli, T.; Burnham, N. A.; Forró, L. Phys. Rev. Lett. 1999, 82, 944.

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For a review of nanotube-reinforced polymers, see: Schulte, K.; Gojny, F. H.; Fiedler, B.; Sandler, J. K. W.; Bauhofer, W. in Polymer Composites, Springer: New York, 2005.

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For a very nice summary of specific stiffness/ specific strength regions for various materials classes see: http://www-materials.eng.cam.ac.uk/mpsite/ interactive_charts/spec-spec/basic.html

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Note: the National Institute of Standards and Technology (NIST) has been recently focused on the development of standard synthesis, purification, and characterization techniques for CNTs (and other nanomaterials). To date, there are a number of competing methods for SWNTs/MWNTs – all citing percent purity values that appear rather arbitrary. Indeed, purchasing a “90% pure SWNT” sample from multiple vendors will result in very different products! In order to continue the rapid progress in CNT synthesis/applications, it is essential that we set up a “gold standard” for CNTs that will immediately tell us what a certain purity level means. That is, if a “60% purity” value is cited, clarifying what the remaining 40% consists of (amorphous carbon, remaining catalytic metal, other nanotube diameters/morphologies, etc.)

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Dai, H. Acc. Chem. Res. 2002, 35, 1035. For a recent article describing the growth mechanism for vertically-aligned CNTs, see: Bedewy, M.; Meshot, E. R.; Guo, H.; Verploegen, E. A.; Lu, W.; Hart, A. J. J. Phys. Chem. C 2009, 113, 20576.

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For example, the CoMoCAT technique can be optimized to predominantly yield (6,5) semiconductor SWNTs. The first precedent for (n,m) control of SWNT growth is: Lolli, G.; Zhang, L.; Balzano, L.; Sakulchaicharoen, N.; Tan, Y.; Resasco, D. E. J. Phys. Chem. B 2006, 110, 2108.

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Considering a VLS growth mechanism, the catalyst nanocluster must be molten during nucleation. However, the growth temperature of carbonaceous nanostructures is much lower than the melting point of binary C/M systems (M = catalytic metals such as Fe, Ni, Co, etc.), which lends credence to the existence of “liquid-like” deformable nanoclusters during growth.

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Titel: Nanomaterials
verfasst von: Bradley D. Fahlman
Verlag: Springer Netherlands
Buch: Materials Chemistry
Print ISBN: 978-94-007-0692-7

Electronic ISBN: 978-94-007-0693-4

Copyright-Jahr: 2011
DOI: https://doi.org/10.1007/978-94-007-0693-4_6

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