Abstract
We report on the synthesis of air-stable aluminum nanoparticles (Al NPs) capped with 1,2-epoxy-9-decene. Long-chain epoxides have proven to be effective capping agents for Al NPs as the epoxide ring is highly susceptible to ring-opening polymerization, leading to the formation of putative polyether loops on the nascent Al NP surface. However, these materials are observed to degrade within several hours to days following exposure to ambient air. By inducing polymerization of the additional terminal alkene functionality on the epoxide, we have produced Al NPs that exhibit both a shelf life of ~6 weeks and a high active Al content. Transmission electron microscopy confirms that these spherical nanostructures, ~25 nm in diameter, are embedded in a covalently bound polymer matrix that serves as a prophylactic barrier against water/air (H2O/O2) degradation, and 27Al solid-state NMR is used to nondestructively confirm the presence of both metallic Al0 and oxidized Al3+. In addition, we have induced polymerization of the epoxide terminal alkene functionality with a long-chain diene monomer, 1,13-tetradecadiene, leading to the formation of Al NPs protected by an extremely hydrophobic polymer matrix. These core–shell nanomaterials also have high active Al contents along with extremely long shelf lives (up to 6 months upon air exposure).
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References
Arora N, Jagirdar BR (2012) Monodispersity and stability: case of ultrafine aluminium nanoparticles (<5 nm) synthesized by the solvated metal atom dispersion approach. J Mater Chem 22:9058. doi:10.1039/c2jm16764f
Aumann CE, Skofronick GL, Martin JA (1995) Oxidation behavior of aluminum nanopowders. J Vac Sci Technol B 13:1178–1183
Bunker CE, Smith MJ, Fernando KAS et al (2010) Spontaneous hydrogen generation from organic-capped Al nanoparticles and water. ACS Appl Mater Interfaces 2:11–14. doi:10.1021/am900757r
Chung SW, Guliants EA, Bunker CE et al (2009) Capping and passivation of aluminum nanoparticles using alkyl-substituted epoxides. Langmuir 25:8883–8887. doi:10.1021/la901822h
Crouse CA, Pierce CJ, Spowart JE (2012) Synthesis and reactivity of aluminized fluorinated acrylic (AlFA) nanocomposites. Combust Flame 159:3199–3207. doi:10.1016/j.combustflame.2012.03.016
Ermoline A, Schoenitz M, Dreizin E, Yao N (2002) Production of carbon-coated aluminum nanopowders in pulsed microarc discharge. Nanotechnology 13:638–643
Esmaeili B, Chaouki J, Dubois C (2011) Nanoparticle encapsulation by a polymer via in situ polymerization in supercritical conditions. Polym Eng Sci 52:637–642. doi:10.1002/pen.22126
Fernando KAS, Smith MJ, Harruff BA et al (2009) Sonochemically assisted thermal decomposition of alane N,N-dimethylethylamine with titanium (IV) isopropoxide in the presence of oleic acid to yield air-stable and size-selective aluminum core–shell nanoparticles. J Phys Chem C 113:500–503. doi:10.1021/jp809295e
Ferreira AR, Kucukbenli E, Leitao AA, de Gironcoli S (2011) Ab initio 27Al NMR chemical shifts and quadrupolar parameters for Al2O3 phases and their precursors. Phys Rev B 84:2351191–2351199
Foley TJ, Johnson CE, Higa KT (2005) Inhibition of oxide formation on aluminum nanoparticles by transition metal coating. Chem Mater 17:4086–4091. doi:10.1021/cm047931k
Glotov OG, Zyryanov V (1991) The effect of pressure on characteristics of condensed combustion products of aluminized solid propellant. Arch Combust 11:251–262
Haber JA, Buhro WE (1998) Kinetic instability of nanocrystalline aluminum prepared by chemical synthesis; facile room-temperature grain growth. J Am Chem Soc 120:10847–10855. doi:10.1021/ja981972y
Hammerstroem DW, Burgers MA, Chung SW et al (2011) Aluminum nanoparticles capped by polymerization of alkyl-substituted epoxides: ratio-dependent stability and particle size. Inorg Chem 50:5054–5059. doi:10.1021/ic2003386
Higa KT, Johnson CE, Hollins RA (1999) Preparation of fine aluminum powders by solution methods. US Patent 5885321
Jouet RJ, Warren AD, Rosenberg DM et al (2005) Surface passivation of bare aluminum nanoparticles using perfluoroalkyl carboxylic acids. Chem Mater 17:2987–2996. doi:10.1021/cm048264y
Li H, Meziani MJ, Lu F et al (2009) Templated synthesis of aluminum nanoparticles—a new route to stable energetic materials. J Phys Chem C 113:20539–20542. doi:10.1021/jp908681p
MacKenzie KJD, Smith ME (2002) Multinuclear solid-state nuclear magnetic resonance of inorganic materials. Pergamon materials series, vol 6. Elsevier, Oxford
Pantoya ML, Granier JJ (2005) Combustion behavior of highly energetic thermites: nano versus micron composites. Prop Explos Pyrotech 30:53–62. doi:10.1002/prep.200400085
Ramaswamy AL, Kaste P (2005) A “nanovision” of the physicochemical phenomena occurring in nanoparticles of aluminum. J Ener Mater 23:1–25. doi:10.1080/07370650590920250
Roy C, Dubois C, Lafleur P, Brousseau P (2004) The dispersion and polymer coating of ultrafine aluminum powders by the zigler natta reaction. Mater Res Soc Symp Proc 800:79–84
Sun J, Pantoya ML, Simon SL (2006) Dependence of sixe and size distribution on reactivity of aluminum nanoparticles in reactions with oxygen and MoO3. Thermochim Acta 444:117–127
Yang SP, Tsai RY (2006) Complexometric titration of aluminum and magnesium ions in commercial antacids. An experiment for general and analytical chemistry laboratories. J Chem Ed 83:906
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We graciously acknowledge the US Air Force Nanoenergetics Program for funding.
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Thomas, B.J., Bunker, C.E., Guliants, E.A. et al. Synthesis of aluminum nanoparticles capped with copolymerizable epoxides. J Nanopart Res 15, 1729 (2013). https://doi.org/10.1007/s11051-013-1729-8
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DOI: https://doi.org/10.1007/s11051-013-1729-8