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Improvements in nanoscale zero-valent iron production by milling through the addition of alumina

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Abstract

A new milling procedure for a cost-effective production of nanoscale zero-valent iron for environmental remediation is presented. Conventional ball milling of iron in an organic solvent as Mono Ethylene Glycol produces flattened iron particles that are unlikely to break even after very long milling times. With the aim of breaking down these iron flakes, in this new procedure, further milling is carried out by adding an amount of fine alumina powder to the previously milled solution. As the amount of added alumina increases from 9 to 54 g l−1, a progressive decrease of the presence of flakes is observed. In the latter case, the appearance of the particles formed by fragments of former flakes is rather homogeneous, with most of the final nanoparticles having an equivalent diameter well below 1 µm and with an average particle size in solution of around 400 nm. An additional increase of alumina content results in a highly viscous solution showing worse particle size distribution. Milled particles, in the case of alumina concentrations of 54 g l−1, have a fairly large specific surface area and high Fe(0) content. These new particles show a very good Cr(VI) removal efficiency compared with other commercial products available. This good reactivity is related to the absence of an oxide layer, the large amount of superficial irregularities generated by the repetitive fracture process during milling and the presence of a fine nanostructure within the iron nanoparticles.

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References

  • Bagchi D, Stohs SJ, Downs BW, Bagchi M, Preuss HG (2002) Cytotoxicity and oxidative mechanisms of different forms of chromium. Toxicology 180(1):5–22

    Article  Google Scholar 

  • Buerge IJ, Hug SJ (1997) Kinetics and pH dependence of chromium (VI) reduction by iron (II). Environ Sci Technol 31(5):1426–1432

    Article  Google Scholar 

  • Casas C, Tejedor R, Rodriguez-Baracaldo R, Benito JA, Cabrera JM (2015) The effect of oxide particles on the strength and ductility of bulk iron with a bimodal grain size distribution. Mater Sci Eng A 627:205–216

    Article  Google Scholar 

  • Crane RA, Scott TB (2012) Nanoscale zero-valent iron: future prospects for an emerging water treatment technology. J Hazard Mater 211:112–125

    Article  Google Scholar 

  • Dickinson M, Scott TB (2011) The effect of vacuum annealing on the remediation abilities of iron and iron–nickel nanoparticles. J Nanopart Res 13(9):3699–3711

    Article  Google Scholar 

  • Gheju M (2011) Hexavalent chromium reduction with zero-valent iron (ZVI) in aquatic systems. Water Air Soil Pollut 222(1–4):103–148

    Article  Google Scholar 

  • Hao L, Lu Y, Asanuma H, Guo J (2012) The influence of the processing parameters on the formation of iron thin films on alumina balls by mechanical coating technique. J Mater Proc Technol 212(5):1169–1176

    Article  Google Scholar 

  • Kerkar M, Robinson J, Forty AJ (1990) In situ structural studies of the passive film on iron and iron/chromium alloys using X-ray absorption spectroscopy. Faraday Discuss Chem Soc 89(P001):1–20

    Google Scholar 

  • Kim HS, AhnJY HwangKY, Kim IK, Hwang I (2010) Atmospherically stable nanoscale zero-valent iron particles formed under controlled air contact: characteristics and reactivity. Environ Sci Technol 44(5):1760–1766

    Article  Google Scholar 

  • Kim HS, Kim T, Ahn JY, Hwang KY, Park JY, Lim TT, Hwang I (2012) Aging characteristics and reactivity of two types of nanoscale zero-valent iron particles (Fe BH and Fe H2) in nitrate reduction. Chem Eng J 197:16–23

    Article  Google Scholar 

  • Klimkova S, Cernik M, Lacinova L, Filip J, Jancik D, Zboril R (2011) Zero-valent iron nanoparticles in treatment of acid mine water from in situ uranium leaching. Chemosphere 82(8):1178–1184

    Article  Google Scholar 

  • Köber R, Hollert H, Hornbruch G, Jekel M, Kamptner A et al (2014) Nanoscale zero-valent iron flakes for groundwater treatment. Environ Earth Sci 72(9):3339–3352

    Article  Google Scholar 

  • Lapuerta S, Moncoffre N, Millard-Pinard N, Jaffrézic H, Bérerd N et al (2006) Role of proton irradiation and relative air humidity on iron corrosion. J Nucl Mater 352(1):174–181

    Article  Google Scholar 

  • Li XQ, Cao J, Zhang WX (2008) Stoichiometry of Cr(VI) immobilization using nanoscale zerovalent iron (nZVI): a study with high-resolution X-ray photoelectron spectroscopy (HR-XPS). Ind Eng Chem Res 47(7):2131–2139

    Article  Google Scholar 

  • Li S, Yan W, Zhang WX (2009) Solvent-free production of nanoscale zero-valent iron (nZVI) with precision milling. Green Chem 11(10):1618–1626

    Article  Google Scholar 

  • Liu Y, Lowry GV (2006) Effect of particle age (Fe0 content) and solution pH on NZVI reactivity: H2 evolution and TCE dechlorination. Environ Sci Technol 40(19):6085–6090

    Article  Google Scholar 

  • Liu ZG, Hao XJ, Masuyama K, Tsuchiya K, Umemoto M, Hao SM (2001) Nanocrystal formation in a ball milled eutectoid steel. Scr Mater 44(8):1775–1779

    Article  Google Scholar 

  • Liu Y, Choi H, Dionysiou D, Lowry GV (2005a) Trichloroethene hydrodechlorination in water by highly disordered monometallic nanoiron. Chem Mater 17(21):5315–5322

    Article  Google Scholar 

  • Liu Y, Majetich SA, Tilton RD, Sholl DS, Lowry GV (2005b) TCE dechlorination rates, pathways, and efficiency of nanoscale iron particles with different properties. Environ Sci Technol 39(5):1338–1345

    Article  Google Scholar 

  • Melitas N, Chuffe-Moscoso O, Farrell J (2001) Kinetics of soluble chromium removal from contaminated water by zerovalent iron media: corrosion inhibition and passive oxide effects. Environ Sci Technol 35(19):3948–3953

    Article  Google Scholar 

  • Mueller NC, Braun J, Bruns J, Černík M et al (2012) Application of nanoscale zero valent iron (NZVI) for groundwater remediation in Europe. Environ Sci Pollut Res 19(2):550–558

    Article  Google Scholar 

  • Mystrioti C, Xenidis A, Papassiopi N (2014) Application of iron nanoparticles synthesized by green tea for the removal of hexavalent chromium in column tests. J Geosci Environ Prot 2(04):28

    Google Scholar 

  • Nanoiron s.r.o. Nanofer 25P (2016) http://www.nanoiron.cz/en/nanofer-25p. Accessed 04 Mar 2016

  • O’Carroll D, Sleep B, Krol M, Boparai H, Kocur C (2013) Nanoscale zero valent iron and bimetallic particles for contaminated site remediation. Advin Water Resour 51:104–122

    Article  Google Scholar 

  • Paesano A Jr et al (2004) Structural and Mössbauer characterization of the ball-milled Fex/(Al2O3)100-x/system. J Appl Phys 96(5):2540–2546

  • Patnaik P (2003) Handbook of inorganic chemicals, vol 28. McGraw-Hill, New York, pp 11–12

    Google Scholar 

  • Phenrat T, Saleh N, Sirk K, Tilton RD, Lowry GV (2007) Aggregation and sedimentation of aqueous nanoscale zerovalent iron dispersions. Environ Sci Technol 41(1):284–290

    Article  Google Scholar 

  • Rodríguez-Baracaldo R, Benito JA, Cabrera JM, Prado JM (2007) Mechanical response of nanocrystalline steel obtained by mechanical attrition. J Mater Sci 42(5):1757–1764

    Article  Google Scholar 

  • Smallman RE, Bishop RJ (1999) Modern physical metallurgy and materials engineering. Butterworth-Heinemann, Oxford, pp 323–325

  • Song H, Carraway ER (2005) Reduction of chlorinated ethanes by nanosized zero-valent iron: kinetics, pathways, and effects of reaction conditions. Environ Sci Technol 39(16):6237–6245

    Article  Google Scholar 

  • Soukupova J et al (2015) Highly concentrated, reactive and stable dispersion of zero-valent iron nanoparticles: direct surface modification and site application. Chem Eng J 262:813–822

    Article  Google Scholar 

  • Tang SC, Lo I (2013) Magnetic nanoparticles: essential factors for sustainable environmental applications. Water Res 47(8):2613–2632

    Article  Google Scholar 

  • Uegami M, Kawano J, Okita T, Fujii Y, Okinaka K, Kayuka K, Yatagi S (2006) Iron particles for purifying contaminated soil or groundwater. US Patent No. 7,022,256

  • Velimirovic M, Schmid D, Wagner S, Micić V, von der Kammer F, Hofmann T (2015) Agar agar-stabilized milled zerovalent iron particles for in situ groundwater remediation. Sci Total Environ 563:713–723

  • Wang CB, Zhang WX (1997) Synthesizing nanoscale iron particles for rapid and complete dechlorination of TCE and PCBs. Environ Sci Technol 31(7):2154–2156

    Article  Google Scholar 

  • Xie Y, Cwiertny DM (2012) Influence of anionic cosolutes and pH on nanoscale zerovalent iron longevity: time scales and mechanisms of reactivity loss toward 1,1,1,2-tetrachloroethane and Cr(VI). Environ Sci Technol 46(15):8365–8373

    Article  Google Scholar 

  • Yan W, Lien HL, Koel BE, Zhang WX (2013) Iron nanoparticles for environmental clean-up: recent developments and future outlook. Environ Sci 15(1):63–77

    Google Scholar 

  • Yu RF, Chi F-H, Cheng W-P, Chang J-C (2014) Application of pH, ORP, and DO monitoring to evaluate chromium(VI) removal from wastewater by the nanoscale zero-valent iron (nZVI) process. Chem Eng J 255:568–576

    Article  Google Scholar 

  • Zhang WX (2006) Dispersed zero-valent iron colloids. US Patent No. 7,128,841 B2

Download references

Acknowledgments

This work was supported by the EU-Project NANOREM (Taking Nanotechnological Remediation Processes from Lab Scale to End User Applications for the Restoration of a Clean Environment, NMP.2012.1.2-1 FP7—Grant Agreement Nr. 309517).

David Ribas is also grateful to the Spanish MEC under the FPI project for the grant awarded to him (ref. BES-2012-052327) and Miroslav Cernik for the support through the “National Programme for Sustainability I” project LO1201 and the OPR&DI project of the Centre for Nanomaterials, Advanced Technologies and Innovation CZ.1.05/2.1.00/01.0005.

The authors would like to thank PometonEspaña and BASF GmbH for their donation of materials to carry out the project.

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Authors and Affiliations

  1. Fundació CTM Centre Tecnològic de Manresa, Plaça de la Ciència 2, 08243, Manresa, Spain

    D. Ribas, V. Martí & J. A. Benito

  2. Department of Chemical Engineering, ETSEIB, Universitat Politècnica de Catalunya, Av. Diagonal 647, 08028, Barcelona, Spain

    D. Ribas & V. Martí

  3. Institute for Nanomaterials, Advanced Technologies and Innovation, Technical University of Liberec, Studentská 1402/2, 461 17, Liberec 1, Czech Republic

    M. Cernik

  4. Department of Materials Science and Metallurgical Engineering, EUETIB, Universitat Politècnica de Catalunya, Comte d’Urgell 187, 08036, Barcelona, Spain

    J. A. Benito

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  1. D. Ribas
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  2. M. Cernik
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  3. V. Martí
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  4. J. A. Benito
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Correspondence to J. A. Benito.

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Ribas, D., Cernik, M., Martí, V. et al. Improvements in nanoscale zero-valent iron production by milling through the addition of alumina. J Nanopart Res 18, 181 (2016). https://doi.org/10.1007/s11051-016-3490-2

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  • DOI: https://doi.org/10.1007/s11051-016-3490-2

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