Hostname: page-component-cd9895bd7-dzt6s Total loading time: 0 Render date: 2024-12-18T21:20:34.017Z Has data issue: false hasContentIssue false
  • English
  • Français

Coprecipitation of Aluminum Goethite and Amorphous Al-Hydroxy-Sulfate Using Urea and Characterization of the Thermal Decomposition Products

Published online by Cambridge University Press:  01 January 2024

Geraldo Magela Da Costa  and
Eddy De Grave
Geraldo Magela Da Costa*
Affiliation:
Chemistry Department, Federal University of Ouro Preto, 35400, Ouro Preto, Brazil
Eddy De Grave
Affiliation:
Department of Physics and Astronomy, University of Ghent, B-9000 Gent, Belgium
*
*E-mail address of corresponding author: [email protected]
Rights & Permissions [Opens in a new window]

Abstract

Core share and HTML view are not available for this content. However, as you have access to this content, a full PDF is available via the ‘Save PDF’ action button.

Aluminum substitution is a common phenomenon in environmental iron oxides and oxyhydroxides, affecting the color, magnetic character, surface features, etc. Several methods for preparing Al-substituted iron oxyhydroxides can be found in the literature, resulting in samples with particular properties. In the present study, the synthesis of aluminum-substituted goethites, AlxFe1-xOOH with 0 ⩽ x ⩽ 0.15, by homogeneous precipitation and the transformation to aluminum-substituted hematites, (AlxFe1-x)O3, are presented. The goethite samples were produced at 90°C from solutions of urea and iron and aluminum nitrates in the presence of ammonium sulfate (GU series). Although attempts were made to incorporate up to 33 mole% of Al into the goethite, only ~15 mole% was found to be within the structure, due to the final pH, ~7, of the synthesis. Another feature of these goethites was a lateral alignment of the tabular particles. By heating batches of the GU samples at 400°C and 800°C, two series of Al-hematites were obtained, denoted here as the HX400 and HX800 samples, respectively. X-ray diffraction, thermal analysis, Karl-Fischer titration, transmission electron microscopy, and Mössbauer spectroscopy were used to characterize the samples. The X-ray patterns showed the samples to be pure iron phases, with particle sizes of ~10 nm for the GU and HX400 samples, and of ~70 nm for the HX800 samples. An inversion in the intensities of the (104) and (110) diffraction peaks of hematite was observed to be dependent on the aluminum substitution and was explained by small particle sizes, shape anisotropy, and the presence of nanopores. The cell parameters of both GU and HX samples showed a small decrease with increasing aluminum substitution up to x ≈ 0.15. The amount of adsorbed sulfate, presumably as an aluminum hydroxy sulfate gel, increased with aluminum substitution in all GU and HX samples, reaching a maximum of ~6.5 wt.% for the highest substitution. Heating at 100°C did not remove all of the adsorbed water, and significantly higher temperatures were required to achieve complete removal. Mossbauer spectra at 295 K and 80 K are typical for small-particle goethite and hematite, and revealed that Al-for-Fe substitution in all samples seems to be limited to ~15 mol.%.

Keywords

Aluminum SubstitutionGoethiteHomogeneous PrecipitationHematite
Type
Article
Information
Clays and Clay Minerals , Volume 64 , Issue 3 , June 2016 , pp. 283 - 298
Copyright
Copyright © Clay Minerals Society 2016

References

Aquino, A.J.A. Tunega, D. Haberhauer, G. Gerzabek, M.H. and Lischka, H., 2008 Acid-base properties of a goethite surface model: A theoretical view Geochimica et Cosmochimica Acta 72 3587–3602.CrossRefGoogle Scholar
Bakardjieva, S. Štengl, V. Šubrt, J. and Većerníková, E., 2005 Characteristic of hydrous iron (III) oxides prepared by homogeneous precipitation of iron (III) sulphate with urea Solid State Sciences 7 367–374.CrossRefGoogle Scholar
Barrero, C.A. Vandenberghe, R.E. and De Grave, E., 1999 The effect of Al-content and crystallinity on the magnetic properties of goethites Hyperfine Interactions 122 39–46.CrossRefGoogle Scholar
Barrero, C.A. Betancur, J.D. Greneche, J.M. Goya, G.F. and Berquó, T.S., 2006 Magnetism in non-stoichiometric goethite of varying total water content and surface area Geophysical Journal International 164 331–339.CrossRefGoogle Scholar
Betancur, J.D. Barrero, C.A. Greneche, J.M. and Goya, G.F., 2004 The effect of water content on the magnetic and structural properties of goethite Journal of Alloys and Compounds 369 247–251.CrossRefGoogle Scholar
Boily, J.F. and Felmy, A.R., 2008 On the protonation of oxoand hydroxo-groups of the goethite (α-FeOOH) surface: A FTIR spectroscopic investigation of surface O-H stretching vibrations Geochimica et Cosmochimica Acta 72 3338–3357.CrossRefGoogle Scholar
Burton, A.W. Ong, K. Rea, T. and Chan, I.Y., 2009 On the estimation of average crystallite size of zeolites from the Scherrer equation: a critical evaluation of its application to zeolites with one-dimensional pore systems Microporous and Mesoporous Materials 117 75–90.CrossRefGoogle Scholar
Cornell, R.M. and Schwertmann, U., 1996 The Iron Oxides Weinheim, Germany VCH Publishers.Google Scholar
da Costa, G.M. Novack, K.M. Elias, M.M.C. and da Cunha, CCRF, 2013 Quantification of moisture contents in iron and manganese ores ISIJ International 53 1732–1738.CrossRefGoogle Scholar
Dang, M.Z. Rancourt, D.G. Dutrizac, J.E. Lamarche, G. and Provencher, R., 1998 Interplay of surface conditions, particle size, stoichiometry, cell parameters, and magnetism in synthetic hematite-like materials Hyperfine Interactions 117 271–319.CrossRefGoogle Scholar
De Grave, E. and Bowen, L.H., 1982 Mössbauer study of aluminum-substituted hematites Journal of Magnetism and Magnetic Materials 27 98–108.CrossRefGoogle Scholar
De Grave, E. Bowen, L.H. Vochten, R. and Vandenberghe, R.E., 1988 The effect of crystallinity and Al substitution on the magnetic structure and Morin transition in hematite Journal of Magnetism and Magnetic Materials 72 141–151.CrossRefGoogle Scholar
Duvigneaud, P.H. and Derie, R., 1980 Shape effects on crystallite size distributions in synthetic hematites from X-ray line-profile analysis Journal of Solid State Chemistry 34 323–333.CrossRefGoogle Scholar
Ford, R.G. and Bertsch, P.M., 1999 Distinguishing between surface and bulk dehydration-dehydroxylation reactions in synthetic goethites by high-resolution thermogravimetric analysis Clays and Clay Minerals 47 329–337.CrossRefGoogle Scholar
Frandsen, C. Legg, B.A. Comolli, L.R. Zhang, H. Gilbert, B. Johnson, E. and Banfield, J.F., 2014 Aggregationinduced growth and transformation of ß-FeOOH nanorods to micron-sized α-Fe2O3 spindles CrystEngComm 16 1451–1458.CrossRefGoogle Scholar
Frost, R.L. Ding, Z. and Ruan, H.D., 2003 Thermal analysis of goethite: relevance to Australian indigenous art Journal of Thermal Analysis and Calorimetry 71 783–797.CrossRefGoogle Scholar
Fysh, S.A. and Clark, P.E., 1982 Aluminous goethite: a Moössbauer study Physics and Chemistry of Minerals 8 180–187.CrossRefGoogle Scholar
Fysh, S.A. and Clark, P.E., 1982 Aluminous hematite: a Mössbauer study Physics and Chemistry of Minerals 8 257–267.CrossRefGoogle Scholar
Ghose, S.K. Waychunas, G.A. Trainor, T.P. and Eng, P.J., 2010 Hydrated goethite (α-FeOOH) (100) interface structure: Ordered water and surface functional groups Geochimica et Cosmochimica Acta 74 1943–1953.CrossRefGoogle Scholar
Gialanella, S. Girardi, F. Ischia, G. Lonardelli, I. Mattarelli, M. and Montagna, M., 2010 On the goethite to hematite phase transformation Journal of Thermal Analysis and Calorimetry 102 867–873.CrossRefGoogle Scholar
Jiang, J.Z. Ståhl, K. Nielsen, K. and da Costa, G.M., 2000 Anisotropic x-ray line broadening in goethite-derived haematite Journal of Physics: Condensed Matter 12 4893–4898.Google Scholar
Langford, J.I. and Wilson, A.J.C., 1978 Scherrer after sixty years: a survey and some new results in the determinations of crystallite size Journal of Applied Crystallography 11 102–113.CrossRefGoogle Scholar
Leetma, K. Gomez, M.A. Becze, L. Guo, F. and Demopoulos, G.P., 2014 Comparative molecular characterization of aluminum hydroxy-gels derived from chloride and sulphate salts Journal of Chemical Technology and Biotechnology 89 206–213.CrossRefGoogle Scholar
Legg, B.A. Zhu, M. Comolli, L.R. Gilbert, B. and Banfield, J.F., 2014 Determination of the three-dimensional structure of ferrihydrite nanoparticle aggregates Langmuir 30 9931–9940.CrossRefGoogle ScholarPubMed
Li, D. Nielsen, M.H. Lee, J.R.I. Frandsen, C. Banfield, J.F. and De Yoreo, J.J., 2012 Direction-specific interactions control crystal growth by oriented attachment Science 336 1014–1018.CrossRefGoogle ScholarPubMed
de Lima Faria, J., 1963 Dehydration of goethite and diaspore Zeitschrift für Kristallographie 119 176–203.CrossRefGoogle Scholar
Löffler, L. and Mader, W., 2006 Anisotropic X-ray peak broadening and twin formation in hematite derived from natural and synthetic goethite Journal of the European Ceramic Society 26 131–139.CrossRefGoogle Scholar
Murad, E. and Johnston, J.H., 1987 Iron oxides and oxyhydroxides Mössbauer Spectroscopy Applied to Inorganic Chemistry 1 507–582.Google Scholar
Naono, H. and Fujiwara, R., 1980 Micropore formation due to thermal decomposition of acicular microcrystals of α-FeOOH Journal of Colloidal and Interface Science 73 406–415.CrossRefGoogle Scholar
Penn, R.L. and Banfield, J.F., 1998 Imperfect oriented attachment: dislocation generation in defect-free nanocrystals Science 281 969–971.CrossRefGoogle ScholarPubMed
Pomiès, M.P. Morin, G. and Vignaud, C., 1998 XRD study of the goethite-hematite transformation: application to the identification of heated prehistoric pigments European Journal of Solid State Inorganic Chemistry 35 9–25.CrossRefGoogle Scholar
Qin, H. Tan, X. Huang, W. Jiang, J. and Jiang, H., 2015 Application of urea precipitation method in preparation of advanced ceramic powders Ceramics International 41 11598–11604.CrossRefGoogle Scholar
Ruan, H.D. and Gilkes, R.J., 1995 Dehydroxylation of aluminous goethite: unit cell dimensions, crystal size and surface area Clays and Clay Minerals 43 196–211.CrossRefGoogle Scholar
Ruan, H.D. Frost, R.L. and Kloprogge, J.T., 2001 The behavior of hydroxyl units of synthetic goethite and its dehydroxylated product hematite Spectrochimica Acta Part A 57 2575–2586.CrossRefGoogle ScholarPubMed
Ruan, H.D. Frost, R.L. Kloprogge, J.T. and Duong, L., 2002 Infrared spectroscopy of goethite dehydroxylation II. Effect of aluminum substitution on the behavior of hydroxyl units. Spectrochimica Acta Part A 58 479–491.Google ScholarPubMed
Schwertmann, U., 1984 The double dehydroxylation peak of goethite Thermochimica Acta 78 39–46.CrossRefGoogle Scholar
Schwertmann, U. and Cornell, R.M., 1991 Iron Oxides in the Laboratory Weinheim, Germany VCH Publishers.Google Scholar
Schwertmann, U. Cambier, P. and Murad, E., 1985 Properties of goethite of varying crystallinity Clays and Clay Minerals 33 369–378.CrossRefGoogle Scholar
Schwertmann, U. Fitzpatrick, R.W. Taylor, R.M. and Lewis, D.G., 1979 The influence of aluminum on iron oxides. Part II. Preparation and properties of A-substituted hematites Clays and Clay Minerals 27 105–112.CrossRefGoogle Scholar
Vandenberghe, R.E. De Grave, E. and de Bakker, P.M.A., 1994 On the methodology of the analysis of Mössbauer spectra Hyperfine Interactions 83 29–49.CrossRefGoogle Scholar
Vandenberghe, R.E. Van San, E. De Grave, E. and da Costa, G.M., 2001 About the Morin transition in hematite in relation with particle size and aluminum substitution Czech Journal of Physics 51 663–675.CrossRefGoogle Scholar
Wells, M.A. Gilkes, R.J. and Anand, R.R., 1989 The formation of corundum and aluminous hematite by the thermal dehydroxylation of aluminous goethite Clay Minerals 24 513–530.CrossRefGoogle Scholar
Willard, H.H. and Tang, N.K., 1937 A study of the precipitation of aluminum basic sulfate by urea Journal of the American Chemical Society 59 1190–1196.CrossRefGoogle Scholar
Zhang, H. and Banfield, J.F., 2014 Interatomic Coulombic interactions as the driving force for oriented attachment CrystEngComm 16 1568–1578.CrossRefGoogle Scholar