Hostname: page-component-586b7cd67f-gb8f7 Total loading time: 0 Render date: 2024-11-20T09:27:20.320Z Has data issue: false hasContentIssue false
  • English
  • Français

Formation Mechanism of Aluminum Hydroxide Polymorphs

Published online by Cambridge University Press:  28 February 2024

A. Violante  and
P. M. Huang
A. Violante
Affiliation:
Dipartimento di Scienze Chimico-Agrarie, Università di Napoli “Federico II”, 80055 Portici, Napoli, Italy
P. M. Huang
Affiliation:
Department of Soil Science, University of Saskatchewan, Saskatoon, Saskatchewan, Canada S7N 0W0
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.

Substantial studies have been carried out to investigate the mechanism of the formation of Al(OH)3 polymorphs. The influence of the nature of Al precipitation products on the formation of Al(OH)3 polymorphs still remains obscure. In this study, X-ray diffraction, infrared and thermal analyses, and electron microscopic observations of the Al precipitates formed at the initial pH 8.2 and at a citric acid/Al molar ratio of 0.01 and aged for 3 hr to 60 days revealed that the transformation from the initially formed noncrystalline materials to pseudoboehmite occurred through the formation of intermediate materials with various degrees of ordering and sizes of particles that apparently had a wide range of solubility. By increasing the pH of the suspension of precipitation products of Al to 10.0 after 3 hr and 3, 11, 31, and 60 days or longer, the crystalline precipitation products were hayerite, nordstrandite and bayerite, nordstrandite and pseudoboehmite, pseudoboehmite and gibbsite, and pseudoboehmite, respectively. This work shows evidence that, as the nature of the starting Al precipitates changed, the rate of their dissolution apparently changed, and various Al(OH)3 polymorphs consequently formed. Therefore, the data substantiate the hypothesis that the mechanism of the formation of an Al(OH)3 polymorph is determined by the rate of its nucleation, which is, in turn, influenced by the rate of dissolution of the noncrystalline or poorly ordered Al-oxides initially formed.

Keywords

Al(OH)3 polymorphsBayeriteGibbsiteNoncrystalline materialsNordstranditePseudoboehmite
Type
Research Article
Information
Clays and Clay Minerals , Volume 41 , Issue 5 , October 1993 , pp. 590 - 597
Copyright
Copyright © 1993, The Clay Minerals Society

Footnotes

1

Boehmite formed at room temperature and one atmosphere pressure is a poorly crystalline, highly defective and/or fine size Al-oxyhydroxide, usually called pseudoboehmite.

References

Aldcroft, D., Bye, G. C. and Hughes, C. A., 1969 Crystallization processes in aluminum hydroxide gels. IV. Factors influencing the formation of the crystalline trihydrox-ides J. Appl. Chem. 19 167 – 172 10.1002/jctb.5010190603.CrossRefGoogle Scholar
Baker, B. R. and Pearson, R. M., 1974 Water content of pseudoboehmite: A new model for its structure J. Catal. 33 265 – 278 10.1016/0021-9517(74)90270-X.CrossRefGoogle Scholar
Bye, G. C. and Robinson, J. G., 1964 Crystallization process in aluminum hydroxide gels Kolloid Z. 198 53 – 60 10.1007/BF01499454.CrossRefGoogle Scholar
Bye, G. C. and Robinson, J. G., 1974 The nature of pseudoboehmite and its role in the crystallization of amorphous aluminum hydroxide J. Appl. Chem. Biotechnol. 24 633 – 637 10.1002/jctb.5020241104.CrossRefGoogle Scholar
Calvet, E., Boivinet, P., Noel, M., Thidon, H., Maillard, A., and Tertian, R., (1953) Contribution a l’etude des gels d’alumine: Bull. Soc. Chim. (France), 99–108.Google Scholar
De Villiers, J. M., 1969 Pedosesquioxides-composition and colloidal interactions in soil genesis during the Quaternary Soil Sci. 107 454 – 461 10.1097/00010694-196906000-00010.CrossRefGoogle Scholar
Huang, P. M., and Violante, A., (1986) Influence of organic acids on crystallization and surface properties of precipitation products of aluminum: in Interaction of Soil Minerals with Natural Organics and Microbes, Huang, P. M., and Schnitzer, M., eds., Soil Sci. Soc. Amer. Spec. Publ. 17, 549–592.CrossRefGoogle Scholar
Hsu, P. H., 1966 Formation of gibbsite from aging hy-droxy-aluminum solutions Soil Sci. Soc. Am. Proc. 30 173 – 176 10.2136/sssaj1966.03615995003000020011x.CrossRefGoogle Scholar
Hsu, P. H., 1967 Effect of salts on the formation of bayerite versus pseudoboehmite Soil Sci. 103 101 – 110 10.1097/00010694-196702000-00003.CrossRefGoogle Scholar
Hsu, P. H., 1988 Mechanisms of gibbsite crystallization from partially neutralized aluminum chloride solutions Clays & Clay Minerals 36 25 – 30 10.1346/CCMN.1988.0360104.Google Scholar
Hsu, P. H., Dixon, J. B. and Weed, S. B., 1989 Aluminum hydroxides and oxyhydrox-ides Minerals in Soil Environments 2 Madison, Wisconsin Soil Sci. Soc. Amer. 331 – 378.Google Scholar
Kodama, H. and Schnitzer, M., 1980 Effect of fulvic acid on the crystallization of aluminum hydroxides Geoderma 24 195 – 205 10.1016/0016-7061(80)90023-3.CrossRefGoogle Scholar
Papee, D., Tertian, R., and Biais, R., (1958) Recherches sur la constitution des gels et des hydrates cristallises d’alumine: Bull. Soc. Chim. (France), 1301–1310.Google Scholar
Serna, C. J., White, J. L. and Hem, S. L., 1977 Hydrolysis of aluminum-tri-(sec-butoxide) in ionic and nonionic media Clays & Clay Minerals 25 384 – 391 10.1346/CCMN.1977.0250603.CrossRefGoogle Scholar
Singer, A. and Huang, P. M., 1993 Humic acid effect on aluminum interlayering in montmorillonite Soil Sci. Soc. Am. J. 57 271 – 279 10.2136/sssaj1993.03615995005700010046x.CrossRefGoogle Scholar
Souza Santos, P., Vallejo-Freire, A. and Souza Santos, H. L., 1953 Electron microscope studies on the aging of amorphous colloid aluminum hydroxide Kolloid Z. 133 101 – 107 10.1007/BF01513437.CrossRefGoogle Scholar
Tettenhorst, R. and Hofmann, A., 1980 Crystal chemistry of boehmite Clays & Clay Minerals 28 373 – 380 10.1346/CCMN.1980.0280507.CrossRefGoogle Scholar
Van Straten, H. A., Holtkamp, T. W. and de Bruyn, P. L., 1984 Precipitation from supersaturated aluminate solutions. 1. Nucleation and growth of solid phases at room temperature J. Colloid Interface Sci. 98 342 – 362 10.1016/0021-9797(84)90159-0.CrossRefGoogle Scholar
Violante, A. and Huang, P. M., 1984 Nature and properties of pseudoboehmites formed in the presence of organic and inorganic ligands Soil Sci. Soc. Am. J. 48 1193 – 1201 10.2136/sssaj1984.03615995004800050049x.CrossRefGoogle Scholar
Violante, A. and Huang, P. M., 1985 Influence of inorganic and organic ligands on the formation of aluminum hydroxides and oxyhydroxides Clays & Clay Minerals 33 181 – 192 10.1346/CCMN.1985.0330303.CrossRefGoogle Scholar
Violante, A., Jackson, M. L., Mortland, M. M. and Farmer, V. C., 1979 Crystallization of nordstrandite in citrate systems and in the presence of montmorillonite Proc. Int. Clay Conf., Oxford, 1978 Amsterdam Elsevier 517 – 525.Google Scholar
Violante, A. and Jackson, M. L., 1981 Clay influence on the crystallization of aluminum hydroxide polymorphs in the presence of citrate, sulfate or chloride Geoderma 25 199 – 214 10.1016/0016-7061(81)90036-7.CrossRefGoogle Scholar
Violante, A. and Violante, P., 1980 Influence of pH, concentration and chelating power of organic anions on the synthesis of aluminum hydroxides and oxyhydroxides Clays & Clay Minerals 28 425 – 434 10.1346/CCMN.1980.0280604.CrossRefGoogle Scholar
Violante, P., Violante, A. and Tait, J. M., 1982 Morphology of nordstrandite Clays & Clay Minerals 30 431 – 437 10.1346/CCMN.1982.0300605.CrossRefGoogle Scholar
Violante, A., Gianfreda, L. and Violante, P., 1993 Effect of prolonged aging on the transformation of short-range ordered aluminum precipitation products formed in the presence of organic and inorganic ligands Clays & Clay Minerals 41 353 – 359 10.1346/CCMN.1993.0410311.CrossRefGoogle Scholar
Violante, A., Palmieri, F. and Buondonno, A., 1989 Influence of temperature and aging on the development of order of Al-oxyhydroxides Travaux ICSOBA 19 341 – 349.Google Scholar
Yoldas, B. E., 1973 Hydrolysis of aluminum alkoxides and bayerite conversion J. Appl. Chem. Biotechnol. 23 803 – 809 10.1002/jctb.5020231103.CrossRefGoogle Scholar
Wefer, K., and Bell, G. M., (1972) Oxides and hydroxides of aluminum: Technical Paper No. 19, Alcoa Research Laboratories, 51 pp.Google Scholar