Structural and magnetic properties, methods of synthesis, and applications of seven iron-(III) oxide polymorphs, including rare beta, epsilon, amorphous, and high-pressure forms, are reviewed. Thermal transformations resulting in the formation of iron oxides are classified according to different parameters, and their mechanisms are discussed. 57 Fe Mo ¨ssbauer spectroscopy is presented as a powerful tool for the identification, distinction, and characterization of individual polymorphs. The advantages of Mo ¨ssbauer spectroscopy are demonstrated with two examples related to the study of the thermally induced solid-state reactions of Fe 2 (SO 4 ) 3 .
Lead-InIron(III) oxide is not only a strategic industrial material but also a convenient compound for the general study of the polymorphism and the mutual polymorphous changes in nanoparticles. The existence of amorphous Fe 2 O 3 and four polymorphs (alpha, beta, gamma, and epsilon) has been established. Their discoveries as well as the majority of formation processes are connected with thermal transformations of iron-bearing materials in an oxidizing atmosphere. 57 Fe Mo ¨ssbauer spectroscopy is a unique method that allows one to distinguish and identify individual structural forms, amorphous and nanostructured Fe 2 O 3 particles, to analyze their magnetic properties and to study their formation mechanism during thermally induced solidstate reactions. In this review, thermal processes resulted in the Fe 2 O 3 formation are classified from different viewpoints and their mechanism is discussed. Applications, structural and magnetic properties, and methods of synthesis of all known forms of iron(III) oxide and their Mo ¨ssbauer characterization are also summarized. A detailed survey of the properties of rare forms (amorphous Fe 2 O 3 , β-Fe 2 O 3 , -Fe 2 O 3 , and highpressure Fe 2 O 3 ) is presented for the first time. With respect to the more known R-Fe 2 O 3 and γ-Fe 2 O 3 , the presented data spring from a series of previous works, including the excellent book by R. M. Cornell and U. Schwertmann. 1 Some unresolved problems, such as the relation between the properties of the original ferrogenous precursor and the structure of the formed iron-(III) oxide, or the experimental possibility to distinguish the amorphous Fe 2 O 3 from nanostructured γ-Fe 2 O 3 or R-Fe 2 O 3 particles are discussed. The value of Mo ¨ssbauer spectroscopy for the characterization of iron(III) oxides produced by thermal processes is demonstrated with two experimental examples taken from our work in the field. † Dedicated to R. L. Mo ¨ssbauer on the occasion of the 40 th jubilee of Nobel Prize presentation.