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The effects of orientation and lamellar spacing on the interface microstructure and corrosion behavior of a directionally solidified (DS) Fe-B alloy in a hot-dip galvanization bath were investigated. The results indicated that the microstructure of the DS Fe-B alloy consisted of oriented α -Fe and Fe 2 B grains. The oriented Fe 2 B with [002] preferred growth orientation displayed low-angle grain boundaries on the Fe 2 B (001) basal plane. The DS Fe-B alloy with Fe 2 B vertical to the corrosion interface possessed the best corrosion resistance to liquid zinc owing to the formation of an interface-pinning multilayer induced by the Fe 2 B orientation. The epitaxially grown columnar ζ-FeZn 13 products were controlled by the geometric constraint of Fe 2 B grain orientation and size, and a mechanism model that explains the interfacial orientation-pinning behavior is discussed in detail. Transmission electron microscopy (TEM) results revealed that the possible orientation relationships of the oriented Fe 2 B and columnar ζ-FeZn 13 products are (001) Fe2B //(−402) ζ-FeZn13 and [002] Fe2B //[110] ζ-FeZn13 . The corrosion damage of the DS Fe-B alloy with Fe 2 B [002] orientation vertical to the corrosion interface in liquid zinc was governed by the competitive mechanisms of Fe 2 B/FeB transformation and microcrack-spallation resistance, which is proposed as being the result of a multiphase synergistic effect in the micro-structures. [ABSTRACT FROM AUTHOR]