ZrTiCuNiBe metallic glasses which can be produced by comparably slow solidification f the liquid melt contain small fractions of primary crystals. These primary crystals were investigated by TEM, TEM/- and SEM/EDX, and FIM/AP. The chemical composition of the crystals was found to the ZrBe₂ with small Ti, Cu and Ni additions. The size, volume fraction and morphology of the primary crystals depend on the cooling rate. The tendency of crystal formation increases with higher Be contents. The crystallization behavior can be correlated to constitutional properties of the quasi-ternary ZrTi-CuNi-Be system. Microdiffraction patterns obtained with a nearly parallel electron beam and a small spot size in connection with CBED and SAD methods were used to identify and characterize the crystal structure and its space group. By these techniques it was found that the crystals had an orthorhombic ordered structure with lattice parameters of a = 0.37 nm, b = 0.66 nm, c = 0.63 nm, and a space group Cmmm(65).

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