Bulk metallic glasses represent a newly developed class of materials. Some metallic glasses possess combinations of very good or even excellent mechanical, chemical and/or magnetic properties uncovering a broad range of both industrial and vital applications. Besides all advantages metallic glasses have also significant drawbacks, which have to be overcome for commercial application. Apart from low critical thicknesses, brittleness and chemical inhomogeneity one important problem of metallic glasses is the lack of an appropriate theory describing their structure. Therefore, the search for new glass forming compositions as well as the improving of existing ones occurs at present by means of trial-and-error methods and a number of empirical rules. Empirical rules for good glass-forming ability of bulk metallic glasses have been established in recent years by Inoue and Egami. Two of these rules, (i) Preference of more than 3 elements and (ii) Need of more than 12 % radii difference of base elements, seem to be closely related to topological (geometrical) criteria. From this point of view topological parameters contribute essentially to the glass-forming ability. The third rule (iii) demands a negative mixing enthalpy of base elements and refers to the chemical interaction of the atoms. The generalized Bernal’s model (hard-sphere approximation) was used for the simulation of monatomic, binary and multi-component structures. Excluding chemical interaction, this method allows the investigation of topological criteria of the glass-forming ability. Bernal’s hard-sphere model was shown to be a good approximation for bulk metallic glasses and metallic liquids and yields good coincidence of experimental and theoretical results. • The Laguerre (weighted Voronoi) tessellation technique was used as the main tool for the structural analysis. Due to very complex structures it is impossible to determine the structure of bulk metallic glasses by means of standard crystallographic methods. • Density, radial distribution function, coordination number and Laguerre polyhedra analysis confirm amorphism of the simulated structures and are in a good agreement with available experimental results. • The ratio of the fractions of non-crystalline to crystalline Laguerre polyhedra faces was introduced as a new parameter . This parameter reflects the total non-crystallinity of a structure and the amount of atomic rearrangements necessary for crystallization. Thus, the parameter is related to the glass-forming ability. It depends strongly on composition and atomic size ratio and indicates a region of enhanced glass-forming ability in binary mixtures at 80 % of small atoms and atomic size ratio of 1.3. All found maxima of parameter for ternary mixtures have compositions and size ratios which are nearly the same as for the binary mixture with the maximum value of . • A new method of multiple-compression was introduces in order to test the tendency towards densification and/or crystallization of the simulated mixtures. The results of the multiple-compression of monatomic mixtures indicate a limiting value of about 0.6464 for the density of the amorphous state. Further densification is necessarily connected to formation and growth of nano-crystalline regions. • The results of the multiple-compression for binary mixtures shows a new maximum of the density at the size ratio of 1.3 and 30 % to 90 % of small atoms. This maximum indicates a local island of stability of the amorphous state. The maximal receivable density without crystallization in this region is enhanced compared to neighbouring regions. • The comparison of the parameter and the density to the distribution of known binary bulk metallic (metal-metal) glasses clearly shows that both parameters play a significant role in the glass-forming ability. • The polyhedra analysis shows regions with enhanced fraction of the icosahedral short-range order (polyhedron (0, 0, 12)) in the binary systems with the maximum at 80 % of small atoms and size ratio of 1.3. Comparison of the distribution of the (0, 0, 12) polyhedra to the distribution of known binary metallic (metal-metal) glasses and to the parameter shows that icosahedral short-range order is not related to the glass-forming ability and is a consequence of the high non-crystallinity (high values of ) of the mixtures and non vice versa. Results for the ternary mixtures confirm this observation. • A new approach for the calculation of the mixing enthalpy is proposed. The new method is based on the combination of Miedema’s semi-empirical model and Laguerre tessellation technique. The new method as well as 6 other methods including the original Miedema’s model were tested for more than 1400 ternary and quaternary alloys. The results show a better agreement with experimental values of the mixing enthalpy for the new model compared to all other methods. The new model takes into account the local structure at atom site and can be applied to all metallic alloys without additional extrapolations if the atomic structure of the considered alloy is known from a suitable atomistic structure model.

Bulk metallic glasses represent a newly developed class of materials. Some metallic glasses possess combinations of very good or even excellent mechanical, chemical and/or magnetic properties uncovering a broad range of both industrial and vital applications. Besides all advantages metallic glasses have also significant drawbacks, which have to be overcome for commercial application. Apart from low critical thicknesses, brittleness and chemical inhomogeneity one important problem of metallic glasses is the lack of an appropriate theory describing their structure. Therefore, the search for new glass forming compositions as well as the improving of existing ones occurs at present by means of trial-and-error methods and a number of empirical rules. Empirical rules for good glass-forming ability of bulk metallic glasses have been established in recent years by Inoue and Egami. Two of these rules, (i) Preference of more than 3 elements and (ii) Need of more than 12 % radii difference of base elements, seem to be closely related to topological (geometrical) criteria. From this point of view topological parameters contribute essentially to the glass-forming ability. The third rule (iii) demands a negative mixing enthalpy of base elements and refers to the chemical interaction of the atoms. The generalized Bernal’s model (hard-sphere approximation) was used for the simulation of monatomic, binary and multi-component structures. Excluding chemical interaction, this method allows the investigation of topological criteria of the glass-forming ability. Bernal’s hard-sphere model was shown to be a good approximation for bulk metallic glasses and metallic liquids and yields good coincidence of experimental and theoretical results. • The Laguerre (weighted Voronoi) tessellation technique was used as the main tool for the structural analysis. Due to very complex structures it is impossible to determine the structure of bulk metallic glasses by means of standard crystallographic methods. • Density, radial distribution function, coordination number and Laguerre polyhedra analysis confirm amorphism of the simulated structures and are in a good agreement with available experimental results. • The ratio of the fractions of non-crystalline to crystalline Laguerre polyhedra faces was introduced as a new parameter . This parameter reflects the total non-crystallinity of a structure and the amount of atomic rearrangements necessary for crystallization. Thus, the parameter is related to the glass-forming ability. It depends strongly on composition and atomic size ratio and indicates a region of enhanced glass-forming ability in binary mixtures at 80 % of small atoms and atomic size ratio of 1.3. All found maxima of parameter for ternary mixtures have compositions and size ratios which are nearly the same as for the binary mixture with the maximum value of . • A new method of multiple-compression was introduces in order to test the tendency towards densification and/or crystallization of the simulated mixtures. The results of the multiple-compression of monatomic mixtures indicate a limiting value of about 0.6464 for the density of the amorphous state. Further densification is necessarily connected to formation and growth of nano-crystalline regions. • The results of the multiple-compression for binary mixtures shows a new maximum of the density at the size ratio of 1.3 and 30 % to 90 % of small atoms. This maximum indicates a local island of stability of the amorphous state. The maximal receivable density without crystallization in this region is enhanced compared to neighbouring regions. • The comparison of the parameter and the density to the distribution of known binary bulk metallic (metal-metal) glasses clearly shows that both parameters play a significant role in the glass-forming ability. • The polyhedra analysis shows regions with enhanced fraction of the icosahedral short-range order (polyhedron (0, 0, 12)) in the binary systems with the maximum at 80 % of small atoms and size ratio of 1.3. Comparison of the distribution of the (0, 0, 12) polyhedra to the distribution of known binary metallic (metal-metal) glasses and to the parameter shows that icosahedral short-range order is not related to the glass-forming ability and is a consequence of the high non-crystallinity (high values of ) of the mixtures and non vice versa. Results for the ternary mixtures confirm this observation. • A new approach for the calculation of the mixing enthalpy is proposed. The new method is based on the combination of Miedema’s semi-empirical model and Laguerre tessellation technique. The new method as well as 6 other methods including the original Miedema’s model were tested for more than 1400 ternary and quaternary alloys. The results show a better agreement with experimental values of the mixing enthalpy for the new model compared to all other methods. The new model takes into account the local structure at atom site and can be applied to all metallic alloys without additional extrapolations if the atomic structure of the considered alloy is known from a suitable atomistic structure model.