The glass-forming Ti75Zr10Si15 and Ti60Zr10Nb15Si15 alloys composed of nontoxic elements may represent new materials for biomedical applications. For this study, melt-spun alloy samples exhibiting glass–matrix nanocomposite structures were subjected to thermal oxidation treatments in synthetic air to improve their surface characteristics. 550 °C was identified as the most appropriate temperature to carry out oxidative surface modifications while preserving the initial metastable microstructure. The modified surfaces were evaluated considering morphological and structural aspects, and it was found that the oxide films formed at 550 °C are amorphous and consist mainly of TiO2; their thicknesses were estimated to be ∼560 nm for Ti75Zr10Si15 and ∼460 nm for Ti60Zr10Nb15Si15. The thermally treated sample surfaces exhibit not only higher roughnesses and higher hardnesses but also improved wettability compared to the as-spun materials. By immersion of oxidized samples in simulated body fluid Ca- and P-containing coatings exhibiting typical morphologies of apatite are formed.

Electrochemical micromachining (ECMM) with microtool electrodes is a promising method for microshaping bulk metallic glasses (BMGs) at room temperature. A key challenge is the control of the electrode reactions to impede the disturbing passive layer formation on machined surface regions. In the example case of a Fe-based glassy Fe65.5Cr4Mo4Ga4P12C5B5.5 alloy, it will be demonstrated that by using an aqueous electrolyte based on 0.1 M H2SO4 solution with up to 0.1 M Fe2(SO4)3 addition and by applying ultrashort voltage pulses, complex microstructures can be machined with high precision. Potentiodynamic polarization measurements reveal that the salt addition reduces the charge transfer resistance of the microtool and therefore, the negative bias potential effect. The free corrosion and passive state of the BMG workpiece are affected, but not the transpassive regime. Systematic ECMM studies were conducted to obtain optimum parameters for shaping complex lateral structures with very smooth and well-defined machining areas.

Five well-known Zr-based alloys of the systems Zr–Cu–Al–(Ni–Nb, Ni–Ti, Ag) (Cu = 15.4–36 at.%) with the highest glass-forming ability were comparatively analyzed regarding their pitting corrosion resistance and repassivation ability in a chloride-containing solution. Potentiodynamic polarization measurements were conducted in the neutral 0.01 M Na2SO4 + 0.1 M NaCl electrolyte and local corrosion damages were subsequently investigated with high resolution scanning electron microscopy (HR-SEM) coupled with energy dispersive x-ray spectroscopy (EDX). Both pitting and repassivation potential correlate with the Cu concentration, i.e., those potentials decrease with increasing Cu content. Pit morphology is not composition dependent: while initially hemispherical pits then develop an irregular shape and a porous rim. Corrosion products are rich in Cu, O, and often Cl species. A combination of low Cu and high Nb or Ti contents is most beneficial for a high pitting resistance of Zr-based bulk metallic glasses. The bulk glassy Zr57Cu15.4Al10Ni12.6Nb5 (Vit 106) and Zr52.5Cu17.9Al10Ni14.6Ti5 (Vit 105) alloys exhibit the highest pitting resistance.

A new technique for micropatterning Fe-based bulk metallic glass surfaces is reported. The transpassive dissolution process is utilized for a defined localized material removal when using a pulsed electrochemical micromachining process. By applying submicrosecond pulses between a work piece and a tool electrode, microholes of high aspect ratio and depth of up to 100 μm can be machined into the bulk glassy Fe65.5Cr4Mo4Ga4P12C5B5.5 alloy. Two potential electrolytes are identified for the machining process. For these electrolytes, different reaction mechanisms are discussed. The possibility of machining more complex structures is demonstrated for the most promising electrolyte, a methanolic H2SO4solution. The impact of the process parameters, pulse length and pulse voltage, on the machining gap and the surface quality of the machined structures is evaluated.

The oxidation behavior of Cu50Zr50 and Cu46Zr46Al8 glasses during continuous heating up to 1073 K has been investigated, with special emphasis on the oxidation resistance in the supercooled liquid (SCL) state. For Cu50Zr50, the oxide layer mostly consists of monoclinic ZrO2 (m-ZrO2), while for Cu46Zr46Al8, the oxide layer consists of two different layers: an outer layer consisting of tetragonal ZrO2 (t-ZrO2) + Al2O3 + metallic Cu (oxidation product from the SCL state of the glass matrix) and inner layer comprised of m-ZrO2 + metallic Cu islands (oxidation product from the crystallized matrix). Cu-enriched regions consisting of Cu51Zr14 (in Cu50Zr50) or AlCu2Zr + Cu70Zr15Al15 + Cu51Zr14 (in Cu46Zr46Al8) are present below the oxide layer. The present study shows that the addition of Al (8 at.%) in Cu50Zr50 results in a significant deterioration of the oxidation resistance in the SCL state since the solutionizing of Al in t-ZrO2 leads to a higher oxygen ion vacancy concentration, thus providing a higher activity of oxygen ions.

The work-hardening mechanisms of the Ti60Cu14Ni12Sn4Nb10 nanocomposite alloy were studied. This material is composed of micrometer-sized dendrites embedded in a nanostructured eutectic matrix and a CuTi2 intermetallic phase. Our study shows that, in the as-quenched state, the nanostructured eutectic matrix behaves softer than the dendrites. During mechanical deformation, both the dendrites and the eutectic matrix harden, whereas the hardness of the CuTi2 intermetallic phase remains unaltered. The high strength of the dendrites is caused by the interplay between solid solution hardening and dislocation networks during plastic flow. Interestingly, the mechanical hardening of the nanoeutectic matrix is also assisted by a martensitic transformation of the NiTi phase. Transmission electron microscopy studies clearly show that the martensitic transformation of this phase is accompanied with grain size refinement, which also plays a role in the deformation-induced mechanical hardening.

Metallic glasses exhibit generally high hardness and elastic modulus values at the expense of very limited plasticity. The incorporation of crystalline particles within an amorphous metallic matrix has been widely reported to improve the performance of these materials by reducing crack propagation. The present work analyzes the influence of nanometer-size ZrC particles on the nano-mechanical behavior of mechanically alloyed Zr55Cu30Al10Ni5 glassy matrix composites. The volume fraction of ZrC particles ranged from zero up to 20 vol. %, showing a critical change in the mechanical behavior between 10 and 20 vol. %, particularly in the elastic response.

Amorphous Zr-(Ti)-(Nb)-Al-Cu-Ni alloy samples were prepared by melt-spinning and copper mould casting in an argon atmosphere and characterized regarding their microstructure and thermal behavior. Their anodization behavior in aqueous environments with pH= 0.5 – 13 was studied by electrochemical polarization techniques in combination with surface analytical investigations, i.e. SEM/EDX, AES. In chloride-containing solutions the macroscopic corrosion resistance of bulk amorphous alloys is affected by the presence of heterogeneities, such as concentrated cluster zones of selected components or crystalline defects. Pitting phenomena are studied in neutral and acidic chloride solutions and as a result a local corrosion mechanism is proposed. The cathodic reactivity of alloy samples at different microstructural states and after pre-etching in fluoride solutions was investigated. After pre-etching melt-spun amorphous samples exhibit a significant increase in surface reactivity as expressed by a drastic increase in electrochemical capacities and in cathodic current densities as well as by a significant reduction of overpotentials for the hydrogen reduction reaction. The hydrogen sorption behavior was studied on samples galvanostatically charged at various cathodic current densities by means of XRD, DSC, TEM and thermal desorption analysis TDA. At room temperature Zr-based alloys absorb hydrogen up to H/M=1.65 mainly by interstitial solution of hydrogen atoms in the amorphous structure. The effect of absorbed hydrogen on the thermal stability and the crystallization behavior is described.

The bulk amorphous Fe-based alloy with the nominal composition Fe65.5Cr4Mo4Ga4P12C5B5.5 was obtained by copper mold casting in different shapes: cylindrical rods with diameters up to 2.5 mm and discs with 10 mm diameter and 1 mm thickness. This alloy exhibits good soft magnetic properties. Using electrochemical investigations we found that the corrosion resistance of this alloy is better than that of usual FeSi steel used for magnetic applications. Beside magnetic properties and corrosion resistance, this alloy exhibits also good mechanical properties. These were investigated by compression tests, nanoindentation and by an ultrasonic technique. The Young's modulus E was found to be around 160 GPa, the yield strength σy is around 2.3 GPa and the fracture strength σf is around 3.23 GPa, together with an elastic strain εe= 1.5% and a fracture strain εf= 2.3%. The hardness was found to be around 10 GPa.