Thermodynamics and kinetics of the undercooled liquid and the glass transition of the Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 alloy

Differential scanning calorimetry (DSC) was used to determine the thermodynamic functions of the undercooled liquid and the amorphous phase with respect to the crystalline state of the Zr41.2Ti13.8Cu12.5Ni10.0Be22.5bulk metallic glass forming alloy. The specific heat capacities of this alloy in the undercooled liquid, the amorphous state and the crystal were determined. The differences in enthalpy, ∆H, entropy, ∆S, and Gibbs free energy, ∆G, between crystal and the undercooled liquid were calculated using the measured specific heat capacity data as well as the heat of fusion. The results indicate that the Gibbs free energy difference between metastable undercooled liquid and crystalline solid, ∆G, stays small compared to conventional metallic glass forming alloys even for large undercoolings. Furthermore, the Kauzmann temperature, TK, where the entropy of the undercooled liquid equals to that of the crystal, was determined to be 560 K. The Kauzmann temperature is compared with the experimentally observed rate-dependent glass transition temperature, Tg. Both onset and end temperatures of the glass transition depend linearly on the logarithm of the heating rate based on the DSC experiments. Those characteristic temperatures for the kinetically observed glass transition become equal close to the Kauzmann temperature in this alloy, which suggests an underlying thermodynamic glass transition as a lower bound for the kinetically observed freezing process

In situ transmission electron microscopy studies of shear bands in a bulk metallic glass based composite

In situ straining transmission electron microscopy (TEM) experiments were performed to study the propagation of the shear bands in the Zr56.3Ti13.8Cu6.9Ni5.6Nb5.0Be12.5 bulk metallic glass based composite. Contrast in TEM images produced by shear bands in metallic glass and quantitative parameters of the shear bands were analyzed. It was determined that, at a large amount of shear in the glass, the localization of deformation occurs in the crystalline phase, where formation of dislocations within the narrow bands are observed

Microstructure Controlled Shear Band Pattern Formation and Enhanced Plasticity of Bulk Metallic Glasses Containing in situ Formed Ductile Phase Dendrite Dispersions

Results are presented for a ductile metal reinforced bulk metallic glass matrix composite based on glass forming compositions in the Zr-Ti-Cu-Ni-Be system. Primary dendrite growth and solute partitioning in the molten state yields a microstructure consisting of a ductile crystalline Ti-Zr-Nb β phase, with bcc structure, in a Zr-Ti-Nb-Cu-Ni-Be bulk metallic glass matrix. Under unconstrained mechanical loading organized shear band patterns develop throughout the sample. This results in a dramatic increase in the plastic strain to failure, impact resistance, and toughness of the metallic glass

Large supercooled liquid region and phase separation in the Zr–Ti–Ni–Cu–Be bulk metallic glasses

Results of calorimetric, differential thermal analysis, and structural measurements are presented for a series of bulk metallic glass forming compositions in the Zr-Ti-Cu-Ni-Be alloy system. The calorimetric data for five alloys, prepared along the tie line between phase separating and nonphase separating compositions, show that the transition from phase separating to nonphase separating behavior is smooth. The bulk glasses near the center of the tie line exhibit large supercooled liquid regions: Delta T approximate to 135 K, the largest known for a bulk metallic glass

Application of bag sampling technique for particle size distribution measurements

Bag sampling techniques can be used to temporarily store an aerosol and therefore provide sufficient time to utilize sensitive but slow instrumental techniques for recording detailed particle size distributions. Laboratory based assessment of the method were conducted to examine size dependant deposition loss coefficients for aerosols held in VelostatTM bags conforming to a horizontal cylindrical geometry. Deposition losses of NaCl particles in the range of 10 nm to 160 nm were analysed in relation to the bag size, storage time, and sampling flow rate. Results of this study suggest that the bag sampling method is most useful for moderately short sampling periods of about 5 minutes

Processing of carbon-fiber-reinforced Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 bulk metallic glass composites

Carbon-fiber-reinforced bulk metallic glass composites are produced by infiltrating liquid Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 into carbon fiber bundles with diameter of the individual fiber of 5 mum. Reactive wetting occurs by the formation of a ZrC layer around the fibers. This results in a composite with a homogeneous fiber distribution. The volume fraction of the fibers is about 50% and the density of the composite amounts to 4.0 g/cm(^3)

Experimental determination of a time–temperature-transformation diagram of the undercooled Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 alloy using the containerless electrostatic levitation processing technique

High temperature high vacuum electrostatic levitation was used to determine the complete time–temperature–transformation (TTT) diagram of the Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 bulk metallic glass forming alloy in the undercooled liquid state. This is the first report of experimental data on the crystallization kinetics of a metallic system covering the entire temperature range of the undercooled melt down to the glass transition temperature. The measured TTT diagram exhibits the expected "C" shape. Existing models that assume polymorphic crystallization cannot satisfactorily explain the experimentally obtained TTT diagram. This originates from the complex crystallization mechanisms that occur in this bulk glass-forming system, involving large composition fluctuations prior to crystallization as well as phase separation in the undercooled liquid state below 800 K

Metallic glass formation in highly undercooled Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 during containerless electrostatic levitation processing

Various sample sizes of Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 with masses up to 80 mg were undercooled below Tg (the glass transition temperature) while electrostatically levitated. The final solidification product of the sample was determined by x-ray diffraction to have an amorphous phase. Differential scanning calorimetry was used to confirm the absence of crystallinity in the processes sample. The amorphous phase could be formed only after heating the samples above the melting temperature for extended periods of time in order to break down and dissolve oxides or other contaminants which would otherwise initiate heterogeneous nucleation of crystals. Noncontact pyrometry was used to monitor the sample temperature throughout processing. The critical cooling rate required to avoid crystallization during solidification of the Zr41.2Ti13.8Cu12.5Ni10.0Be22.5 alloy fell between 0.9 and 1.2 K/s

Interfacial instability-driven amorphization/nanocrystallization in a bulk Ni45Cu5Ti33Zr16Si1 alloy during solidification

We report on experimental evidence for local amorphization/nanocrystallization at the interfaces between the B2-ordered Ni(Ti,Zr) phase and the NiTiZr phase with P63/mmc during solidification of a multicomponent Ni45Cu5Ti33Zr16Si1 alloy. So far there are several well-known mechanisms for interfacial amorphization in the solid state but no interfacial instability-driven amorphization/nanocrystallization during transition from liquid to solid state has been reported to our knowledge. The curvature of the interfacial area of the ordered Ni(Ti,Zr) phase is locally negative accompanying reverse atomic diffusion. This results in the frustration of the strong ordering tendency of the Ni(Ti,Zr) phase, and induces local amorphization/nanocrystallization

Correlation between fracture surface morphology and toughness in Zr-based bulk metallic glasses

Fracture surfaces of Zr-based bulk metallic glasses of various compositions tested in the as-cast and annealed conditions were analyzed using scanning electron microscopy. The tougher samples have shown highly jagged patterns at the beginning stage of crack propagation, and the length and roughness of this jagged pattern correlate well with the measured fracture toughness values. These jagged patterns, the main source of energy dissipation in the sample, are attributed to the formation of shear bands inside the sample. This observation provides strong evidence of significant “plastic zone” screening at the crack tip