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208 Advances in Crystallization Processes

liquid. Among the aforementioned consolidation methods, it has recently been shown that ECAP is a particular effective and novel approach used for the consolidation of amorphous powders. ECAP is a method for subjecting a volume fraction of materials to severe shear deformation by forcing them around a mold corner (Karaman, et al., 2004; Robertson, et al., 2003; Zhang, et al., 2006b). The advantages of ECAP have allowed to fabricate bulk materials

In order to utilize the viscous flow of amorphous phase, the crystallization of an amorphous alloys must be well controlled. Therefore, the temperature–time– transformation (TTT) diagram should be determined for the selected amorphous powders by measuring the onset time of the exothermic reaction due to crystallization on the DSC curves during isothermal annealing (e.g. see Fig. 12 (a)), where the sample was heated to the selected annealing temperature(s) in the supercooled liquid region, and the time that the sample began to crystallize (the onset of an exothermic reaction) was recorded. Fig. 12 (b) shows an example of the TTT diagram for the amorphous Ti50Cu18Ni22Al4Sn6 powders, which provides a window for processing in supercooled liquid state. The temperature and the time before crystallization (or the time to remain in the fully amorphous state at a certain temperature) exhibits approximately a linear relationship. At a given heating rate, the lower the temperature is, the longer the time is for the supercooled liquid to remain stable without crystallization. For the same temperature, the time window is longer at a faster heating rate. Therefore, for the ECAP processing at a given length of the can, it is necessary to select a suitable extrusion temperature (*T*e) and extrusion rate (*v*e). Two extrusion temperatures (700 and 705 K) near the calorimetric glass transition temperature (*T*g) were used in when with extrusion rate of 0.40 mm s-1 (Zhang, et al., 2006b). By using ECAP with these processing parameters, bulk nanocrystal-amorphous composites with a relative density about 97% have been achieved from the amorphous Ti50Cu18Ni22Al4Sn6 powders. Full densification was not reached, mainly owing to that the powders experienced insufficient shear deformation and that partial crystallization occurred

Karaman et al (Karaman, et al., 2004) has optimized the ECAP process to consolidate the gas-atomized Vitreloy 106a (Zr58.5Nb2.8Cu15.6Ni12.8Al10.3) powder in supercooled liquid region at different strain rates and temperatures. The microstructure of all consolidates shows significant particle deformation. The increase in aspect ratio of particles due to shear strain is correlated with the extrusion temperature. Extrusions processed close to glass transition temepraure showed significant porosity. There is an increase in the consolidate hardness, depending on the extrusion temperature. Compression experiments on the consolidated V106a shows that good consolidate samples have strength levels of 1500 – 1700 MPa, which are comparable to that of cast V106 (Zr57Nb5Al10Cu15.4Ni12.6). In spite of some nanocrystallization and short-range order formation upon processing, most of the fracture surfaces of the consolidates show shear banding and well-developed vein

patterns, typical fracture characteristics of amorphous alloys with good ductility.

The amorphous alloys have attracted widespread research interests because of their technological promise for practical applications due to execellent properties and scientific

with large cross-sections.

during ECAP processing (Zhang, et al., 2006b).

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**Section 3** 

**Crystallization of Nanomaterials** 

