Thermal Stability and Kinetics of Binary Cu65Hf35 Bulk Metallic Glass

We investigate the thermal stability and kinetics of Cu65Hf35 bulk metallic glass （BMG）. Cu65Hf35 glassy rods in diameter up to 2 mm are prepared by a conventional copper mould suction casting. Kinetics of glass transition and crystallizations are investigated and the ideal glass transition temperature of the alloy is obtained. It is found that the dependence of crystallization temperature of the BMG on the heating rates follows the Vogel-Fhlcher- Tammann （VFT） non-linear relationship rather than the Kissinger and Lasocka linear fittings. The long-term thermal stability of the BMG is investigated by means of continuous crystallization diagrams obtained from the extension of VFT analysis. It is suggested that ideal glass transition and crystallization temperatures can also be regarded as the long-term stability criteria of the BMG.     

Role of Ag microalloying on glass forming ability and crystallization kinetics of ZrCoAgAlNi amorphous alloy

Bulk metallic glasses(BMGs) with new chemical compositions(ZrCoAgAlNi) were fabricated and the effects of Ag minor addition on the glass forming ability(GFA) and crystallization kinetics were studied. The x-ray diffraction(XRD) test was applied to identify the amorphousness of BMGs or possible crystalline phases. Using differential scanning calorimeter(DSC), the thermal stability and crystallization kinetics under a non-isothermal condition at the different heating rates were studied. Considering the heating rate dependency of glass transition and crystallization kinetics, the activation energy was evaluated and measured for the mentioned processes. It was revealed that the rise in Ag content led to the decrease in activation energy for glass transition, while the activation energy for crystallization increased. The thermal stability and GFA were also studied and it was found that the Ag addition strongly affected the inherent features of BMGs. With the increase in Ag content, the atomic mobility and structural rearrangement changed in the material and consequently, the GFA and thermal stability were significantly improved.     

A Kinetic Transition from Low to High Fragility in Cu-Zr Liquids

Researchers have reported that Cu-Zr liquids are kinetically strong at the best glass-forming compositions. Here we systematically study the temperature dependence of viscosity and diffusion of Cu-Zr liquids using molecular dynamics simulations, and the results illustrate that the better glass formers are actually more fragile close to the glass transition. There is a kinetic transition from low to high fragility when the optimal glass-forming liquids are quenched into glass states. This transition is associated with the more rapid decrease of the excess entropy of the liquids above and close to the glass transition temperature, Tg, compared to other compositions. Accompanied by the transition to high fragility, peaks in the thermal expansivity and specific heat are observed at the optimal compositions. Furthermore, the Stokes Einstein relation is examined over a wide composition range for Cu-Zr alloys, and the results indicate that glass-forming ability closely correlates with dynamical heterogeneity.     

Glass Formation Ability and Kinetics of the Gd55A120Ni25 Bulk Metallic Glass

We report a new bulk glass-forming alloy GdssA12oNi25. The bulk sample of the alloy is prepared in the shape of rods in diameter 2ram by suction casting. The rod exhibits typical amorphous characteristics in the x-ray diffraction pattern, paramagnetic property at 30OK, distinct glass transition and multi-step crystallization behaviour in differential scanning calorimetry traces. The gJass formation ability of the alloy is investigated by using the reduced glass transition temperature Trg and the parameter γ- Kinetics of glass transition and primary crystallization is also studied. The fragility parameter m obtained from the Vogel-Fulcher-Tammann dependence of glass transition temperature Tg on In φ （φ is the heating rate） classifies the bulk metallic glasses into the intermediate category according to Angell＇s classification.     

Formability and Thermal Stability of Ce62Al15Fe8Co15 Bulk Metallic Glass

The formability and thermal stability of Ce62Al15Fe8Co15 bulk metallic glass （BMG） are studied by x-ray diffraction （XRD） and differential scanning calorimetry. The critical diameter of Ce62Al15Fe8Co15 BMG predicted by the parameter γ is about 3.1 mm, which is roughly in agreement with the XRD results. Stability of the BMG is investigated by means of continuous crystallization diagrams obtained from the extension of the Kissinger and Vogel-Fulcher-Tammann （VFT） equations comparatively. It is found that the dependence of crystallization temperature of the BMG on heating rates follows a nonlinear relationship rather than Kissinger and Lasoka＇s linear fittings. The thermal stability of the BMG is investigated by the VFT equation.     

New criterion in predicting glass forming ability of various glass-forming systems

It has been confirmed that glass-forming ability （GFA） of supercooled liquids is related to not only liquid phase stability but also the crystallization resistance. In this paper, it is found that the liquid region interval （T1 - Tg） characterized by the normalized parameter of Tg/T1 could reflect the stability of glass-forming liquids at the equilibrium state, whilst the normalization of supercooled liquid region △Tx=（Tx - Tg）, i.e. △Tx/Tx （wherein T1 is the liquidus temperature, Tg the glass transition temperature, and Tx the onset crystallization temperature） could indicate the crystallization resistance during glass formation. Thus, a new parameter, defined as ζ = Tg/T1＋△Tx/Tx is established to predict the GFA of supercooled liquids. In comparison with other commonly used criteria, this parameter demonstrates a better statistical correlation with the GFA for various glass-forming systems including metallic glasses, oxide glasses and cryoprotectants.     

Pd-Si Binary Bulk Metallic Glass Prepared at Low Cooling Rate

We report that binary bulk metallic glasses can be made up to 6ram in diameter in a Pd Si ahoy system by air cooling at slow cooling rate (about 8 K/s). The high stability of the undercooled liquid and the large glass-forming ability (GFA) of the binary alloy are contributed to the removing of heterogeneous impurities in the alloy melt by employing the fluxing technique. It has been found that decreasing cooling rate can increase the supercooled liquid region and thermal stability of the glassy alloy. After fluxing, a wider supercooled liquid region (△T = 58 K) and higher glass-forming ability have been obtained in a Pd81Si19 binary glassy alloy prepared by slow cooling rate.     

A Modified Glass Formation Criterion for Various Glass Forming Liquids with Higher Reliability

A modified indicator of the glass forming ability （GFA） from the previous 7 = Tx/（Tl ＋ Tg） for various glass forming liquids is proposed based on a conceptual approach which combines more acceptable physical metallurgy views in terms of the time-temperature-transformation diagrams. It is found that the glass forming ability for glass forming liquids is closely associated mainly with two factors, i.e. （2Tx - Tg） and Tl （wherein Tx is the onset crystallization temperature, Tg the glass transition temperature, and Tl the liquidus temperature）, and could be predicated by a unified parameter γm defined as （2Tx - Tg）/Tl. This approach is confirmed and validated by experimental data in various glass forming systems including oxide glasses, cryoprotectants and metallic glasses, which all shows a higher reliability when their glass forming ability is predicted by the modified parameter.     

Fragile-to-Strong Transition in Al-Ni-M （M=La,Pr, Nd） Metallic Glasses

We study the dynamic behavior of marginal metallic glass-forming liquids Al-Ni-M （M=La, Pr, Nd） in terms of liquid fragility in high and low temperature regions. The liquids are extremely fragile above the liquidus temperature T liq, but become rather strong near the glass transition temperature Tg. The strength of the transition is inversely correlated with the fragility index at Tg. This relation is discussed in terms of potential energy landscape.     

A comparative study of the structure and crystallization of bulk metallic amorphous rod Pr60Ni30Al10 and melt-spun metallic amorphous ribbon Al87Ni10Pr3

Pr-based bulk metallic amorphous （BMA） rods （Pr60Ni30Al10） and Al-based amorphous ribbons （Al87Ni10Pr3） have been prepared by using copper mould casting and single roller melt-spun techniques, respectively. Thermal parameters deduced from differential scanning calorimeter （DSC） indicate that the glass-forming ability （GFA） of Pr60Ni30Al10 BMA rod is far higher than that of Al87Ni10Pr3 ribbon. A comparative study about the differences in structure between the two kinds of glass-forming alloys, superheated viscosity and crystallization are also made. Compared with the amorphous alloy Al87Ni10Pr3, the BMA alloy Pr60Ni30Al10 shows high thermal stability and large viscosity, small diffusivity at the same superheated temperatures. The results of x-Ray diffraction （XRD） and transmission electron microscope （TEM） show the pronounced difference in structure between the two amorphous alloys. Together with crystallization results, the main structure compositions of the amorphous samples are confirmed. It seems that the higher the GFA, the more topological type clusters in the Pr-Ni-Al amorphous alloys, the GFAs of the present glass-forming alloys are closely related to their structures.     

Formation of Pd-Ni Based Bulk Metallic Glasses

Bulk metallic glasses are prepared in Pd4o.sNi4o.sSixP19-x （x = 0-14 at.%） alloys by a combination of flux treatment and water quenching technique. It is found that the thermal stability of the Pd4o.sNi4o.sSixP19=x glassy alloys depends on the addition of Si content. Among the Pd4o.sNi4o.sSixP19=x glassy alloys studied, the Pd4o.sNi4o.sSisPls bulk metallic glass exhibits the largest supercooled liquid region （△T = 119 K） and the highest activation energy of crystallization （283.3k J/tool）, showing enhanced glass formation ability and extraordinary glassy thermal stability.     

Thermal stability,crystallization, and magnetic properties of FeNiBCuNb alloys

Amorphous(Fe_(40)Ni_(40)B_(19)Cu_1)_(100-x)Nb_x(x = 1, 3, 5, 7) ribbons are prepared by using the melt-spinning method. We find that the glass forming ability(GFA) of the as-melt spun ribbons is significantly improved by adding Nb element. In addition, the thermal stability evaluated in steps of ?T = T_(x2)-T_(x1) effectively increases from 16 K to 75 K with Nb content increasing. The as-melt spun(Fe_(40)Ni_(40)B_(19)Cu_1)_(97) Nb_3 ribbon exhibits a lowest coercivity of 2 A/m and relatively large saturation magnetization of 103.7 A·m~2/kg and thus it can be further treated by being annealed at 809 K. The crystallization behavior is confirmed to be determined by two individual crystallization processes corresponding to the precipitation of(Fe,Ni)_(23) B_6 phase and γ-(Fe,Ni) phase. With increasing annealing time, the single(Fe,Ni)_(23)B_6 phase can be transformed into a mixture of(Fe,Ni)_(23)B_6 and γ-(Fe,Ni) phase, and the grain size of γ-(Fe, Ni) phase increases from 5 nm to 80 nm while the grain size of(Fe,Ni)_(23)B_6 remains almost unchanged. Finally, we find that the grain growth in each of(Fe,Ni)_(23)B_6 and γ-(Fe, Ni) deteriorates the overall magnetic properties.     

High-zirconium bulk metallic glasses with high strength and large ductility

In this paper,high-zirconium Zr66+2xAl9-x(Ni1/3Cu2/3) 25-x(x=0,1,2 at.%) bulk metallic glasses with high strength and large ductility were fabricated by copper mould casting.The effects of zirconium content on the glass-forming ability(GFA),thermal properties and mechanical properties were investigated using X-ray diffractometer(XRD),differential scanning calorimeter(DSC),and mechanical testing system in compressive and three-point bending modes,respectively.The high-zirconium BMGs show the critical diameters of 3-5 mm,the supercooled liquid region ranging from 70 K to 99 K,and the yield strength of over 1700 MPa.The Zr 70 Al 7(Ni1/3Cu2/3) 23 BMG exhibits a large compressive plastic strain up to 21% and a high notch toughness value of 60.6 MPa m 1/2.The increase in Zr content results in the decrease in GFA and thermostability,and in the improvement of plasticity under compressive and three-point bending conditions.The superior plasticity of high-zirconium BMGs is attributed to their high Poisson’s ratio and small elastic modulus ratio /B.     

Abnormal relaxation kinetics in D-mannitol glass confined by nanoporous alumina

The relaxation kinetics and phase transformations of the confined D-mannitol(DM) in nanoporous alumina are studied in-situ using a high-precision nano-calorimeter. We find that the crystallization behavior can be suppressed when it is confined in nanopores smaller than 50 nm. The confined DM glass has a much smaller fragility(～76) than free DM glass(～125), confirming the enhanced glass-forming ability. It is intriguing that during isothermal annealing both the confined and free DM glasses relaxation kinetics experience two relaxation stages that have distinct activation energies. The relaxation activation energy of the confined glass is about 25%-29% smaller than the free glass, which is attributed to the reduced dimensionality. The abnormal kinetics observed in the confined DM glass open a new avenue for preparing stable glasses.     

Double spin-glass-like behavior and antiferromagnetic superexchange interaction between Fe~(3+) ions in α-Ga_(2-x)Fe_xO_3(0≤x≤0.4)

Single phase of Fe3+-doped α-Ga2-xFexO3(α-GF x O, x = 0.1, 0.2, 0.3, 0.4) is synthesized by treating the β-Ga2-x Fe x O3(β-GF x O) precursors at high temperatures and high pressures. Rietveld refinements of the X-ray diffraction data show that the lattice constants increase monotonically with the increase of Fe3+content. Calorimetric measurements show that the temperature of the phase transition from α-GF x O to β-GF x O increases, while the associated enthalpy change decreases upon increasing Fe3+content. The optical energy gap deduced from the reflectance measurement is found to decrease monotonically with the increase in Fe3+content. From the measurements of magnetic field-dependent magnetization and temperature-dependent inverse molar susceptibility, we find that the superexchange interaction between Fe3+ions is antiferromagnetic. Remnant magnetization is observed in the Fe3+-doped α-GF x O and is attributed to the spin glass in the magnetic sublattice. At high Fe3+doping level(x = 0.4), two evident peaks are observed in the image part of the AC susceptibility χ ac. The frequency dependence in intensity of these two peaks as well as two spin freezing temperatures observed in the DC magnetization measurements of α-GF0.4O is suggested to be the behavior of two spin glasses.     

Small activation entropy bestows high-stability of nanoconfined D-mannitol

It has been a long-standing puzzling problem that some glasses exhibit higher glass transition temperatures(denoting high stability) but lower activation energy for relaxations(denoting low stability). In this paper, the relaxation kinetics of the nanoconfined D-mannitol(DM) glass was studied systematically using a high-precision and high-rate nanocalorimeter.The nanoconfined DM exhibits enhanced thermal stability compared to the free DM. For example, the critical cooling rate for glass formation decreases from 200 K/s to below 1 K/s; the Tg increases by about 20 K–50 K. The relaxation kinetics is analyzed based on the absolute reaction rate theory. It is found that, even though the activation energy E~*decreases,the activation entropy S~*decreases much more for the nanoconfined glass that yields a large activation free energy G~*and higher thermal stability. These results suggest that the activation entropy may provide new insights in understanding the abnormal kinetics of nanoconfined glassy systems.     

The relationship between viscosity and glass forming ability of Al-(Ni)-Yb alloy systems

The dynamic viscosity of Al-Yb and Al-Ni-Yb superheated melts was measured using a torsional oscillation viscometer. The results show that the temperature dependence of viscosity fits the Arrhenius law well and the fitting factors are calculated. The amorphous ribbons of these alloys were produced by the melt spinning technique and the thermal properties were characterized by using a differential scanning calorimetry (DSC). E (the activation energy for viscous flow), which reflects the change rate of viscosity, has a good negative relation with the GFA in both Al-Yb and Al-Ni-Yb systems. However, there is no direct relation between liquidus viscosity (ηL) and GFA. The superheated fragility M can predict GFA in Al-Yb or Al-Ni-Yb alloy system.     

Isothermal crystallization in Ce70Ga6Cu24 bulk metallic glass

The isothermal crystallization behaviors in a newly developed CeGaCu bulk metallic glass have been investigated through the classic differential scanning calorimeter(DSC) method. It is found that the apparent activation energy(Ea) strongly depends on the fraction(x) of isothermal crystallization. Johnson-Mehl-Avrami(JMA) formula was used to analyze the mechanism of crystallization and the obtained Avrami exponent(n) was discovered to show an obvious correlation with the crystallization fraction x. With the help of the relation between Ea and n, the nucleation and growth activation energies, En and Eg, were estimated to be 214–304 kJ/mol and 91 kJ/mol, respectively. This result suggests that the main energy barrier against crystallization in the present glass should be the nucleation of nucleates, rather than the growth of crystals. Such a large En is also believed to be responsible for the good glass forming ability of the CeGaCu alloy.     

Critical behaviours and magnetic properties of three-dimensional bond and anisotropy dilution Blume——Capel model in the presence of an applied field

This paper studies the critical behaviours and magnetic properties of three-dimensional bond and anisotropy dilution Blume--Capel model (BCM) in the presence of an applied field within the effective field theory. The trajectory of tricritical point, reentrant transitions and degenerate patterns of anisotropy are obtained both for the bond and the anisotropy dilutions. The global phase diagrams demonstrate unusually reentrant phenomena. The temperature dependences of magnetization curves undergo remarkable spin glass behaviour at low temperatures, and transform from ferromagnetism to paramagnetism at high temperature in applied fields. Temperature dependence of magnetic susceptibility curve is in qualitative agreement with experimental result.