Influence of the molten quenching temperature on the thermal physical behavior of quenched Zr-based metallic glasses

Thermo-physical behavior of some Zr-based metallic glasses prepared by different molten quenching temperatures was studied by Differential scanning calorimetry (DSC) measurements. The characteristic thermo-physical properties are normally used for evaluating the glass-forming ability (GFA) of metallic glasses. Our results show that the glass transition temperature, crystallization temperature and supercooled liquid region of these metallic glasses increased with increasing the molten quenching temperature. Their glass-forming abilities were discussed in terms of the GFA criterion γ and the reduced glass transition temperature, T_rg, using these thermo-physical properties.     

Thermal behaviour of Pd40Cu30Ni10P20 bulk metallic glass

The thermal behaviour of differently milled Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glass through the glass transition has been investigated by in situ high-energy synchrotron X-ray diffraction. Repeated heating and cooling were performed between the glassy and the supercooled liquid state. The changes in positions and intensities of the first and second diffraction maxima of the as-milled powder indicate irreversible changes during first heating up to the glass transition temperature T_g due to structural relaxation. After annealing, reversible structural changes with temperature are observed upon heating and cooling in the glassy phase, and in the supercooled liquid state respectively. The shift in the position of the first maximum scales approximately with the linear thermal expansion for the glassy state; however, this relation does not hold for the supercooled liquid. The structural transition from the glass to the supercooled liquid at the glass transition temperature is reflected by the intensity of the diffraction maxima and by a reversed temperature dependence of the position of the second diffuse maximum below and above T_g. The changes of the glass structure for the decrease of free volume by annealing are found to be different from those observed for the reversible volume expansion or shrinkage by varying the temperature. Therefore, the shift of the first diffuse maximum position of bulk metallic glasses cannot be used as a measure of the change in free volume.     

Compositional dependence of thermal stability, glass-forming ability and fragility index in some Se-Te-Sn glasses

Non-isothermal DSC thermograms were obtained for the ternary Se₉₀Te_10−xSn_x (x = 2, 4, 6 and 8) chalcogenide glasses in order to determine the melting temperature T_m, glass transition temperature T_g, onset T_c and peak T_p temperatures of crystallization. These temperatures were utilized to investigate the thermal stability through the calculations of temperature difference (T_c − T_g), the glass transition activation energy E_t, the parameter S and the average value of crystallization rate factor 〈K_p〉. In addition, the glass forming ability was estimated by the criteria of reduced glass transition temperature, T_rg and Hruby parameter H_R. The fragility index m for the present glasses was determined in order to see whether these materials are obtained from strong or fragile glass-forming liquid. Results reveal that, both thermal stability and glass forming ability exhibit a maximum at x = 4 at.% of Sn. Meanwhile, the prepared glasses were obtained from strong glass-forming liquid as evident from the fragility index calculations. The compositional dependence of the above parameters was discussed on the basis of Philips and Thorpe topological model and the critical composition occurs at an average coordination number 〈r〉 = 2.16 but not 2.40. This is due to the formation of iono-covallent bonds when the glass doped with heavy elements like Sn.     

A new glass-forming ability criterion for bulk metallic glasses

A new indicator of glass-forming ability (GFA) for bulk metallic glasses (BMGs) is proposed based on crystallization processes during cooling and reheating of the supercooled liquid. The interrelationship between this new parameter and the critical cooling rate or critical section thickness is elaborated and discussed in comparison with two other representatives, i.e. reduced glass transition temperature T_rg (=T_g/T_l, where T_g and T_l are the glass transition temperature and liquidus temperature, respectively) and supercooled liquid range ΔT_xg (=T_x−T_g, where T_x is the onset crystallization temperature and T_g the glass transition temperature). Our results have shown that ΔT_xg alone cannot infer relative GFA for BMGs while the new parameter γ, defined as T_x/(T_g+T_l), has a much better interrelationship with GFA than T_rg. An approximation of the critical cooling rate and critical section thickness for glass formation in bulk metallic glasses is also formulated and evaluated.     

一种具有优异玻璃形成能力的Zr50Ti5Cu27Ni10Al8大块非晶合金的开发

多组元的Zr基非晶合金成分的复杂性对开发具有优异玻璃形成能力的Zr基非晶合金提出巨大的挑战。另外,大部分Zr基非晶合金含有有毒元素Be或者贵金属。因此,采用一种简单有效的方法开发无毒无贵金属元素的多组元Zr基非晶合金十分必要。本文中采用二元共晶比例法和部分元素替代法快速的开发出了一种新的临界尺寸大于10mm的 Zr50Ti5Cu27Ni10Al8非晶合金。这个非晶合金的热稳定性和硬度也通过原位高温X射线衍射和纳米压痕方法测量得出。     

Glass formation,thermal and mechanical properties of ZrCuAlNi bulk metallic glasses

The glass forming ability, thermal and mechanical properties of some ZrCuAlNi bulk metallic glasses were analyzed. The compositions of the alloys were theoretically determined with the dense packing and kinetic fragility index models. Cylindrical and conical ingots were produced by copper mould suction-casting under Ar atmosphere. The conical ingots were characterized by means of X-ray diffraction in order to determine the glassy structure. It was found that both alloys have a critical glassy diameter, D_c, of 3 mm. Thermal behaviours were investigated by differential scanning calorimetry at heating rates of 0.5, 0.67 and 0.83 K/s. The gamma parameter γ, supercooled liquid region ΔT_x, and reduced glass transition temperature T_rg, of the experimentally obtained glasses indicated high glass forming ability. The glassy compositions showed a fragility index of ～40 GPa. The compression test of the investigated alloys was carried out at a strain rate of 0.016 s^?1, obtaining a elastic modulus of ～83 GPa, total deformation of ～5%, yield strength of 1.6 GPa and hardness of 4 GPa. It was concluded that the use of the dense packing and kinetic fragility index models helped to predict glass-forming compositions in the family alloy investigated.     

Synthesis of Fe–Cr–Mo–C–B–P bulk metallic glasses with high corrosion resistance

Bulk metallic glasses with a maximum thickness (t_max) of 1.0–2.7 mm were synthesized in the Fe₄₃Cr₁₆Mo₁₆(C, B, P)₂₅ system over a wide composition range by copper mold casting. They exhibit a large supercooled liquid region (ΔT_x) of 40–90 K and a high reduced glass transition temperature (T_g/T_l) of 0.54–0.60, indicating high glass-forming ability (GFA) and high thermal stability of the supercooled liquid. The critical cooling rate for glass formation was evaluated to be of the order of 10² K s⁻¹. The bulk metallic glasses exhibited high corrosion resistance in aggressive HCl solutions. The alloying element P has a beneficial effect on corrosion resistance.     

Boss formability of a Zr-based bulk metallic glass

Macroscopic solid-to-solid hot formability of a Zr-based bulk metallic glass has been investigated in this study by applying a boss forming process within supercooled liquid region (SLR). The morphology and microstructures after boss forming were first examined by using an optical microscopy (OM), a field emission scanning electron microscope (FE-SEM), X-ray diffraction (XRD), and transmission electron microscope (TEM). The variation of thermal properties before and after boss forming was also analyzed by using a differential scanning calorimeter (DSC). The glass transition temperature, T_g and the crystallization onset temperature, T_{x, onset} were found to decrease with increasing test time and temperature. Macroscopic extrusion formability was found to match well with the results predicted through a processing map based on a dynamic materials model (DMM). The specimens were found to form well under the conditions of high temperature and slow punch jig speed. A FEM simulation study has also been carried out to understand the causes of piping problem. A sound boss without a pipe could be formed by reducing the flow rate difference in the contact and the core sites.     

Impact Conditions for Cold Spraying of Hard Metallic Glasses

As compared to thermal spray techniques, cold spraying allows to retain metastable phases of the feedstock material like amorphous structures, due to lower process gas temperatures. Compared to crystalline metals, metallic glasses are brittle at ambient temperature but viscous at higher temperatures. Therefore, cold spray parameters must be optimized for conditions that allow softening of the amorphous spray material for successfully producing coatings. For this study, a FeCoCrMoBC metallic glass was used that in comparison to others offers advantages with respect to higher hardness, less costly feedstock powder, and minimum reactivity with the environment. Necessary impact conditions were investigated to meet the window of deposition in cold gas spraying. According to calculations and cold spray experiments, neither the glass transition temperature T _g nor the melting temperature T _m can describe required conditions for bonding. Thus, a so called softening temperature between the glass temperature and the melting temperature had to be defined to calculate the critical velocity of metallic glasses. With respect to the bonding mechanism, impact morphologies could prove that a transition to viscous flow gets more prominent for harsher spray conditions. By sufficiently exceeding the critical condition for bonding, coatings with rather dense microstructures can be processed at deposition efficiencies of about 70%. The coatings have a hardness of 1100?HV 0.3, but the results also demonstrate that further work is still needed to explore the full potential for bulk metallic glasses.     

Effect of Te additions on the glass transition and crystallization kinetics of (Sb15As30Se55)100−xTex amorphous solids

Differential scanning calorimetry results under non-isothermal conditions of chalcogenide (Sb₁₅As₃₀Se₅₅)_100?xTe_x (where 0 ≤ x ≤ 10 at.%) glasses are reported and discussed. The dependence of the characteristic temperatures “glass transition temperature (T_g), the crystallization onset temperature (T_c) and the crystallization temperature (T_p)” on the heating rate (β) utilized in the determination of the activation energy for the glass transition (E_g), the activation energy for crystallization (E_c), the glass thermal stability (ΔT = T_c ? T_g) and the Avrami exponent (n). The composition dependence of the T_g, E_g, and E_c were discussed in terms of the chemical bond approach, the average heats of atomization and the cohesive energy (CE). The diffractogram of the transformed material shows the presence of some crystallites of AsSb, Sb₄Te₆, As₂Se₃ and Sb₂Se₃ in the residual amorphous matrix.     

Thermal, mechanical, and upconversion properties of Er/Yb co-doped titanate glass prepared by levitation method

A novel Er³⁺/Yb³⁺ co-doped titanate glass sphere with diameter of 3.5 mm has been successfully fabricated by levitation method. Its thermal stability, mechanical property and upconversion behavior were investigated. The glass transition temperature T_g, onset crystallization temperature T_c, and peak crystallization temperature T_p, are as high as 820, 895 and 902 °C, respectively. Its Vickers hardness is found to be up to 7.85 GPa. Intense green and red upconversion emissions were obtained in this glassy sample upon 980 nm excitation. The results illustrate good potential of this class of material for practical application in frequency upconversion device. In addition, it is found that heating treatment above T_p can reduce the efficiency of upconversion fluorescence as well as deteriorate the mechanical property, due to the occurrence of La₄Ti₉O₂₄ crystals.     

Atomic scale calculation of the free volume in Zr2Ni metallic glass

How to evaluate the free volume in metallic glasses is a long-standing question in the field of metallic glasses. In this paper, a new approach at the atomic level to calculate free volume has been developed and applied in the Zr₂Ni metallic glass. The glass transition and volume change during the cooling of Zr₂Ni metallic liquid were investigated by molecular dynamics (MD). The MD resultant glass transition temperature (T_g) is about 700 K, which is close to the experimental value of 662.8 K obtained from differential scanning calorimetry (DSC). According to our method, the free volume in Zr₂Ni metallic glass was determined to be ～4.1% at T_g, which is comparable with the experimental results reported in other metallic glasses. Moreover, the probability distribution of free volume in our case can be fitted well by that given by Turnbull and Cohen, confirming the rationality of our method.     

Diffusion and viscous flow in bulk glass forming alloys

We review radiotracer diffusion and isotope measurements in bulk glass forming alloys from the glassy state to the equilibrium melt and compare diffusion and viscous flow. In the glassy as well as in the deeply supercooled state below the critical temperature T_c, where the mode coupling theory predicts a freezing-in of liquid-like motion, very small isotope effects indicate a highly collective hopping mechanism. Not only in the glassy state but also in the supercooled state below T_c the temperature dependence of diffusion is Arrhenius-like with an effective activation enthalpy. A clear decoupling takes place between the diffusivities of the individual components of the alloys and between time scales related to diffusive transport and viscous flow. While the component decoupling is small for the smaller components a vast decoupling of more than 4 orders of magnitude is observed in Pd–Cu–Ni–P alloys between the diffusivity of the large majority component Pd and of the smaller components at the glass transition temperature T_g. The diffusivities of all components merge close to the critical temperature T_c of mode coupling theory. Above T_c, the onset of liquid-like motion is directly evidenced by a gradual drop of the effective activation energy. This strongly supports the mode coupling scenario. The isotope effect measurements show atomic transport up to the equilibrium melt to be far away from the regime of uncorrelated binary collisions. For Pd, in contrast to the behavior of single component molecular glass formers, the Stokes–Einstein equation even holds in the entire temperature range below T_c over at least 14 orders of magnitude. Apparently, the majority component Pd forms a slow subsystem in which the other elements move fast. Rearrangement of the Pd atoms thus determines the viscous flow behavior. The decoupling of atomic mobility seems to arise from a complex interplay between chemical short order and atomic size effects that gets more pronounced on approaching the glass transition temperature. The ability of the bulk glass forming alloys to form a slow subsystem in the liquid state appears to be a key to the understanding of their excellent glass forming properties.     

Temperature–stress phase diagram of strain glass Ti48.5Ni51.5

The temperature and stress dependence of the properties of a recently discovered strain glass Ti_48.5Ni_51.5, which is a glass of frozen local lattice strains, was investigated systematically. It was found that the ideal freezing temperature (T₀) of the strain glass decreases with increasing stress. When the stress exceeds a critical value σ_c(T), the pseudo-B2 strain glass transforms into B19′ martensite. However, the stress–strain behavior associated with such a stress-induced transition showed a crossover at a crossover temperature T_CR, which is ∼20 K below T₀. Above T_CR, the sample showed superelastic behavior; however, below T_CR, the sample demonstrated plastic behavior. More interestingly, the σ_c vs. temperature relation for unfrozen strain glass obeys the Clausius–Clapyeron relationship, whereas that for frozen strain glass disobeys this universal thermodynamic law. A phenomenological explanation is provided for all the phenomena observed, and it is shown that all the anomalous effects come from the broken ergodicity of the glass system and a temperature-dependent relative stability of the martensitic phase. Based on experimental observations, a temperature–stress phase diagram is constructed for this strain glass, which may serve as a guide map for understanding and predicting the properties of strain glass.     

Embrittlement of Zr-based bulk metallic glasses

Embrittlement of Zr_46.75Ti_8.25Cu_7.5Ni₁₀Be_27.5 and Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glasses (BMGs) is studied after annealing at temperatures below and above the glass transition temperature T_g for time scales comparable with structural relaxation and crystallization. The effect of annealing on the bending ductility, the isoconfigurational elastic constants, the structure and the thermal stability is examined. The embrittlement during sub-T_g annealing originates from structural relaxation and can be reversed by subsequently annealing for a short duration above T_g. The embrittlement kinetics correlate with the structural relaxation. However, only a fraction of relaxation time at a given temperature (<T_g) is sufficient to embrittle the BMG significantly. Above T_g, plasticity is retained for annealing far beyond the relaxation time but, instead, embrittlement is caused by crystallization. The magnitude of the decrease in Poisson’s ratio is insufficient to explain the severe embrittlement within the framework of a critical value as previously suggested.     

Devitrification and phase transformation of (Ti0.5Cu0.25Ni0.15Sn0.05Zr0.05)100 − xMox metallic glasses

The thermal stability and the crystallization behavior of the melt-spun ribbons of (Ti_0.5Cu_0.25Ni_0.15Sn_0.05Zr_0.05)_100 − xMo_x metallic glasses were investigated in terms of the thermal analysis. The crystallization during the glass devitrification and the solidification of the liquid for the alloys exhibit a strong similarity.     

Devitrification behavior and some electrical properties of GeSeTl chalcogenide glass

The activation energy of crystallization E_c of GeSe₃Tl_0.3 and GeSe₄Tl_0.3 chalcogenide glasses was calculated from the shift of the DTA exothermic peaks with changing the heating rate. Values of E_c were calculated by different methods and it was found that it decreases with increasing Se content.Amorphous thin films of the present glasses were prepared using thermal evaporation technique. Electrical conductivity and I-V characteristics have been studied at temperatures below the glass transition temperature T_g and over a wide range of thickness (57.4-680 nm). The dc conductivity was linear in the Arrhenius Plot in the considered temperature range and increases with the increase of Se content. The activation energy for the dc conduction ΔE_σ is decreased with increasing Se content and film thickness. The observed compositional dependence of ΔE_σ has been correlated with the increase of weak Se-Se bond density at the expense of strong Ge-Se bond density. I-V characteristic curves indicates the memory type switching phenomenon for these compositions and it is explained in accordance with the electrothermal model initiated from Joule heating of a current channel.     

FRICTION WELDING OF Zr55Al10Ni5Cu30 BULK METALLIC GLASS

采用摩擦焊对Zr₅₅Al₁₀Ni₅Cu₃₀块体金属玻璃进行了焊接, 当焊机主轴转速为4.0×10³---5.0×10³ r/min, 摩擦压力为80---100 MPa, 摩擦时间为0.2---0.4 s, 顶锻压力和保压时间分别为200 MPa和2 s时, 能够成功实施Zr₅₅Al₁₀Ni₅Cu₃₀金属玻璃的焊接. 用SEM, XRD和TEM观察分析未检测到晶化相, 焊缝处金属仍保持非晶状态. 金属玻璃的塑性在玻璃转变点T_g附近随温度变化很大, 在T_g以上具有良好的塑性变形能力, 这是实施摩擦焊焊接的重要基础.     

The synthesis and properties of Zr-based metallic glasses and glass-matrix composites

In this article, the formation of metallic glass composites in the system Zr/Ti-Al-Cu-Ni by partial devitrification or by blending with second-phase particles through solid-state processing is discussed with respect to the effect of second phases on the thermal stability of the glassy matrix and on mechanical properties. The composites exhibit no significant reduction of the supercooled liquid region as compared to the particle-free metallic glass. The viscosity of the supercooled liquid increases with an increasing volume fraction of particles. The mechanical behavior was characterized by microhardness measurements and constant compression rate tests. At room temperature, there is a significant increase in yield strength with an increasing volume fraction of crystalline phases. At temperatures around the glass transition, the influence of these nanoscaled particles is of minor importance. Rather, the homogeneous flow of the composites is determined by Newtonian viscous flow of the amorphous matrix. This opens a promising route for easy shaping of complex parts of bulk metallic glasses at temperatures that are above T_g. For more information, contact J.H. Ecker, IFW Dresden, Institute of Metallic Materials, P.O., Box 27 00 16, Dresden D-01171, Germany; telephone 49-351-4659-602; fax 49-351-4659-541; e-mail j.eckert@ifw-dresden.de.     

Enthalpy relaxation in Cu46Zr45Al7Y2 and Zr55Cu30Ni5Al10 bulk metallic glasses by differential scanning calorimetry (DSC)

Structural relaxation process in Cu₄₆Zr₄₅Al₇Y₂ and Zr₅₅Cu₃₀Ni₅Al₁₀ bulk metallic glasses during annealing below the glass transition temperature T_g was investigated by differential scanning calorimetry (DSC). The features of enthalpy relaxation are sensitive to both annealing temperature and annealing time. For a given annealing time t_a, the results indicated that the relaxation time t_a decreases with increasing the annealing temperature T_a, in good agreement with results relative to other bulk metallic glasses. Additionally, the enthalpy relaxation behaviour of the bulk metallic glasses appears independent on the cooling rate used before the physical aging experiments, i.e. on the initial as-cast state. The recovered enthalpy evolution of the bulk metallic glasses is well described by the Kohlrausch–Williams–Watts (KWW) exponential relaxation function as ΔH(T_a) = ΔH_eq{1 ? exp[?(t_a/τ)^β]}. Kohlrausch exponent β and enthalpy relaxation time τ are sensitive to the composition of the bulk metallic glasses. Finally, the influence of different heating treatment processes on the enthalpy relaxation in the bulk metallic glasses is presented and shows that this phenomenon is mainly reversible. The structural relaxation behaviour is interpreted by free volume model and quasi-point defects model. Kinetic fragility parameters m in Cu₄₆Zr₄₅Al₇Y₂ and Zr₅₅Cu₃₀Ni₅Al₁₀ bulk metallic glasses are 72 and 69, respectively, indicating therefore that these alloys are intermediate glasses.Crystallization process was also investigated by DSC experiments. According to the Kissinger model, corresponding activation energy is 3.18 eV in Cu₄₆Zr₄₅Al₇Y₂, and 3.19 eV in Zr₅₅Cu₃₀Ni₅Al₁₀, respectively.