Saturated magnetization and glass forming ability of soft magnetic Fe-based metallic glasses

Saturated magnetization (B_s) and glass forming ability (GFA) are two important attributes of soft magnetic metallic glasses (MGs), both of which are affected by the local short-range order in amorphous structures. Based on the notion of free electron transfer, we propose a set of simple rules for the calculation of B_s from the chemical composition of soft magnetic Fe-based alloys. Through the comparison of the experimentally measured B_s and theoretically calculated B_s, we show that the soft magnetic Fe-based MGs can be generally categorized into two types: one has its GFA correlated positively with the ferromagnetic weakness and the other has its GFA correlated negatively with the ferromagnetic weakness. Finally, the structural mechanisms behind these correlations are discussed.     

微量元素对Cu-Zr-Al块体金属玻璃形成能力及力学性能的影响

研究微量元素Ag、Ti、Ga、Ni和Sn对Cu55Zr38Al7铜基块体金属玻璃形成能力及力学性能的影响。结果表明:添加2%(摩尔分数)的Ag、Ti或Ga均可以提高Cu55Zr38Al7合金的玻璃形成能力;用6%的Ag替代Cu,玻璃棒的临界直径可从2 mm增加到4 mm;因此,替代化学性质相似的元素或者扩大合金系的原子尺寸范围对提高玻璃形成能力具有显著的效果;然而,添加微量元素均不同程度地降低Cu-Zr-Al金属玻璃的硬度。断口表面形貌显示;微量相似元素替代影响基体在压缩过程中剪切带的繁殖;在微量元素替代的伪四元铜基块体金属玻璃中,2%Ti和2%Ag替代可分别获得最大压缩强度2 163 MPa和最大压缩应变8.7%。因此,通过添加微量元素可以调谐金属玻璃的玻璃形成能力和力学性能。     

Effect of silver on the glass forming ability of MgCuGdY bulk metallic glasses

Bulk metallic glasses have been synthesized in the Mg_xCu_yAg_zGd₁₀ and Mg_xCu_yAg_zGd₉Y₂ systems by HF melting and injection in conical and cylindrical shape copper moulds in order to determine their critical diameter and to prepare samples for mechanical tests. Silver can be substituted either to the copper or to the magnesium leading to different alloys whose properties have been measured by differential scanning calorimetry (DSC) curves and X-ray analyses. Up to a high diameter (10 mm), they present the structure of bulk metallic glasses. The effect of silver is in general to reduce the glass transition region (ΔT = T_x − T_g) but with an increase of the critical diameter which is not in agreement with glass forming ability (GFA) criteria when choosing ΔT as so, however the γ = T_x/(T_g + T_l) parameter is in agreement with the GFA as the γ parameter is increasing when the critical diameter is increasing. The effect of silver in the gadolinium–yttrium-based alloys is to decrease the ΔT range from 69 K without silver to 40 K with 9 at.% of Ag. Mechanical measurements made by compression tests at room temperature show that these alloys stay brittle with an elastic limit above 800 MPa but with no improvement of plasticity due to silver.     

Structure and transformation behaviour of rapidly solidified Ni–Al–Hf alloys

Rapidly solidified Ni–Al–Hf alloys of ternary eutectic compositions were studied by X-ray diffractometry, transmission electron microscopy and differential scanning calorimetry. Ni₆₆Hf₂₀Al₁₄ amorphous alloy with relatively high Hf/Al ratio showed high tensile strength of 1600 MPa and high thermal stability against crystallization. The formation of a nanoscale metastable intermetallic compound having a body-centered cubic lattice with a lattice parameter of a=1.22 nm was observed in the alloys with higher Al than Hf content. The transformation of an amorphous+metastable cubic mixture to AlNi₃ produces AlNi₃ of the same composition as the AlNi₃ phase formed on rapid solidification. Pm m AlNi₃ phase can dissolve up to 11 at.% Hf.     

Thermodynamic and topological instability approaches for forecasting glass-forming ability in the ternary Al–Ni–Y system

A thermodynamic approach to predict bulk glass-forming compositions in binary metallic systems was recently proposed. In this approach, the parameter γ* = ΔH^amor/(ΔH^inter − ΔH^amor) indicates the glass-forming ability (GFA) from the standpoint of the driving force to form different competing phases, and ΔH^amor and ΔH^inter are the enthalpies for glass and intermetallic formation, respectively. Good glass-forming compositions should have a large negative enthalpy for glass formation and a very small difference for intermetallic formation, thus making the glassy phase easily reachable even under low cooling rates. The γ* parameter showed a good correlation with GFA experimental data in the Ni–Nb binary system. In this work, a simple extension of the γ* parameter is applied in the ternary Al–Ni–Y system. The calculated γ* isocontours in the ternary diagram are compared with experimental results of glass formation in that system. Despite some misfitting, the best glass formers are found quite close to the highest γ* values, leading to the conclusion that this thermodynamic approach can be extended to ternary systems, serving as a useful tool for the development of new glass-forming compositions. Finally the thermodynamic approach is compared with the topological instability criteria used to predict the thermal behavior of glassy Al alloys.     

Effect of copper addition on the glass forming ability of a Fe–Co based alloy

The effect of copper addition on the glass forming ability of Fe₃₆Co₃₆Nb₄Si_4.8B_19.2 bulk metallic glass is studied. With 0.6 at% of copper addition, the critical size of the glassy rod formed is enlarged from 2 to 4 mm. Differential scanning calorimetry (DSC) study shows that the copper addition depressed the phase separation before the eutectic transformation upon cooling. And the crystallization of the alloy with copper addition is carried through three stages upon heating. Energy dispersive spectroscopy study shows that the copper addition reduces the oxygen content of the alloy.     

Effect of Ce addition on the microstructure and damping properties of Cu–Al–Mn shape memory alloys

The effect of rare earth element Ce addition on the microstructure, martensitic transformation, mechanical properties and damping behavior of the Cu–Al–Mn shape memory alloys (SMAs) had been investigated. It is shown that the Ce addition makes the grain refinement and affects the martensitic transformation temperature. The tensile strength and the ductility of the Cu–Al–Mn alloys can be enhanced by the Ce addition. Damping capacity tan δ of the martensite for the Cu–Al–Mn–Ce alloys is strain amplitude dependent. The Ce addition has obvious effects on the damping properties of the martensite. With the increase of the Ce content, the damping capacity increases initially and then decreases.     

Evaluation of glass forming ability of alloys

Key step of exploiting a new type BMG (Bulk Metallic Glass) is quickly judging GFA (Glass Forming Ability) of the alloys. The mole melting heats of BMGs are calculated using the weighted averages principle. The reliability and limitation of Trg criterion for CFA are discussed. The reason why Trg of BMGs is larger than 0.5 is discussed. Two new criteria for GFA, △Hmg and △Gg, are proposed. GFA sequence of BMGs is calculated using the △Hmg criterion, the result agrees with that of A. Inoue and the Rc criterion. Furthermore, as an example, the Rc of the alloys developed by Chuang DONG et al is calculated using the △Hmg and △Gg. The ascending sequence of these alloys calculated with the △Hmg criterion agrees with that of Chuang DONG et al. On the contrary, the result by the △Gg criterion is in contrary with Chuang DONG et al, indicating that the △Hmg criterion is better and more convenient than the △Gg criterion. Calculation showed that the optimum △Hmg iS -15.16 k J/mol.     

Synthesis and characterization of amorphous Zr-based alloys with Ta and W additions

A reference Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ bulk metallic glass as well as a number of alloys obtained by addition of refractory elements Ta or W (combined with Sn) to the main Zr–Cu–Al–Ni system were elaborated by mould casting, twin roll casting and planar flow casting. The chemical compositions were chosen according to empirical rules, and as combinations of the binary eutectics for strongly interacting elements, taking into account the corresponding enthalpies of mixing. Optical microscopy, X-ray diffractometry, differential thermal analysis, differential scanning calorimetry, scanning electron microscopy and tensile mechanical testing were used to characterize the fully and partially obtained amorphous materials. Correlation of glass forming ability, thermodynamic parameters, crystallization behaviour and mechanical properties with chemical composition and production technology is discussed.     

反复熔炼对Zr基大块非晶合金玻璃形成能力的影响

研究了反复熔炼对Zr60Al15Ni25和Zr65Al7.5Ni10Cu17.5合金的玻璃形成能力的影响。DSC分析表明，随着熔炼次数的增多，Zr60Al15Ni25非晶合金的玻璃转变温度和晶化开始温度都提高，而Zr60Al7.5Ni10Cu17.5非晶合金的特征温度基本没有发生变化。Zr60Al15Ni25合金的熔化焓由于反复熔炼而降低，在热力学上有利于非晶相的形成。根据反复熔炼对铸锭凝固组织进而对合金熔体中的短程序的影响，讨论了玻璃形成能力的变化及原子间的结合力对短程序尺寸的影响，分析了2种合金对反复熔炼处理的敏感性的不同。     

Effects of minor Cu and Si additions on glass forming ability and mechanical properties of Co-Fe-Ta-B Bulk metallic glass

Effect of Cu and Si substitutions for Co and B on the glass forming ability (GFA) of Co_(43-x)Cu_xFe₂₀Ta_5.5B_(31.5-x)Si_y (x=0-1.5 and y=5-10) were systematically investigated by X-ray diffraction, optical microscopy, scanning electron microscopy, and differential scanning calorimetry. In order to evaluate the contribution of copper and silicon, appropriate amounts of copper and silicon were individually introduced to the base alloy composition. By using the effects of copper and silicon together, significant enhancement was obtained and the critical casting thickness (CCT) of the base alloy was increased three times from 2 mm to 6 mm. Moreover, mechanical properties of the alloys were examined by compression tests and Vickers hardness measurements. The compression test results revealed that the glassy alloys having enhanced GFA shows high strength of about 3500-4000 MPa. In addition, existence of (Co,Fe)₂B and (Co,Fe)_20.82Ta_2.18B₆ crystalline phases in glassy matrix influences the hardnesses of the alloys compared to monolitic glassy structure having hardness of about 1200 Hv.     

Chemical and thermodynamic properties of several Al–Ni–R systems

The standard enthalpies of formation at 300 K of the RNiAl phases (R=rare earth) have been obtained by using a high temperature direct reaction drop calorimeter and an aneroid isoperibol calorimeter. State and composition of the samples were checked by X-ray diffraction analysis. Metallographic examination was performed and the phases were further identified by electron microscopy and electron probe microanalysis. The results obtained are discussed and compared with those available for the binary RNi₂ and RAl₂ compounds.     

Nd对块体Mg-Cu-Y-Nd非晶合金玻璃形成能力的影响

在非真空熔炼条件下采用工业纯原材料和负压铜模吸铸法制备Mg65Cu25Y10-xNdx(x=0,2,4,6,8,10)棒状试样,利用差示扫描量热(DSC)和X射线衍射(XRD)等方法分析Nd对Mg-Cu-Y-Nd非晶合金玻璃形成能力的影响。结果表明:Nd的含量(x)为0,4,6成分的合金试样具有完全非晶态组织,且x=4时具有最大的玻璃形成能力,其约化玻璃转变温度(Trg)为0.592,过冷液相区宽度(ΔTx)高达66 K;当x为2,8,10时,由于合金成分明显偏离共晶成分,玻璃形成能力降低,试样只含有少量非晶,且主要呈晶体组织特征。     

HRTEM study of crystallization of Zr–Cu–Ni metallic glass

Employing differential scanning calorimetry (DSC) and high-resolution transmission electron microscopy (HRTEM), the micromechanism for crystallization of Zr₇₀Cu₂₀Ni₁₀ metallic glass under isothermal annealing conditions has been investigated. It is found that the relationship between the annealing temperature and the peak position, incubation time and ending time in the isothermal annealing DSC traces of Zr₇₀Cu₂₀Ni₁₀ metallic glass obeys a first-order exponential function. However, the time–temperature transformation curves of Zr₇₀Cu₂₀Ni₁₀ metallic glass at different crystallized volume fractions can be well fitted by a second-order exponential function. It is observed that at the initial crystallization stage some ordered atomic clusters precipitate first, acting as nucleation sites and facilitating the subsequent crystallization process, and the crystal growth process mainly proceeds through the atomic depositing on the previously formed crystals. This behavior confirms that the new micromechanism for crystallization of amorphous alloys proposed by Lu and Wang can also be applied to the new series of zirconium based amorphous alloys.     

A new Cu–Hf–Al ternary bulk metallic glass with high glass forming ability and ductility

We have discovered a new Cu-based bulk metallic glass (BMG). Although of a simple Cu₄₉Hf₄₂Al₉ ternary composition, the as-cast alloy is a monolithic, uniform BMG with a critical diameter as large as 10 mm. The width of the supercooled liquid region ΔT_x and the reduced glass transition temperature T_rg for this glass are 85 K and 0.62, respectively. In addition to its high glass-forming ability and high density of 11 g/cc, this BMG exhibits high ductility with a compressive plastic strain of 11–13%, making it a good candidate for applications as well as for studies of deformation behavior of Cu-based BMGs.     

Effect of ageing on transformation kinetics and internal friction of Ni-rich Ni–Ti alloys

In Ni-rich Ni–Ti alloys the ageing treatments create finely dispersed Ti₃Ni₄ precipitates in the B2-based matrix. Formed precipitates are known to influence the phase transformation temperatures and to facilitate the R-phase transformation. In addition to the change in the phase transformation behaviour, the ageing treatments are also reported to affect internal friction and mechanical properties of Ni–Ti alloys.In the present work, by means of systematic DSC and DMA studies the effects of the ageing treatments on the phase transformation as well as on the internal friction and mechanical properties of Ni-rich Ni–Ti alloy were studied. As an extension to earlier studies, the present study concentrates both on the effects of the ageing time and the ageing temperature systematically. By combining the results of the DSC measurements of phase transformation behaviour to the DMA measurements of internal friction and mechanical behaviour of the Ni-rich Ni–Ti alloy, the present study gives yet unpublished information about the comprehensive effects of the ageing treatments on these alloys. These results enable to control the phase transformation temperatures, internal friction and mechanical properties of the Ni-rich Ni–Ti alloy by selecting the suitable ageing treatment.Results showed that the noticed effects of the ageing treatments on mechanical properties could be explained with the changes in the size, distribution, density and coherency of the formed Ti₃Ni₄ precipitates. The high internal friction values can be explained as the contribution of the internal stress fields and increased amount of mobile interfaces as the result of the formed Ti₃Ni₄ precipitates. The amount of mobile interfaces seems to be more dominant factor for the increased internal friction value than the effect of the internal stress fields. Therefore, the optimal internal friction values can be obtained with a proper aging treatment which will yield a high density of small Ti₃Ni₄ precipitates.     

Hydrogen solution properties in a series of amorphous Zr–Hf–Ni alloys at elevated temperatures

Amorphous alloys are anticipated as new membrane materials for high purity hydrogen production, as substitutes for expensive palladium alloys. For amorphous Zr–Ni-based alloys reported to date, hydrogen permeability increases with Zr content. Hydrogen solution properties in a series of amorphous Zr–Hf–Ni ternary alloys were measured carefully using the Sieverts method and residual hydrogen measurements to investigate the reason. Results indicate that hydrogen solubility in the ternary alloys increases with increasing Zr to improve hydrogen permeability, not because of the geometrical atomic structure but because of higher hydrogen affinity of Zr than that of Hf. Increased permeability with Zr in other amorphous Zr–Ni-based alloys is also expected to be attributable to the same reason. Additionally, hydrogen was found with low mobility, and was not removable even after 10 h evacuation at 573 K; the importance of decreasing low mobility hydrogen as a countermeasure against hydrogen embrittlement was pointed out. Equilibrium hydrogen concentration was found not to obey Sieverts’ law with respect to hydrogen pressure. Rather, it was linear roughly to the quarter power. Parameters to reproduce pressure–composition isotherms were determined using Kirchheim's theory.     

The effect of Hf substitution for Zr on glass forming ability and magnetic property of FeCoZrMoBAlY bulk metallic glasses

Bulk metallic glasses (BMGs) Fe₆₁Co₆Zr_8−xHf_xMo₇B₁₅Al₁Y₂ (x = 0–8) have been produced by copper mold casting technique using industrial raw materials. The effect of substitution of Hf for Zr on the glass forming ability (GFA) and the magnetic property has been studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and superconducting quantum interference device (SQUID). It was found that the substitution of an appropriate amount of Hf for Zr can improve the GFA of the base alloy Fe₆₁Co₆Zr₈Mo₇B₁₅Al₁Y₂, as demonstrated by the increase in reduced glass transition temperature T_rg (=T_g/T_l) and GFA parameters of γ (=T_x/T_g + T_l) and δ (=T_x/T_l − T_g). The Fe₆₁Co₆Zr₅Hf₃Mo₇B₁₅Al₁Y₂ alloy exhibits the highest GFA with the largest T_rg (0.612) and δ (1.633), and can cast a fully amorphous rod in 3 mm diameter. The substitution of Hf for Zr also enhances the magnetic properties, as verified by the increase in saturation magnetization (M_s) in the alloy of Fe₆₁Co₆Zr₃Hf₅Mo₇B₁₅Al₁Y₂, whose M_s is approximately 1.5 times higher than that of the base alloy (x = 0) at room temperature. Finally, the effect of the substitution of Hf for Zr on glass forming ability and magnetic properties is discussed.     

Thermodynamic model for glass forming ability of ternary metallic glass systems

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Influence of Pd on crystallization of Al–Ni–Sm-based ribbons

The five-stage devitrification of rapidly quenched Al₈₉Ni₆Sm₅ and Al₈₆Ni₆Sm₅Pd₃ ribbons has been studied by differential scanning calorimetry and electrical resistivity measurements. The formed phases have been identified by X-ray diffraction, transition electron microscopy and high-temperature differential thermal analysis. In the first stage spherical fcc-Al nano-particles develop with a very high density. After the sequential formation and modification of the grown phases the equilibrium fcc-Al, Al₃Ni, Al₃Sm, Al₄Sm and Al₁₁Sm₃, eventually, equivalent with the equilibrium phases in related master-alloys have been developed. The stabilizing effect of Pd on both thermodynamics and kinetics of individual transformations has been analyzed.