Universal basis underlying temperature, pressure and size induced dynamical evolution in metallic glass-forming liquids

The dramatic temperature-dependence of liquids dynamics has attracted considerable scientific interests and efforts in the past decades, but the physics of which remains elusive. In addition to temperature, some other parameters, such as pressure, loading and size, can also tune the liquid dynamics and induce glass transition, which makes the situation more complicated. Here, we performed molecular dynamics simulations for Ni_(50)Zr_(50) bulk liquid and nanodroplet to study the dynamics evolution in the complex multivariate phase space, especially along the isotherm with the change of pressure or droplet size. It is found that the short-time Debye–Waller factor universally determines the long-time relaxation dynamics no matter how the temperature, pressure or size changes. The basic correlation even holds at the local atomic scale. This finding provides general understanding of the microscopic mechanism of dynamic arrest and dynamic heterogeneity.

Effects of rare-earth elements on the glass-forming ability and mechanical properties of Cu_(46)Zr_(47-x)Al_7M_x(M = Ce,Pr,Tb,and Gd) bulk metallic glasses

Cu46Zr47-xA17Mx （M = Ce, Pr, Tb, and Gd） bulk metallic glassy （BMG） alloys were prepared by copper-mold vacuum suction casting. The effects of rare-earth elements on the glass-forming ability （GFA）, thermal stability, and mechanical properties of Cu46Zr47-xA17Mx were investigated. The GFA of Cu46Zr47-xA17Mx （M = Ce, Pr） alloys is dependent on the content of Ce and Pr, and the optimal content is 4 at.%. Cu46Zr47-xA17Thx（X = 2, 4, and 5） amorphous alloys with a diameter of 5 mm can be prepared. The GFA of Cu46Zr47-xA17Gdx（x = 2, 4, and 5） increases with increasing Gd. Tx and Tp of all decrease. Tg is dependent on the rare-earth element and its content. ATx for most of these alloys decreases except the Cu46Zra2Al7Gd5 alloy. The activation energies △Eg, △Ex, and △Ep for the Cu46Zr42A17Gd5 BMG alloy with Kissinger equations are 340.7, 211.3, and 211.3 kJ/mol, respectively. These values with Ozawa equations are 334.8, 210.3, and 210.3 kJ/mol, respec- tively. The Cu46Zr45Al7Tb2 alloy presents the highest microhardness, Hv 590, while the Cu46Zr43A17Pr4 alloy presents the least, Hv 479. The compressive strength （at.f.） of the Cu46Zra3A17Gd4 BMG alloy is higher than that of the Cu46Zr43Al7Tb4 BMG alloy.

Glass-forming ability, microhardness, corrosion resistance, and dealloying treatment of Mg60.xCu40Ndx alloy ribbons

The influence of Nd addition on the glass-forming ability(GFA), microhardness, and corrosion resistance of Mg_(60-x)Cu_(40)Nd_x(x = 5, 10, 15, 20, and 25, at%) alloys were investigated by differential scanning calorimetry, Vickers-type hardness tests, and electrochemical methods. The results suggest that the GFA and microhardness of the amorphous alloys increase until the Nd content reaches 20at%. The corrosion potential and corrosion current density obtained from the Tafel curves indicate that the Mg_(35)Cu_(40)Nd_(25) ternary alloy exhibits the best corrosion resistance among the investigated alloys. Notably, nanoporous copper(NPC) was synthesized through a single-step dealloying of Mg_(60-x)Cu_(40)Nd_x(x = 5, 10, 15, 20, and 25) ternary alloys in 0.04 mol·L^(-1) H_2SO_4 solution under free corrosion conditions. The influence of dealloying process parameters, such as dealloying time and temperature, on the microstructure of the ribbons was also studied using the surface diffusivity theory. The formation mechanism of dealloyed samples with a multilayered structure was also discussed.

Measurement scheme to detect α relaxation time of glass-forming liquid

A measurement scheme for detecting theαrelaxation time(τ)of glass-forming liquid is proposed,which is based on the measured ionic conductivity of the liquid doped with probing ions by low-and middle-frequency dielectric spectroscopy and according to the Nernst-Einstein,Stokes-Einstein,and Maxwell equations.The obtainedτvalues of glycerol and propylene carbonate by the scheme are consistent with those obtained by traditional dielectric spectroscopy,which confirms its reliability and accuracy.Moreover,theτof 1,2-propanediol in a larger temperature range is compared with existing data.

Formation and thermal stability of Cu-Zr-Al-Er bulk metallic glasses with high glass-forming ability

The formation and thermal stabilities of Cu46.25Zr46.25xAl7.5Erx (x=0 to 8) bulk metallic glasses (BMGs) were investigated. The addition of a small amount of Er (2at%) for replacing Zr effectively improves the glass-forming ability of Cu46.25Zr46.25Al7.5 alloy, and the glassy rod with a diameter of at least 12 mm can be formed. The glass transition temperature (Tg), temperature interval of su- percooled liquid region △Tx (=Tx-Tg), and reduced glass transition temperature Trg (=Tg/Tl) of Cu46.25Zr44.25Al7.5Er2 glassy alloy are 699 K, 62 K and 0.607, respectively.

Glass-forming Ability and Chemical Stability of Magneto-optical Glass Heavily Doped with Rare Earth Oxide

The glass-forming region of B2O3-Al2O3-SiO2 （BAS） glass heavily doped with rare earth oxides was investigated by an effective method, and the chemical stability was investigated by powder method. Influences of rare earth oxides on the glass-forming ability and the chemical stability of the BAS glass were also discussed. The experimental results show that the BAS glass-forming region expands firstly with the increase of the Tb2O3 content up to 30mol% and then shrinks. The acid-resistant capacity of the BAS glass doped with rare earth oxides is the lowest, the water-resistant capacity is secondary, and the alkali-resistant capacity is the best. Besides, the glass chemical stability can be improved by doping appropriate amount of rare earth oxides. Moreover, the stronger the ionic polarization ability of the rare earth ions is, the better the chemical stability of the BAS glass will be.

Formation and Mechanical Properties of Zr-Nb-Cu-Ni-Al-Lu Bulk Glassy Alloys with Superior Glass-Forming Ability

Glass-forming ability（GFA） and mechanical properties of（Zr_（0.58）Nb_（0.03）Cu_（0.16）Ni_（0.13）Al_（0.10））_（100-x）Lu_x（x= 0-3 at%） alloys have been investigated.The GFA of Zr_（58）Nb_3Cu_（16）Ni_（13）Al_（10） alloy is dramatically enhanced by adding Lu.The（Zr_（0.58）Nb_（0.03）Cu_（0.16）Ni_（0.13）Al_（0.10））_（98）Lu_2 alloy possesses the highest GFA in the studied Zr-Nb-Cu-Ni-Al-Lu alloys,with its critical diameter for glass formation reaching 20 mm by copper-mould casting method,while that of the Lu-free Zr_（58）Nb_3Cu_（16）Ni_（13）Al_（10） alloy is 7 mm.The critical diameters of（Zr_（0.58）Nb_（0.03）Cu_（0.16）Ni_（0.13）Al_（0.10））_（100-x）Lu_x（x =1 at%and 3 at%） alloys are 15 mm and 12 mm,respectively.The Lu addition to Zr_（58）Nb_3Cu_（16）Ni_（13）Al_（10） alloy induces the change of initial crystallization phases from face-centred-cubic Zr_2Ni and tetragonal Zr_2Ni phases for the Lu-free Zr_（58）Nb_3Cu_（16）Ni_（13）Al_（10） alloy to an icosahedral quasi-crystalline phase for the Lu-doped alloys,which may be the origin for the enhanced GFA of the Lu-doped alloys.The compressive fracture strength and plastic strain of the bulk glassy（Zr_（0.58）Nb_（0.03）Cu_（0.16）Ni_（0.13）Al_（0.10））_（98）Lu_2 alloy are1 610 MPa and 1.5%,respectively.

Correlation between the glass-forming ability and activation energy of crystallization for Zr_(75-x)Ni_(25)Al_x metallic glasses

The thermal stability and the kinetics of glass transition and crystallization for Zr75-xNi25Alx （x = 8-15） metallic glasses were investigated using differential scanning calorimetry （DSC） under continuous heating conditions. The apparent activation energy of glass transition rises monotonously with the A1 content increasing; the activation energy of crystallization increases with A1 changing from 8at% to 15at%, and then decreases with A1 further up to 24at%, which exhibits a good correlation to the thermal stability and the glass-forming ability （GFA）. The Zr60Ni25A115 metallic glass with the largest supercooled liquid region and GFA possesses the highest activation energy of crystallization. The relation between the thermal stability, GFA and activation energy of crystallization was discussed in terms of the primary precipitated phases.

Effect of Al Addition on the Glass-Forming Ability and Magnetic Properties of a Gd-Co Binary Amorphous Alloy

The glass-forming ability （CFA） and magnetic properties of the Cd50 Co50-based amorphous alloy with AI addition substitution for Co are investigated. It is found that the CFA and magneto-caloric effect of the Gd50Co45Al5 amorphous alloy are better than Cd50Co50 amorphous alloy. The maximum magnetic entropy change （-△ Sm^peak） and the magnetic refrigerant capacity- of the amorphous alloy under a field of 5 T are about 6.64 J·kg^-1 K^-1 and 764 J·kg^-1, respectively. The field dependence of magnetic entropy change meets the one predicted by the mean field theory, which is investigated for a better understanding of the magneto-caloric behaviors of the Gdso Co45Al5 amorphous alloy.

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.

Ferromagnetic Fe-based Amorphous Alloy with High Glass-forming Ability

A ferromagnetic amorphous Fe73Al4Ge2Nb1 P10C6B4 alloy with high glass-forming ability was synthesized by melt spinning. The supercooled liquid region before crystallization reaches about 65.7 K. The crystallized structure consists of a-Fe, Fe3B, FeB, Fe3P and Fe3C phases. The Febased amorphous alloy exhibits good magnetic properties With a high saturation magnetization and a low saturated magnetostriction. The crystallization leads to an obvious decrease in the soft magnetic properties.

Non-monotonic temperature evolution of nonlocal structure–dynamics correlation in CuZr glass-forming liquids

The structure–dynamics correlations in a nonlocal manner were investigated in CuZr metallic glass-forming liquids via classical molecular dynamics simulations.A spatial coarse-graining approach was employed to incorporate the nonlocal structural information of given structural order parameters in the structure–dynamics relationship.It is found that the correlation between structure order parameters and dynamics increases with increasing coarse-graining length and has a characteristic length scale.Moreover,the characteristic correlation length exhibits a non-monotonic temperature evolution as temperature approaches glass transition temperature,which is not sensitive to the considered structure order parameters.Our results unveil a striking change in the structure–dynamics correlation,which involves no fitting theoretical interpretation.These findings provide new insight into the structure–dynamics correlation in glass transition.

Vaporization and Thermodynamics of Glass-Forming Oxide Melts: Mass Spectrometric Study and Modeling

Information on the vaporization processes and thermodynamic properties of glass-forming oxide melts in the systems MgO-B2O3-SiO2, CaO-B2O3-SiO2, SrO-B2O3-SiO2, BaO-B2O3-SiO2, PbO-B2O3-SiO2, CdO-B2O3-SiO2, ZnO-B2O3-SiO2, Bi2O3-B2O3-SiO2 and Bi2O3-GeO2-SiO2 together with the earlier obtained data is discussed. These data were obtained by high-temperature mass spectrometric method. Various types of vapor species were found over oxide systems studied such as the associated, dissociated and polymerized products of vaporization. The regularities of the vaporization of the binary and multicomponent glass-forming oxide melts were illustrated and discussed from the point of view of the acid-base concept. Results on determination of thermodynamic functions in oxide systems were considered taking into account the main requirements for the confirmation of their reliability. The generalized lattice theory of associated solutions was used for the calculation of thermodynamic properties of the ternary silicate melts studied. Using this approach the different levels of deviations from the ideality in the melts under investigation were clarified. The relative numbers of bonds of various types formed in the melts considered were also calculated based on the generalized lattice theory of associated solutions.

Effects of Mo additions on the glass-forming ability and magnetic properties of bulk amorphous Fe-C-Si-B-P-Mo alloys

Glass formation, mechanical and magnetic properties of the Fe76-xC7.0Si3.3B5.0P8.7Mox (x=0, 1 at.%, 3 at.% and 5 at.%) alloys prepared using an industrial Fe-P master alloy have been studied. With the substitution of Mo for Fe, glass-forming ability (GFA) was significantly enhanced and fully amorphous rods with a diameter of up to 5 mm were produced in the alloy with 3% Mo. The Mo-containing amorphous alloys also exhibited high fracture strength of 3635–3881 MPa and excellent magnetic properties including a high saturation magnetization of 1.10–1.41 T, a high Curie temperature and a low coercive force. The unique combination of high GFA, high fracture strength and excellent magnetic properties make the newly developed bulk metallic glasses viable for practical engineering applications.

Glass-forming ability and corrosion performance of Mn-doped Mg-Zn-Ca amorphous alloys for biomedical applications

In the present work, ribbon and 2-mm rod samples of Mg-Zn-Ca-Mn alloys were prepared by meltspinning and copper mold injection methods, respectively. Effects of Mn doping on glass-forming ability and corrosion performance in simulated body fluid of Mg65Zn30Ca5 alloy were studied through X-ray diffraction, scanning electron microscopy, differential scanning calorimeter, and electrochemical and immersion tests. Results show that with the Mn addition increasing, all the ribbon samples are completely in amorphous state. However, the microstructure of 2-mm rod samples transfers from fully amorphous for the Mn-free alloy to almost polycrystalline state with precipitated Mg, Mn, and MgZn phases. Glass-forming ability of Mg65Zn30Ca5 alloy is decreased by Mn addition. Results of electrochemical and immersion tests demon- strate that the Mn-doped samples exhibit more negative corrosion potential and larger corrosion current density, suggesting that the corrosion resistance decreases with doping amount of Mn element increasing.

Correlation between superheated liquid fragility and potential energy landscape in Gd-and Pr-based glass-forming alloys

The kinetic viscosities of superheated liquids on the Gd-based bulk glass-forming alloys are measured by an oscillating viscometer in a high vacuum atmosphere. According to the viscosity data,the parameters of superheated liquid fragility,M,are calculated. Based on the values of M in Gd-and Pr-based (cited from the lit-erature) glass-forming alloys,we find that there is a linear correlation between M and the absolute value of mixing enthalpy,|ΔHmix|,in an alloy system with the same base element,and the larger M,the smaller |ΔHmix|. The alloy with larger M exhibits the larger height of energy barriers separating the minima on the potential energy landscape.

Effects of pressure on structure and dynamics of metallic glass-forming liquid with miscibility gap

The metallic liquid with miscibility gap has been widely explored recently because of the increasing plastic deformation ability of phase-separated metallic glass. However, the poor glass-forming ability limits its application as the structural materials due to the positive mixing enthalpy of the two elements. Since high pressure is in favor of the formation of the glass, the effect of pressure on the structural and dynamical heterogeneity of phase-separated CusoAgso liquid is inves- tigated by molecular dynamics simulation in the pressure range of 0-16 GPa. The results clearly show that the pressure promotes the formation of metallic glass by increasing the number of fivefold symmetry cluster W and dynamical relaxation time; meanwhile, the liquid-liquid phase separation is also enhanced, and the homogenous atom pAlrs show stronger interaction than heterogeneous atom pAlrs with increasing pressure. The dynamical heterogeneity is related to the formation of fivefold symmetry clusters. The lower growing rate of W at higher pressure with decreasing temperature corresponds to the slow increase in dynamical heterogeneity. The pressured glass with miscibility gap may act as a candidate glass with improved plastic formation ability. The results explore the structural and dynamical heterogeneity of phase-separated liquid at atomic level.

Comparative Study of the Magnetic Properties and Glass-Forming Ability of Fe-Based Bulk Metallic Glass with Minor Mn, Co, Ni, and Cu Additions

Fe43MsCra5Mo14C15B6Y2 （M = Mn, Co, Ni, and Cu in at.%） bulk metallic glasses （BMGs） are synthesized using the suction casting technique, and the glass-forming ability （GFA）, microstructure, and thermal and magnetic properties of these glasses are extensively examined using X-ray diffraction, differential scanning calorimeter, and vibrating sample magnetometer techniques. Among the four BMG alloys, Fe43NisCr15Mo14C15B6Y2 exhibits the lowest coercivity and the highest saturation magnetization, Curie temperature, effective magnetic moment, and GFA. By contrast, Fe43MnsCrlsMo14C15B6Y2 presents the poorest magnetic properties, such as the highest coercivity and the lowest saturation magnetization, Curie temperature, and effective magnetic moment. Fe43Cu5Cr15MolaC15B6Y2 demonstrates the lowest thermal stability and GFA. The observed thermal, structural, and magnetic properties of these BMG alloys are discussed in terms of the kinetics of BMG synthesization and the formation of different ferromagnetic, ferrimagnetic, and antiferromagnetic phases.

Designing metallic glasses with optimal combinations of glass-forming ability and mechanical properties

It is a long-standing challenge to search for metallic glasses(MGs)with optimal combinations of glassforming ability(GFA),strength and toughness in the vast compositional space.By taking into account both recently developed ellipse criterion and temperature-based GFA criterion,here we established quantitative correlations among compositions,elastic constants,GFA and mechanical properties of MGs,which enable to predict the GFA,fracture strength and fracture surface simultaneously in advance once the compositions of MGs are determined.Experimental data confirm the validity of this approach in prediction.Finally,a strategy for designing MGs with optimal combinations of strength,toughness and GFA is proposed,which allows for high-throughput discovering glass formers with excellent mechanical properties.

Data-driven glass-forming ability criterion for bulk amorphous metals with data augmentation

A data augmentation technique is employed in the current work on a training dataset of 610 bulk metallic glasses(BMGs),which are randomly selected from 762 collected data.An ensemble machine learning(ML)model is developed on augmented training dataset and tested by the rest 152 data.The result shows that ML model has the ability to predict the maximal diameter Dmaxof BMGs more accurate than all reported ML models.In addition,the novel ML model gives the glass forming ability(GFA)rules:average atomic radius ranging from 140 pm to 165 pm,the value of TT/(T-T)(T-T)being higher than 2.5,the entropy of mixing being higher than 10 J/K/mol,and the enthalpy of mixing ranging from-32 k J/mol to-26 k J/mol.ML model is interpretative,thereby deepening the understanding of GFA.