Formation, Structure and Properties of Bulk Metallic Glasses

Bulk metallic glasses with up to 72 mm critical section thickness have been obtained by conventional casting techniques and the properties of these materials, particularly the mechanical and magnetic properties have been studied. These materials have been demonstrated to have novel properties which are fundamentally different from their crystalline counterparts. The recent status of research and development in formation, structure and properties of bulk metallic glasses is reviewed. The techniques to produce such bulk glasses are summarized and the glass forming ability and the critical cooling rate of these materials are discussed. Further consideration of the development and application of this new class of materiaIs will be proposed.

Formation and corrosion properties of Fe-based bulk metallic glasses

Bulk metallic glass （BMG） formation was explored in the Fe-B-Si-Nb alloy system though combined use of the atomic cluster line approach and the minor alloying strategy. The basic ternary compositions in the Fe-B-Si system were determined by the intersection points of two cluster lines, namely, Fe-B cluster to Si and Fe-Si cluster to B. 3at% -4at% Nb was added to the quaternary Fe-B-Si-Nb alloy. The casting experiments revealed that good glass-forming ability （GFA） occurred at the （Fe73.4Si8.2B18.4）96Nb4 composition, and 3-mm diameter BMG samples were made. The glass transition temperature （Tg）, crystallization temperature （Tx）, and supercooled liquid region （△Tx=Tx-Tg） of this BMG were measured to be 866, 889, and 23 K, respectively. The BMG shows a high Vickers hardness of about Hv 1164, a Young＇s modulus of 180 GPa, and a good corrosion resistance in the solutions of 1 mol/L HCl and 3wt% NaCl.

Preparation and Mechanical Properties of Misch Metal Based Bulk Metallic Glasses

The formation, thermal stability and mechanical properties of Misch metal （Mm）-based alloy bulk metallic glasses （BMGs） with composition of Mm55Al25Cu10Ni5Co5 were investigated by means of X-ray diffraction, differential scanning calorimetry, differential thermal analysis and compression test. The results indicate that the Mm-based BMGs exhibit a distinct glass transition and a wide supercooled liquid region Δ Tx（ 〉 60 K） before crystallization. The alloy can be fabricated into bulk glassy form of 3 mm in diameter by copper mold casting methods. Compared with the La55Al25Cu10 Ni5Co5 BMG, the Mm55Al25Cu10Ni5Co5 BMG shows higher compression fracture strength and lower cost. A new parameter γ and melting temperature Tl are closely correlated with the glass forming ability （GFA） of Mm-based alloys.

Bulk metallic glasses formed by alloying the Cu_6Zr_5 cluster

The bulk metallic glass formation in the Cu-Zr-M ternary systems by alloying of a binary basic Cu6Zr5 cluster was inves- tigated, where M stands for Sn, Mo, Ta, Nb, Ag, Al and Ti. The Cu6Zr5 cluster is a capped Archimedean antiprism that characterizes the local structure of the Cu10Zr7 crystalline phase. This cluster composition almost superposes with Cu-Zr eutectic Cu0.56Zr0.44. A se- ries of alloys along the cluster line (Cu6Zr5)1-xMx were examined for their glass forming abilities. Alloy rods with a diameter of 3 mm were prepared by copper mould suction casting method and analyzed by XRD and thermal analysis. The Cu-Zr based bulk metallic glasses were discovered with minor Nb, Sn, Mo, Ta additions (≤2at%) and Al, Ti, Ag (8at%≤concentration≤9at%). The alloying mechanism was discussed in the light of atomic size, cluster-linking structure and electron concentration factors.

Crystallization Kinetics of Misch Metal Based Bulk Metallic Glasses

The crystallization kinetics of Mm55Al25Cu10Ni5Co5 bulk metallic glass （BMG） was investigated by means of differential scanning calorimetry （DSC） in the mode of continuous heating or isothermal annealing. It was found that the apparent activation energy Eg, Ex and Ep of the BMG calculated by Kissinger＇s method were 189.58, 170.68 and 170.41 kJ·mol^-1, respectively, which was bigger than those of La55Al25Cu10Ni5Co5 BMG indicating that thermal stability of the former was higher than that of the latter. The local activation energy obtained using Ozawa equation decreased as crystallization proceeded except for the initial stage. The Avrami exponents were calculated to be in the range of 3.26 - 5.23 for different crystallization stages and isothermal temperatures. This implied that crystallization of Mm55Al25Cu10Ni5Co2 BMG was governed by diffusion-controlled three-dimensional growth with either reduced or increased nucleation rate, depending on isothermal temperature. Inconsistency of thermal stability with glass-forming ability for Mm（La）-Al-Cu-Ni-Co BMGs was discussed.

Glass formation of ternary Sm-based Sm-Al-Co bulk metallic glasses

Ternary Sm-based Sm-Al-Co alloys at specific compositions designed using an e/a- and cluster-related criteria exhibit high glass forming abilities and form bulk glassy rods of 3 mm in diameter by a copper mold suction-casting method. Four composi- tions of bulk metallic glasses (BMGs) are Sm50Al25Co25, Sm52Al24Co24, Sm54Al23Co23 and Sm56Al22Co22, which all satisfy a constant conduction electron concentration of 1.5. Among them, the BMG exhibiting the largest reduced glass transition temperature (Trg) is Sm50Al25Co25, which reaches 0.648. The glass transition temperature Tg and the onset crystallization temperature Tx of this alloy are respectively 579 and 640 K at a heating rate of 20 K/min.

Crystallization mechanism of CeAlFeCo bulk metallic glasses

Crystallization behaviors of Ce60Al15Fe5+xCo20-x(x=0,5,10) bulk metallic glasses(BMGs) were studied by means of differential scanning calorimeter(DSC) and X-ray diffraction(XRD).The crystallization processes of different samples were simulated by JMA equation.Experimental results demonstrated that incubation and crystallization time increased with decreasing isothermal temperature for the same sample.The crystallization mechanism of CeAlFeCo BMGs was discussed.

Modeling of Microimprinting of Bulk Metallic Glasses

A finite element analysis （FEA） model has been developed to analyze microimprinting of bulk metallic glasses （BMG） near the glass transition temperature （Tg）. The results reveal an approximately universal imprinting response for BMG, independent of surface feature length scale. The scale-independent nature of BMG imprinting derives from the flow characteristics of BMG in the temperature range above Tg. It also shows that the lubrication condition has a mild influence on BMG imprinting in the temperature range above Tg.

Compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni bulk metallic glasses

Starting from the quaternary Cu47Ti34Zr11Ni8 alloy, the compositional dependence of thermal and elastic properties of Cu-Ti-Zr-Ni alloys was systematically investigated. Quaternary Cu-Ti-Zr-Ni alloys can be cast directly from the melt into copper molds to form fully amorphous strips or rods with the thickness of 3-6 mm. The evidence of the amorphous nature of the cast rods was provided by X-ray spectra. The measured glass transition temperature （Tg） and crystallization temperature （Tx） were obtained for the alloys using differential scanning calorimetry （DSC） at the heating rate of 20 K/s. In the results, the differences between the glass temperature and the crystallization temperature （△Tx=Tx-Tg） are measured with values ranging up to 33-55 K. The reduced glass transition temperature （Trg）, which is the ratio of the glass temperature to the liquidus temperature （T3, is often used as an indication of the glass-forming ability of metallic alloys. For the present Cu-Ti-Zr-Ni alloys, this ratio is typically in the range of 0.5838-0.5959, characteristic of metallic alloys with good glass-forming ability. The elastic constants for several selected alloys were measured using ultrasonic methods. The values of the elastic shear modulus, bulk modulus, and Poisson＇s ratio were also given.

Mechanical behavior of Cu-Zr bulk metallic glasses (BMGs): A molecular dynamics approach

In the present work, three-dimensional molecular dynamics simulation is carried out to elucidate the nanoinden- tation behaviors of CuZr Bulk metallic glasses （BMGs）. The substrate indenter system is modeled using hybrid interatomic potentials including both many-body Finnis Sinclair （FS） and two-body Morse potentials. A spherical rigid indenter （diameter= 60 A（1 A = 10 ^-10 m）） is employed to simulate the indentation process. Three samples of BMGs including Cu25Zr75, CusoZr50, and Cu75Zr25 are designed and the metallic glasses are formed by rapid cooling from the melt state at about 2000 K. The radial distribution functions are analyzed to reveal the dynamical evolution of the structure of the atoms with different compositions and different cooling rates. The mechanical behavior can be well understood in terms of load-depth curves and Hardness-depth curves during the nanoindentation process. Our results indicate a positive linear relationship between the hardness and the Cu concentration of the BMG sample. To reveal the importance of cooling rate provided during the processing of BMGs, we investigate the indentation behaviors of CusoZr50 at three different quenching rates. Nanoindentation results and radial distribution function （RDF） curves at room temperature indicate that a sample can be made harder and more stable by slowing down the quenching rate.

A cluster line approach to finding new Fe-B-Y-Nb-Zr bulk metallic glasses

The glass forming ability of the [(Fe12/13Y1/13)100?xBx]96Nb2Zr2 (x=9–26) system was investigated using a series of cluster lines. Three types of clusters, an icosahedron (Fe12Y), a capped Archimedes anti-prism (Fe8B3) and a capped trigonal prism (Fe9B), as well as a binary eutectic (Fe83B17) were considered. Bulk glassy alloy rods of 3 mm in diameter were synthesized using a copper mold suction-casting method. The glass transition temperature was observed for all samples in the boron range of 15.9at%-25.7at%, with the alloy at 15.9at% of boron having the best thermal properties. The ferrous-based bulk metallic glasses (BMG) obtained have high reduced glass transition temperatures with the maximum reaching 0.63 and large supercooled liquid regions with the maximum reaching 111 K. Magnetic testing revealed a large value of coercive force and remanent magnetization, being 11 kA/m and 0.1 T, re- spectively.

Bulk Metallic Glasses in Sm-Cu-Ni-Al Alloy Systems

A new series of Sm-Cu-Ni-Al bulk metallic glasses were prepared by suction casting. Their glass-forming ability and thermal stability were investigated by X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The results of DSC indicate that the alloy components strongly affect the widths of supercooled liquid region (ΔT_x=T_x-T_g onset). The widths of supercooled liquid region for Sm_ 70-xCu_xNi_ 10Al_ 20 (x=12.5, 15.0, 17.5), Sm_ 65-xCu_ 15Ni_xAl_ 20 (x=8, 10, 12) and Sm_ 75-xCu_ 15Ni_ 10Al_x (x=15, 20, 25) increase first and then decrease with the increase of x atomic fraction. And Sm_ 55Cu_ 15Ni_ 10Al_ 20 alloy was found to be with the largest width and it can be cast into bulk metallic glass with up to 3 mm in diameter. The glass-forming ability of the alloys was explained in terms of Miedema′s theory, electronegativity difference and atomic size parameter of the amorphous alloys.

Effect of Friction Stir Welding on Bulk Metallic Glasses

In order to enlarge the size of bulk metallic glasses(BMGs),two Cu_(36)Zr_(48)Al_(8)Ag_(8) BMGs plates were successfully welded by friction stir welding(FSW)without obvious crystallization.The effect of friction stir welding on microstructure and mechanical properties of the BMGs was investigated.X-ray diffraction(XRD)and scanning electron microscope(SEM)were used to evaluate the changes of the crystalline particles in the BMGs.Nanoindentation was applied to analyze the changes of the amorphous matrix.Micro-hardness of the stir zone before and after FSW was tested to explore changes of the mechanical properties.Results show that the original Al3Zr particles in the BMGs were refined and some cavities parallel to the rotating direction of the pin were observed in the amorphous matrix after FSW.Furthermore,micro-hardness of the stirred zone rises approximately 50 Hv compared with the as-cast sample due to structure relaxation of the amorphous matrix.

LaGa-based bulk metallic glasses

We report the formation of La Ga-based bulk metallic glasses. Ternary La–Ga–Cu glassy rods of 2–3 mm in diameter can be easily formed in a wide composition range by the conventional copper mold casting method. With minor addition of extra elements such as Co, Ni, Fe, Nb, Y, and Zr, the critical diameter of the full glassy rods of the La–Ga–Cu matrix can be markedly enhanced to at least 5 mm. The characteristics and properties of these new La Ga-based bulk metallic glasses with excellent glass formation ability and low glass transition temperature are model systems for fundamental issues investigation and could have some potential applications in micromachining field.

Observation and computer simulation of multicomponent chemical short-range order (MCSRO) for the bulk metallic glasses

The atomic configuration of chemical short-range order (CSRO) for the Zr-base metallic glasses was investigated by using nano-diffraction and high resolution transmission electronic microscopy (HRTEM) technology with a beam size of 0.5 nm. It is il- lustrated that the pattern of atomic configuration of CSRO might have various compound counterparts because of the chemical inter- action of bonding atoms. Some atomic configuration of MCSRO is similar to the icosahedral structure with 10-fold symmetry of very weak spots. In deed, the nano-beam technology could clearly detect the evolution of atomic configuration in nanometer scale during the transformation from the metallic melt to the primary crystallization. The local atomic configuration of CSRO is also investigated by molecular dynamics simulation (MD) for the Zr2Ni compound in a wider temperature range. The CSRO in the melt could be pic- torially demonstrated as distorted coordination polyhedron of the compound structure and/or the structure similar to cubo-octahedron analogs. The MD simulation illustrates that the atomic packing of long-range order disappears just above the melting point, but the chemical interaction of bonding atoms still exists that leads to form the various CSRO with the atomic configuration similar to stable or metastable unit cell of Zr2Ni compound. The icosahedral polyhedron became more abundance as the overheating temperature was raised.

In Vivo Investigation of Zr-Based Bulk Metallic Glasses Sub-Periosteally Implanted on the Bone Surface

Bulk metallic glasses (BMG) show higher strength and lower Young’s modulus than SUS 316L stainless steel and Ti-6Al-4V alloys. This study aimed to investigate the reaction of Zr-based BMG sub-periosteally implanted on the surface of the rat femur, thereby evaluate the possibility of the BMG as biomaterials for osteosynthetic devices. Zr65Al7.5Ni10Cu17.5 BMG ribbons with 10 mm length, 2 mm width and 0.5 mm thickness were implanted sub-periosteally on the femur surface in three male Wistar rats for 6 weeks. Systemic effects were evaluated by measuring Cu and Ni levels in the blood, and local effects were evaluated by the histological observation of the surrounding soft tissues in contact with the BMG. The reaction of the surface of the BMG was examined with scanning electron microscopy. No increase of Cu and Ni levels in the blood was recognized. In the scanning electron microscopy observation, spherical deposits which were considered as sodium chloride crystals were observed. Neither breakage nor pitting corrosion was noted. BMG will be a promising metallic biomaterial for osteosynthetic device that must be removed.

Role of yttrium in glass formation of Ti-based bulk metallic glasses

Starting with Zr of two different purities, Ti-based bulk metallic glasses （BMGs） with a nominal composition of Ti40Zr25Cu12Ni3Be20 were prepared. The effect of the addition of yttrium at levels of 0.2 at.%, 0.4 at.%, 0.5 at.%, 0.6 at.%, and 1 at.% on the glass forming ability （GFA） of the alloy has been investigated by means of metallography, X-ray diffraction, and differential scanning calorimetry. Experimental data in-dicates that high impurity content dramatically reduces the glass forming ability. Microalloying with 0.5 at.% Y is effective in suppressing the crystalline phase formation and alleviating the detrimental effect of oxygen in the low-purity alloy. On the contrary, in the alloy contain-ing high-purity element, the effective yttrium addition is less than 0.4 at.%. The results indicate that the beneficial effect of the optimum dopants is mainly due to scavenging the oxygen impurity via the formation of innocuous phase.

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.

Room temperature plastic deformation behavior of ZrCuNiAl bulk metallic glasses

The Zr62.55Cu17.55Ni9.9Al10 bulk metallic glass （BMG） was prepared by using copper-mold suction-casting. X-ray diffraction and differential scanning calorimetry were utilized to determine its structure and thermal stability. Uniaxial compression and Rockwell indenta- tion tests were adopted to study the plastic deformation behavior at room temperature. The results show that the glass transition temperature and the onset temperature of exothermic reaction of the BMG are 651.5 and 748 K, respectively. During the compression test, the BMGs undergo an engineering strain of about 2.5%, i.e., true strain of 2.8%, and then fracture. The BMGs deform via the formation and propagation of shear bands. Under indentation loading, the BMGs deform through the formation of radiation-like and circular shear bands. The circular shear bands form earlier than the radiation-like ones, The formation mechanism of shear bands in the BMGs was analyzed and discussed.