Solidification structures in rapidly quenched Cu-Ti-Zr alloys

The melt-spinning and pulsed laser-quenching techniques were used to generate fast cooling rates necessary to form metallic glass in ternary Cu-Ti-Zr alloys. Even though the cooling rates generated during melt-spinning were much lower than those generated during pulse laser-quenching, the amount of glass obtained in the melt spun alloys was much larger than in the laser-quenched alloys. The microstructure of the laser-quenched alloys consisted of metallic glass and a fine microcrystalline fcc phase, whereas the melt-spun ribbons of the same compositions were completely amorphous. Glass transition temperature trends in the ternary system were determined from alloys of composition traversing linearly from the binary Cu-Ti side to the Cu-Zr side. These trends showed a nearly linear change of T_g with composition.     

Development of bulk metallic glasses based on the Dy-Al binary eutectic composition

A series of dysprosium-based ternary, quadruple, and quintuple bulk metallic glasses （BMGs） based on Dy-Al binary eutectic composition were obtained with the partial substitution of Co, Gd, and Ni elements, for dysprosium. The results showed that the Dy31Gd25Co20Al24 alloy, which had the best glass forming ability （GFA）, could be cast into an amorphous rod with a diameter of 5 ram. The GFA of alloys was evaluated on the basis of the supercooled liquid region width, 7 parameter, the formation enthalpy, and the equivalent electronegativity difference of amorphous alloys. It was found that the eutectic composition was closely correlated with the GFA of the Dy-based BMGs.     

Prediction of Glass-Forming Compositions in Metallic Systems: Copper-Based Bulk Metallic Glasses in the Cu-Mg-Ca System

A novel methodology for predicting specific compositions for glass-forming alloys based on efficiently packed atomic cluster selection, liquidus lines, and ab initio calculations is presented. This model has shown applicable adaptation to many known metallic and ceramic oxide glass-forming systems and has led to the discovery of soon to be reported Ag- and Zn-based bulk metallic glasses (BMGs). As a model system, glass formation in the Cu-Mg-Ca ternary system has been assessed using this alloy design methodology, which has led to the discovery of a number of Cu-based BMGs with compositions ranging from Cu-33 to 55 at. pct, Mg-18 to 45 at. pct, and Ca-18 to 36 at. pct. Included in this work are the calculated values of associated cluster binding energies and correlations between physical and thermal properties of these glassy compositions, which show significant physical evidence to support the likely existence of such clusters.     

Structure and formation of the metastable phasem-TiBe

The metastable ordered phasem-TiBe was discovered in the course of studying liquidquenched Ti-Be and Ti-Be-Zr alloys. m-TiBe forms, together with the α-Ti solid solution, on heating binary (and ternary) metallic glasses to 700°C and is also observed directly in as-quenched alloys lying outside the composition limits for glass formation. This phase has a B2 (CsCl-type) crystal structure. Its existence can be justified in terms of crystal chemical factors leading to the conclusion that TiBe most likely does not appear as an equilibrium phase in normally cooled alloys due to the greater stability of the Laves phase TiBe₂.     

Glass formation and nanocrystallization in Zr based alloys

In the present paper bulk glass forming behaviour of some of Zr based Ni, Cu, Al and Ti bearing alloys has been investigated. Examination of the as solidified microstructure of these alloys in the partially crystalline state has shown that the predominance presence of the Zr₂Ni or its derivatives phases as the phases competing with glass formation whereas in the fully amorphous microstructure, quenched-in nuclei and the atomic short range order existing in the amorphous phase were observed. The aim of the microstructural examinations of the fully amorphous phase was to ascertain the nature and morphology of the quench-in nuclei. In the partially crystalline microstructures, study of the crystalline phases competing with glass formation has helped in better understanding of the solidification process during BMG formation. The kinetics of crystallization of the as solidified Zr based bulk metallic glasses were studied by differential scanning calorimetry (DSC) and crystallized microstructures were examined by conventional and high-resolution electron microscopy. The activation energies of crystallization and the Avrami exponent have been evaluated. The Avrami exponent values have been rationalized in terms of the observed nucleation and growth behaviour of the phases forming on crystallisation. Conditions of crystallization leading to the formation of nanocrystals have been identified.     

Fe60CoxZr10Mo5W2B23-x(x=1,3,5,7,9)块状金属玻璃的非晶形成能力

The bulk Fe60CoxZr10Mo5W2B23-x (x= 1, 3, 5, 7, 9) amorphous rods with diameters of1.5 mm were successfully prepared by copper mold casting method with the low purity raw materials.The amorphous and crystalline states, and thermal parameters, such as the glass transition temperature (Tg), the initial crystallization temperature (Tx), the supercooled liquid region (ΔTx = TxTg), the reduced glass transition temperature Trg (Tg/Tm, Tm: the onset temperature of melting of the alloy, and Tg/T1, T1 : the finished temperature of melting of the alloy) were investigated by X-ray diffractometry (XRD) and differential scanning calorimetry (DSC) analysis. Glass forming ability of Fe60CoxZr10Mo5W2B23-x (x=1, 3, 5, 7, 9)bulk metallic glasses has been studied. According to the results, the alloy (x=7) with the highest Trg (Tg/T1 =0. 607, Tg/T1 =0.590) value, has the strongest glass forming ability among these alloys because its composition is near eutectic composition.The wide supercooled liquid region over 72 K indicates the high thermal stability for this alloy system.This bulk metallic glass exhibits quite high strength (Hv 1020). The success of production of the Febased bulk metallic glass with industrial materials is of great significance for the future progress of basic research and practical application.     

Crystallization studies in the aluminum-rich corner of the aluminum-iron-manganese system

A method for determining the compositional areas of primary crystallization of Al-Fe-Mn alloys has been developed and used for the determination of the locations of the eutectic troughs, the ternary eutectic point, and the corresponding variation in composition of the FeAl₃ and (FeMn)Al₆ phases in the aluminum-rich corner of this system. The method uses slow crystallization in a relatively large and well stirred bath of alloy while periodically taking small samples of slurry at temperature by sucking these into silica tubes, followed by quenching and metallographic and electron probe examination. Growth of individual rounded aluminum and polygonal intermetallic crystals was observed during crystallization along the eutectic troughs.     

Determination of eutectic compositions in complex metal systems

The zone-melting technique has been used for determining eutectic compositions in complex metal systems. The application of this technique is demonstrated in a ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic; in a quaternary system, Al-Mg-Zn-Si, in which the eutectic composition is unknown, and in a complex system, Al-Mg-Zn-Cu-Sn-Pb, in which the eutectic composition cannot possibly be determined using the conventional method. The advantages and disadvantages of the unique approach for the determination of the eutectic composition are discussed.     

Ni-Nb-Ta bulk metallic glasses designed by a cluster-plus-glue atom model

The formation of Ni-based ternary Ni-Nb-Ta bulk metallic glasses (BMGs) is explored in this work. Alloy compositions are designed by the cluster-plus-glue atom model based on a eutectic-related binary cluster Ni-Ni₆Nb₆, which is derived from the binary eutectic crystalline phase NiNb (Fe₇W₆ type). According to the cluster-plus-glue atom model, the well-known binary BMG-forming composition Ni₆₂Nb₃₈ can be described by a composition formula [Ni-Ni₆Nb₆]Ni₃ = Ni_62.5Nb_37.5. With an aim to further improve the glass-forming ability of the Ni-Nb alloy, Ta is selected as an alloying addition to partially replace Nb in the [Ni-Ni₆Nb₆]Ni₃ composition formula. The experimental results verified that BMGs with a critical size of 3 mm can be achieved at compositions [Ni-Ni₆Nb_6−xTa_x]Ni₃ (x = 0.9 ∼ 1.1). Thermal and mechanical properties of the obtained BMG alloys are also investigated.     

Microstructures of Al–Cu–Ag Ternary Eutectics Under Near-Isothermal Conditions

The three-phase eutectic microstructures in Al–Cu–Ag ternary alloys are complex and only directional solidification (DS) structures have been systematically studied in the literature. In order to better understand the large variation of eutectic structures in this system, three off-eutectic alloys in the vicinity of the nonvariant eutectic composition were solidified in a differential scanning calorimeter (DSC). The DSC was operated between 450 and 550 °C and at a heating and cooling rate of 1 °C/min to produce near-isothermal conditions. The intermetallic phase ζ-Ag₂Al is found to behave like pure metallic phase and forms primary dendrites. The ζ-Ag₂Al phase has a regular morphology in eutectics, while the θ-Al₂Cu exhibits big anisotropy of intermetallic nature and shows elongated morphology in the unconstraint grown eutectics. Three basic eutectic structures are categorized based on the relative phase arrangement: (1) semi-regular eutectic with elongated θ-Al₂Cu; (2) regular eutectic with rod-like ζ-Ag₂Al embedded in θ-Al₂Cu and (3) irregular eutectic with θ-Al₂Cu in ζ-Ag₂Al. They have nearly the same phase fraction and composition but distinct phase size distribution. The DSC eutectic structures are compared with reported DS eutectic structures.     

Metastability and thermophysical properties of metallic bulk glass forming alloys

The absence of crystallization over a wide time/temperature window can be used to produce bulk metallic glass by relatively slow cooling of the melt. For a number of alloys, including several multicomponent Zr-based alloys, the relevant thermodynamic and thermomechanical properties of the metastable glassy and undercooled liquid states have been measured below and above the glass transition temperature. These measurements include specific heat, viscosity, volume, and elastic properties as a function of temperature. As a result, it becomes obvious that the maximum undercooling for these alloys is given by an isentropic condition before an enthalpic or isochoric instability is reached. Alternatively, these glasses can also be produced by mechanical alloying, thus replacing the thermal disorder by static disorder and resulting in the same thermodynamic glass state. During heating through the undercooled liquid, a nanoscale phase separation occurs for most glasses as a precursor of crystallization. This article is based on a presentation made in the “Structure and Properties of Bulk Amorphous Alloys” Symposium as part of the 1997 Annual Meeting of TMS at Orlando, Florida, February 10–11, 1997, under the auspices of the TMS-EMPMD/SMD Alloy Phases and MDMD Solidification Committees, the ASM-MSD Thermodynamics and Phase Equilibria, and Atomic Transport Committees, and sponsorship by the Lawrence Livermore National Laboratory and the Los Alamos National Laboratory.     

Bulk amorphous metallic alloys: Synthesis by fluxing techniques and properties

Bulk amorphous alloys having dimensions of at least 1 cm in diameter have been prepared in the Pd-Ni-P, Pd-Cu-P, Pd-Cu-Ni-P, and Pd-Ni-Fe-P systems using a fluxing and water-quenching technique. The compositions for bulk glass formation have been determined in these systems. For these bulk metallic glasses, the difference between the crystallization temperature (T _x) and the glass transition temperature (T _g, ΔT=T _x−T _g) ranges from 60 to 110 K. These large values of ΔT open the possibility for the fabrication of amorphous near-net-shaped components using techniques such as injection molding. The thermal, elastic, and magnetic properties of these alloys have been studied, and we have found that bulk amorphous Pd₄₀Ni_22.5Fe_17.5P₂₀ has spin glass behavior for temperatures below 30 K. This article is based on a presentation made in the “Structure and Properties of Bulk Amorphous Alloys” Symposium as part of the 1997 Annual Meeting of TMS at Orlando, Florida, February 10–11, 1997, under the auspices of the TMS-EMPMD/SMD Alloy Phases and MDMD Solidification Committees, the ASM-MSD Thermodynamics and Phase Equilibria, and Atomic Transport Committees, and sponsorship by the Lawrence Livermore National Laboratory and the Los Alamos National Laboratory.     

Ball milling-induced nanocrystal formation in aluminum-based metallic glasses

Various experimental techniques have been used to investigate the effect of mechanical milling on the structural stability of rapidly solidified aluminum-based metallic glasses. Using transmission electron microscopy (TEM) and X-ray diffraction methods, the formation of nanocrystalline Al particles in some ball-milled Al-rich metallic glasses (such as Al₉₀Fe₅Gd₅ and Al₉₀Fe₅Ce₅) is clearly observed. For other compositions with lower Al concentration such as Al₈₅Ni₅Y₁₀, no such phase transformation can be detected by TEM or X-ray. However, differential scanning calorimetry (DSC) measurements show that the crystallization peaks of the ball-milled Al₈₅Ni₅Y₁₀ metallic glass shifted to higher temperatures, while the crystallization enthalpy associated with the first exothermic peak decreased to a lower value, revealing that certain structural changes have taken place as a result of mechanical deformation. The compositional dependence of the structural stability of Al-based metallic glasses against mechanical deformation suggests that the nanocrystal formation induced by a deformation process is different from that caused by a thermal process. The large plastic strain induced atomic displacements and the enhancement of atomic mobility during the deformation process, are the possible mechanisms of mechanical deformation-induced crystallization. Our results demonstrate a new way of obtaining nanophase glassy composite alloy powders which are suitable for engineering applications upon further consolidation processing.     

Crystallization kinetics of amorphous magnesium-rich magnesium-copper and magnesium-nickel alloys

Amorphous magnesium-rich alloys Mg _y X_1-y (X=Ni or Cu and 0.82<y<0.89) have been produced by melt spinning. The crystallization kinetics of these alloys have been determined by in situ X-ray diffraction (XRD) and isothermal and isochronal differential scanning calorimetry (DSC) combined with ex situ XRD. Microstructure analysis has been performed by means of transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS). Crystallization of the Mg-Cu alloys at high temperature takes place in two steps: primary crystallization of Mg, followed by simultaneous crystallization of the remaining amorphous phase to Mg and Mg₂Cu. Crystallization of the Mg-Cu alloys at low temperatures takes place in one step: eutectic crystallization of Mg and Mg₂Cu. Crystallization of the Mg-Ni alloys for a Mg content, y>0.85, takes place in two steps: primary crystallization of Mg and of a metastable phase (Mg_∼5.5Ni, with Mg content y=0.85), followed by the decomposition of Mg_∼5.5Ni. Crystallization of the Mg-Ni alloys for a Mg content y<0.85 predominantly takes place in one step: eutectic crystallization of Mg and Mg₂Ni. Within the experimental window applied (i.e., 356 K<T<520 K and 0.82<y<0.89), composition dependence of the crystallization sequence in the Mg-Cu alloys and temperature dependence of the crystallization sequence in the Mg-Ni alloys has not been observed.     

A study of a cellular phase transformation in the ternary Ni- Ai- Mo alloy system

Orthorhombic Ni₃Mo has been observed as a product of a cellular precipitation reaction occurring at grain boundaries in both Ni-12Al-15Mo and a ternary eutectic Ni-12.8Al-22.2Mo (compositions in at. pct) when heat treated at intermediate temperatures (600 to 850 °C). Convergent beam electron diffraction and energy dispersive X-ray spectroscopy techniques have been employed to characterize the structure and composition of this phase in these alloys. Since this phase is usually heavily faulted, the diffraction symmetries are reduced, causing ambiguities in analysis. Therefore, a binary (nominally) stoichiometric Ni₃Mo alloy was produced and heat treated in a manner designed to minimize faulting. Convergent beam patterns obtained from this material exhibited symmetries that identify it as having the mmm point group; further analysis of the diffraction patterns led to the conclusion that the space group is Pmmn. These patterns were then used to aid in the interpretation of those taken from the ternary alloys. Orthorhombic Ni₃Mo was also observed within the grains of the ternary eutectic alloy following prolonged aging treatments; the orientation relationship between the Ni3Mo and the fee matrix was determined to be identical with that in the cellularly transformed regions.     

球磨法制备Mg-Cu非晶态合金粉末

本文研究了Mg—Cu二元相图的三个共晶点成分配方和两个化合物成分配方在球磨条件下非晶态合金的形成能力。XRD结果显示：除一个共晶点成分配方外，其它所有成分配方都能形成非晶态合金；非晶形成能力由大到小依次为MgCu2(化合物)，Mg58Cu42(共晶点)，Mg2Cu(化合物)，Mg85Cu15(共晶点)，Mg22Cu78(共晶点)。显然，作为选择非晶态合金成分的判据来说，Schwarz与Johnson的两个条件准则比Davies的共晶线准则更加合适。非晶形成的过程是：首先发生Mg在Cu中的固溶，随后形成过饱和固溶体，最后过饱和固溶体失稳形成非晶态合金。     

Microstructure and properties of duplex δ-Al3(Ti, V)/β-(Ti, V) alloys

The microstructures of multiphase intermetallic alloys with compositions Al₇₀Ti₁₀V₂₀ and Al₆₂Ti₁₀V₂₈ based on the trialuminide Al₃Ti have been characterized, following chill casting and postsolidification heat treatment, using a combination of scanning electron microscopy and transmission electron microscopy (TEM). Evidence of a eutectic reaction of the form L → δ-Al₃(Ti, V)+ζ-Al₈V₅, not previously reported in the Al-Ti-V system, has been observed in both alloys solidified at sufficient levels of undercooling. The ζ phase is replaced by metallic β-(Ti, V) phase during subsequent heat treatment in the range 1073 to 1273 K, and differential thermal analysis (DTA) of samples prean-nealed at 1173 K revealed an endothermic peak at ∼1560 K, consistent with equilibrium eutectic melting of the form (δ+β) → L. Although the chill-cast alloys retained metastable intermediate high-temperature phases, duplex metallic-intermetallic microstructures, containing uniform fine-scale distributions of metallic β-(Ti, V) solid solution in a δ-Al₃(Ti, V) intermetallic matrix, have been produced in both alloys during isothermal heat treatments at temperatures in the range 1073 to 1273 K. For both alloys, the bulk Vickers hardness of such microstructures remained in excess of that of binary Al₃Ti, while in the Al₆₂Ti₁₀V₂₈ alloy, where the increased volume fraction of β phase took the form of a near-continuous network within δ matrix, there was evidence arising from indentation tests of a substantial improvement in the cracking resistance compared to both chill-cast ternary alloy and binary Al₃Ti.     

Prediction of Bulk Metallic Glass Formation in Cu–Zr–Ag–Hf System by Thermodynamic and Topological Modeling

Cu based bulk metallic glasses (BMGs) are widely studied because of their high glass forming ability (GFA) and interesting combination of properties such as high strength coupled with good ductility and low cost. With these attributes, Cu based BMGs are being projected as promising materials for practical applications. The process of glass formation in metallic systems is a challenging task and alloys should be cooled from the liquid state at rates faster than a critical cooling rate (R_c) to resist crystallization. Interestingly, composition plays an important role in achieving easy glass formation, which is usually measured in terms of R_c. In the present work, attempt has been made to identify the composition for easy glass formation in Cu based quaternary system by theoretical approach. A GFA parameter P_HS, which is a product of enthalpy of chemical mixing (?H_chem) and mismatch entropy normalized with Boltzmann??s constant (?S_??/k_B) is used to identify the best glass forming composition in Cu?CZr?CAg?CHf system. Further, a new parameter P_HSS, which is a product of P_HS and configurational entropy (??S_config/R) is found to illustrate strong correlation with GFA. An attempt has also been made to correlate P_HSS parameter with critical diameters and R_c using reported data in Cu?CZr?CAg?CHf system.     

Crystallization of amorphous Fe- P- C alloys

The transformation of amorphous Fe-P-C alloys from the amorphous state to crystalline state was studied by differential scanning calorimetry (DSC), X-ray diffractometry (XRD) and transmission electron microscopy (TEM). Compositions included iron and phosphorus rich alloys and alloys with compositions near the eutectic composition. The crystallization of Fe-P-C alloys proceeded by the following processes: for the iron rich alloy, bcc α Fe precipitated first; for the phosphorus rich alloy, Fe₂P and iron carbide precipitated first; for the alloys near the eutectic line, the eutectic reactions dominated, although some α Fe or Fe₂P plus iron carbide crystals were observed. The composition dependence of the transformation can be explained successfully by a free energy model with the help of the phase diagram. From DSC and TEM results, the nucleation rate of the α Fe precipitate decreased with time in the Fe rich alloys according to the recrystallization theory of Avrami. Formerly Research Fellow in the Department of Metallurgy and Materials Science, University of Pennsylvania This paper is based on a presentation made at a symposium on “Recovery Recrystallization and Grain Growth in Materials” held at the Chicago meeting of The Metallurgical Society of AIME, October 1977, under the sponsorship of the Physical Metallurgy Committee.     

Structure and phase composition of alloys of the Al-Ce-Cu system in the region of the Al-Al<Subscript>8</Subscript>CeCu<Subscript>4</Subscript> quasi-binary join

Phase diagram of the Al-Cu-Ce system is investigated in the region of the quasi-binary join Al-Al₈CeCu₄. The parameter of the eutectic reaction L → (Al) + CeCu₄Al₈ are found: T = 610°C; composition 14% Cu and 7% Ce. This eutectic has a dispersed structure, and the ternary compounds, which is involved in the eutectic, is capable to fragmentation and spheroidism in the course of heating starting from 540°C. It is shown that the region of optimal compositions of alloys based on the eutectic (Al) + CeCu₄Al₈ lies in narrow limits. This is caused by the fact that an abrupt decrease of the solidus and, as a consequence, significant broadening of the crystallization range occurs at a relatively small deviation from the ratio Cu: Ce = 2.