Kinetics of non-isothermal crystallization in Cu50Zr43Al7 and (Cu50Zr43Al7)95Be5 metallic glasses

The crystallization kinetics of Cu₅₀Zr₄₃Al₇ and (Cu₅₀Zr₄₃Al₇)₉₅Be₅ metallic glasses was studied using differential scanning calorimetry (DSC) at four different heating rates under non-isothermal condition. The glass transition temperature T _g, the onset temperature of crystallization T _x, and the peak temperature of crystallization T _p of the two metallic glasses were determined from DSC curves. The values of various kinetic parameters such as the activation energy of glass transition E _g, activation energy of crystallization E _p, Avrami exponent n and dimensionality of growth m were evaluated from the dependence of T _g and T _p on the heating rate. The values of E _g and E _p, calculated from many different models, are found to be in good agreement with each other. The average values of the Avrami exponent n are (2.8 ± 0.4) for Cu₅₀Zr₄₃Al₇ metallic glass and (4.2 ± 0.3) for (Cu₅₀Zr₄₃Al₇)₉₅Be₅ metallic glass, which are consistent with the mechanism of two-dimensional growth and three-dimensional growth, respectively. Finally, the parameter H _r, S, and crystallization enthalpy ΔH _c are introduced to estimate the glass-forming ability and thermal stability of metallic glasses. The result shows that the addition of Be improves the glass-forming ability and thermal stability of Cu₅₀Zr₄₃Al₇ metallic glass.     

Effect of reversible structural relaxation on diffusion in bulk metallic glasses

Long time relaxation at temperatures below the calorimetric glass transition causes reversible structural changes in metallic glasses. The resulting enthalpy recovery was measured by means of DSC in Zr_46.8Ti_8.2Cu_7.5Ni₁₀Be_27.5- and Pd₄₀Cu₃₀Ni₁₀P₂₀-bulk glass annealed for different times at 553 K and 542 K, respectively. Relaxation times of about 10⁶ s and 10⁴ s, respectively, were determined. The diffusion coefficients of B, Fe and Co were measured above and below the calorimetric glass transition temperature. Whereas the temperature dependence of these diffusion coefficients in the non-relaxed glasses shows “non-linear” Arrhenius behaviour with a break near the glass transition, the diffusion in the long time relaxed glasses follows a uniform temperature dependence over the entire temperature range with considerably reduced diffusion coefficients below the glass transition. This behaviour can be reversed by annealing the relaxed glasses again at higher temperatures indicating the strong effect of the reversible structural relaxation on the diffusion coefficients.     

Synthesis of Cu3Sn Alloy Nanocrystals through Sequential Reduction Induced by Gradual Increase of the Reaction Temperature

Cu₃Sn alloy nanocrystals are synthesized by sequential reduction of Cu and Sn precursors through a gradual increase of the reaction temperature. By transmission electron microscopy (TEM), energy‐dispersive X‐ray spectroscopy (EDS), UV/Vis spectroscopy, and X‐ray diffraction (XRD) analyses, the alloy formation mechanism of Cu₃Sn nanocrystals has been studied. The incremental increase of the reaction temperature sequentially induces the reduction of Sn, the diffusion of Sn into the preformed Cu nanocrystals, resulting in the intermediate phase of Cu–Sn alloy nanocrystals, and then the formation of Cu₃Sn alloy nanocrystals. We anticipate that the synthesis of Cu₃Sn alloy nanocrystals encourages studies toward the synthesis of various alloy nanomaterials.     

Effect of hydrofluoric acid treatment on the crystallisation behaviour of Zr–Ti–Cu–Al–Ni metallic glass

The surface of the metallic glass Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ has been modified by hydrofluoric acid (HF) etching treatment. The devitrification and crystallisation process has been mainly studied by isothermal differential scanning calorimetry (DSC), X-ray diffractometry (XRD) and scanning electron microscopy (SEM). The nucleation-growth process is the mechanism of crystallisation; nevertheless the JMA-model is not applicable in every situation. Alternative methods are used to interpret the data. Results show the devitrification process is strongly affected by surface nucleation, which depends on the surface topology. Zr₃Al₂ is the first phase formed on the concave areas whereas the quasicrystalline and Zr₂Ni-based phases appears in the flatter ones. Nevertheless, the presence of an oxide surface layer acts upon the surface nucleation and dwarfs the consequences of such topological differences. Moreover, the quasicrystalline formation appears also to be in competition with the parallel formation of ZrO₂ due to thermal re-oxidation during the DSC experiments.     

Hydrogen in amorphous TM33Zr67 (TM=Fe, Co, Ni) alloys

Hydrogen sorption properties and some corresponding changes in the crystallization of amorphous TM₃₃Zr₆₇ (TM=Fe, Co, Ni) alloys have been investigated. Relatively large amount of hydrogen was found to dissolve into the amorphous alloys during electrochemical hydrogen charging. The microstructural evolution during annealing of H-charged Ni₃₃Zr₆₇ was studied as well. The weaker bonded hydrogen desorbs in a large temperature range (440–625 K) before the crystallization of the amorphous alloys to start. A hydride phase (ZrH₂) was found to form during annealing the H-charged amorphous Ni₃₃Zr₆₇ alloy. During heating at constant heating rate the hydride decomposes at about 715 K and formation of Zr₂Ni immediately takes place. The final microstructure of the Zr₂Ni, crystallized from the H-charged matrix, is noticeably finer compared to the material crystallized from the H-free amorphous alloy, most probably due to the higher temperature of Zr₂Ni formation in the H-charged amorphous alloy than in the H-free sample.     

Biocorrosion and biocompatibility of Zr–Cu–Fe–Al bulk metallic glasses

Owing to their unique chemo‐physical and structural characteristics, amorphous bulk metallic glasses (BMGs) are of great demand for fabrication of variety of advanced and innovative products including surgical and biomedical tools and devices. In this study, a series of Ni‐free Zr‐based BMGs in Zr–Cu–Fe–Al system are fabricated using copper‐mold casting technique, and their biocorrosion and biocompatibility are evaluated with respect to their corrosion behavior in the phosphate buffered saline (pH = 7.4) solution. Anodic polarization curves, scanning electron microscopy combined with energy‐dispersive X‐ray, and wettability analyses are conducted to characterize the surfaces of BMG samples. The biocompatibility of the BMG and control samples is studied by comparing cell–substrate interactions among different samples. It is found that Zr₆₀Cu₂₀Fe₁₀Al₁₀ displays a higher passive region compared with that of Zr₆₀Cu_22.5Fe_7.5Al₁₀, but both BMGs exhibit lower corrosion resistance compared with Ti–6Al–4V alloy. By addition of titanium to Zr–Cu–Fe–Al system (Zr₆₀Ti₆Cu₁₉Fe₅Al₁₀), a significant increase in the passive region of the polarization curve is detected. The cell culture experiments reveal that the number of attached and grown cells is significantly higher on the surface of the treated BMGs as compared with Ti–6Al–4V substrates and the culture plate as controls. There is no noticeable difference in cellular morphology among the BMG samples, and no cytotoxicity is detected. We speculate that the interaction of water molecules and matrix proteins with the surfaces of BMGs plays an important role in cell–substrate interactions and improved cell response. Copyright © 2013 John Wiley & Sons, Ltd.     

Analysis of thermodynamic behaviour of bulk metallic glass forming melts and glass forming ability

The thermodynamic behaviour of bulk metallic glass (BMG) forming melts have been studied by analyzing the temperature dependence of the Gibbs free energy difference (∆G), entropy difference (∆S) and enthalpy difference (∆H)between the undercooled melt and the corresponding equilibrium solid phases. The study is made by calculating∆G, ∆S and ∆H in the entire temperature range T _m (melting temperature) to T _g (glass transition temperature) using the expressions obtained on the basis of Taylor’s series expansion. The entire analysis is made for La-based five samples of BMGs; La₅₅Al₂₅Ni_20, La₅₅Al₂₅Ni₁₅Cu₅, La₅₅Al₂₅Ni₁₀Cu₁₀, La₅₅Al₂₅Ni₅Cu_15, and La₅₅Al₂₅Ni₅Cu₁₀Co₅ and a comparative study is also performed between present results and results obtained in the framework of expressions proposed by earlier workers. An attempt has also been made to study the glass forming ability for BMGs.     

Effect of Transition Metals (Cu, Co and Fe) on the Autothermal Reforming of Methane over Ni/Ce0.2Zr0.1Al0.7Oδ Catalyst

The transition metals (Cu, Co, and Fe) were applied to modify Ni/Ce0.2Zr0.1 Al0.7Oδcatalyst. The effects of transition metals on the catalytic properties of Ni/Ce0.2Zr0.1 Al0.7Oδautothermal reforming of methane were investigated. The Ni-supported catalysts were characterized by XRD, TPR and XPS. Tests in autothermal reforming of methane to hydrogen showed that the addition of transition metals (Cu and Co) significantly increased the activity of catalyst under the conditions of lower reaction temperature, and Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδwas found to have the highest conversion of CH4 among all catalysts in the operation temperatures ranging from 923 K to 1023 K. TPR, XRD and XPS measurements indicated that the cubic phases of CexZr1-xO2 solid solution were formed in the preparation process of catalysts. Strong interaction was found to exist between NiO and CexZr1-xO2 solid solution. The addition of Cu improved the dispersion of NiO, inhibited the formation of NiAl2O4, and thus significantly promoted the activity of the catalyst Ni/Cu0.05Ce0.2Zr0.1Al0.65Oδ.     

Thermodynamics of Zr<Subscript>52.5</Subscript>Cu<Subscript>17.9</Subscript>Ni<Subscript>14.6</Subscript>Al<Subscript>10</Subscript>Ti<Subscript>5</Subscript> bulk metallic glass forming alloy

Recently, multicomponent glass forming alloys have been found which exhibit extraordinary glass forming ability and cooling rates of less than 100 K/s are sufficient to suppress nucleation of crystalline phases and consequently bulk metallic glass (BMG) is formed. The undercooled melts of BMG systems have high thermal stability in the undercooled region. Therefore, it is interesting to study the thermodynamics of such materials. This article investigates the thermodynamic behavior of a BMG system namely Zr_52.5Cu_17.9Ni_14.6Al₁₀Ti₅ by estimating the Gibbs free energy difference ΔG, entropy difference ΔS, enthalpy difference ΔH between the undercooled liquid and corresponding equilibrium crystalline solid phase, in the entire temperature range from T _m to T _K. Glass forming ability (GFA) of this system has been investigated through various GFA parameters indicating the degree of ease of glass formation.     

Skeletal Ni Catalysts Prepared from Amorphous Ni–Zr Alloys: Enhanced Catalytic Performance for Hydrogen Generation from Ammonia Borane

Skeletal Ni catalysts were prepared from Ni–Zr alloys, which possess different chemical composition and atomic arrangements, by a combination of thermal treatment and treatment with aqueous HF. Hydrogen generation from ammonia borane over the skeletal Ni catalysts proceeded efficiently, whereas the amorphous Ni–Zr alloy was inactive. Skeletal Ni prepared from amorphous Ni₃₀Zr₇₀ alloy had a higher catalytic activity than that prepared from amorphous Ni₄₀Zr₆₀ and Ni₅₀Zr₅₀ alloys. The atomic arrangement of the Ni–Zr alloy also strongly affected the surface structure and catalytic activities. Thermal treatment of the amorphous Ni–Zr alloys at a temperature slightly lower than the crystallization temperature led to an increase of the number of surface‐exposed Ni atoms and an enhancement of the catalytic activities for hydrogen generation from ammonia borane. The skeletal Ni catalysts also showed excellent durability and recyclability.     

Autothermal Reforming of Methane over Ni Catalysts Supported on CuO-ZrO2-CeO2-Al2O3

Ni catalysts supported on various mixed oxides of Al2O3 with rare earth oxide and transitional metal oxides were synthesized. The studies focused on the measurement of the autothermal reforming of methane to hydrogen over Ni catalysts supported on the mixed oxide ZrxCe30-xAl70Oδ (x=5, 10, 15). The catalytic performance of Ni/Zr10Ce20Al70Oδ was better than that of other catalysts. XRD results showed that the addition of Zr to Ni/Ce30Al70Oδ prevented the formation of NiAl2O4 and facilitated the dispersion of NiO. Effects of CuO addition to Zr10Ce20Al70Oδ were also investigated. The activity of Ni catalyst supported on CuO-ZrO2-CeO2-Al2O3 was somewhat affected and the Ni/Cu5Zr10Ce20Al65Oδ showed the best catalytic performance with the highest CH4 conversion, yield of H2, selectivity for H2 and H2/CO production ratio in operation temperatures ranging from 650 to 750℃.     

Ti-Zr-V-Cr-Ni固溶体贮氢合金电极的制备和电化学性能

根据工作环境的要求,镍-金属氢化物电池不仅要满足电源在室温时的工作需要,还应满足在不同工作条件下的需求,如高温、低温等,这就需要电极在较宽的温度范围内具有优异的性能。改性的AB5合金电极在343K时的放电容量能达到265mAh·g-1左右(截止电压为0.5V,相对于Hg/HgO参比电极)[     

Examination of phase changes in the CuAl high-temperature shape memory alloy with the addition of a third element

In the present study, a ternary CuAl-based alloy was produced by adding 2% chromium, niobium, titanium and hafnium instead of 2% copper from the Cu₈₈Al₁₂ (% in mass) shape memory alloy, and the phase changes in the alloy were examined. As a result of the X-ray analyses performed at room temperature, the α phase, which is rich in copper, was detected in the main sample, i.e., the Cu₈₈Al₁₂ alloy, and the β ₁ ¹ and γ ₁ ^? phases were detected in the four of the Cu₈₆Al₁₂Cr₂, Cu₈₆Al₁₂Nb₂, Cu₈₆Al₁₂Ti₂ and Cu₈₆Al₁₂Hf₂ alloys. All of phases were clearly seen in SEM images. As a result of the mapping performed during chemical analysis, it was observed clearly that there appeared a precipitation phase in the Cu₈₆Al₁₂Cr₂, Cu₈₆Al₁₂Nb₂, Cu₈₆Al₁₂Ti₂ alloys due to the additions. It was also observed that the additions were effective in forming a martensite phase in the Cu₈₈Al₁₂ alloy. In differential scanning calorimetry (DSC) measurements, which were taken to support these measurements, no martensitic phase transformations were detected in dual primary alloy (Cu₈₈Al₁₂); however, a clear martensite phase transformation was detected in ternary alloys (Cu₈₆Al₁₂Cr₂, Cu₈₆Al₁₂Nb₂, Cu₈₆Al₁₂Ti₂ and Cu₈₆Al₁₂Hf₂) in the first DSC measurement. Then, when the DSC cycle was applied to the ternary alloy, both the austenite transformation and martensite transformation temperatures were clearly seen, and it was claimed that all the alloys showed high-temperature shape memory alloy properties.     

Preparation of Ag nanocrystals embedded silicate glass by field-assisted diffusion and its properties of optical absorption

Ag nanocrystals embedded silicate glass was successfully prepared by solid-state field-assisted diffusion, combined with post-annealing process. The changes of glass structure, the chemical states of Ag and O species, the microstructures of Ag nanocrystals, as well as the properties of optical absorption were studied for the as-diffused and post-annealed samples. The result showed that after the field-assisted diffusion process, some Ag⁺ ions replaced the alkaline ions in the glass matrix. Meanwhile, other Ag⁺ ions were reduced to Ag⁰ atoms occupying the interspaces of the network and Ag⁰ atoms clusters with small size were formed. This caused the relaxation of the glass network and the deceasing of force constant for Si–O linkage. After post-annealing process, bigger size of Ag nanoparticles were formed, which caused the peak corresponding to the surface plasmon resonance (SPR) observed.     

Interaction of CO with Cu5OZr50 metallic glass surface

The adsorption of CO has been studied on the surface of a Cu₅₀Zr₅₀ metallic glass using X-ray and ultraviolet photoelectron spectroscopic techniques. CO dissociates on both these surfaces leading to the formation of graphitic and carbidic carbon species on the surface. However a reversal in intensity of the two species is observed on the metallic glass surface compared to that on the Zr metal surface. While Zr gets oxidised due to the oxygen produced as a result of the dissociation of CO, Cu remains unoxidised. Contribution No. 501 from the Solid State and Structural Chemistry Unit.     

The electrochemical properties of Al–Si–Ni alloys composed of nanocrystal and metallic glass for lithium-ion battery anodes

Melt-spun Al_75?X Si₂₅Ni _X (X?=?2, 4, 7, and 10?mol%) alloys were investigated as anode materials for lithium-ion batteries. The Al₆₈Si₂₅Ni₇ anode showed a maximum capacity of 840?mA?h?g^?1 at the fifth cycle and maintained 661?mA?h?g^?1 after 40 cycles with a high coulumbic efficiency of 93%. The specific capacity increased as the decrease in the Ni content during the first 20 cycles, but the cycle performance became poorer. For the Al₆₅Si₂₅Ni₁₀ anode, the specific capacity increased slowly as the cycles increased and reached 370?mA?h?g^?1 after 40 cycles. When the Al₆₈Si₂₅Ni₇ ribbons were annealed, their initial capacity became higher, but much poorer cycle performance and low coulumbic efficiency occurred. Except Al₆₅Si₂₅Ni_10, the AlLi compound could be detected in the anodes after lithiation. However, the capacity faded rapidly due to the formation of excessive AlLi in the Al₇₃Si₂₅Ni₂ and annealed Al₆₈Si₂₅Ni₇ anodes. The experiments revealed that the as-quenched ribbons consisted of the nanoscaled α-Al, metallic glass and α-Si, and their fractions were dependent on the Ni content. The α-Al was a supersaturated solid solution of Si and Ni in fcc-Al. For the as-quenched Al₆₈Si₂₅Ni₇ ribbons, the α-Al grains were embedded in the amorphous matrix. It can be understood that metallic glass can store Li, and the supersaturated solid solution can store Li even more easily compared with other known Al–Si-based alloys. A conclusion can be drawn that the microstructure that the nanoscaled α-Al embedded in the metallic glass matrix is beneficial to improve the structure stability, restrain serious structural evolution, and limit the volume variation and pulverization during electrochemical cycles.     

TPR investigations on the reducibility of Cu supported on Al2O3, zeolite Y and SAPO-5

Reducibility of Cu supported on Al₂O₃, zeolite Y and silicoaluminophosphate SAPO-5 has been investigated in dependence on the Cu content using a method combining conventional temperature programmed reduction (TPR) by hydrogen with reoxidation in N₂O followed by a second the so-called surface-TPR (s-TPR). The method enables discrimination and a quantitative estimation of the Cu oxidation states +2, +1 and 0. The quantitative results show that the initial oxidation state of Cu after calcination in air at 400 °C, independent on the nature of the support, is predominantly +2. Cu²⁺ supported on Al₂O₃ is quantitatively reduced by hydrogen to metallic Cu⁰. Comparing the TPR of the samples calcined in air and that of samples additionally pre-treated in argon reveals that in zeolite Y and SAPO-5 Cu²⁺ cations are stabilized as weakly and strongly forms. In both systems, strongly stabilized Cu²⁺ ions are not auto-reduced by pre-treatment in argon at 650 °C, but are reduced in hydrogen to form Cu⁺. The weakly stabilized Cu²⁺ ions, in contrast, may be auto-reduced by pre-treatment in argon at 650 °C forming Cu⁺ but are reduced in hydrogen to metallic Cu⁰.     

Room-Temperature Synthesis of Copper and Silver, Nanocrystalline Chalcogenides in Mixed Solvents

Copper and silver nanocrystalline chalcogenides, Cu_2−xSe, Cu₂Te, Ag₂Se, and Ag₂Te, have been successfully synthesized in a mixture of ethylenediamine and hydrazine hydrate as a solvent at room temperature. Products showed different morphologies, such as nanotubes, nanorods, and nanoparticles. The results indicated that the coordination and chelation abilities of ethylenediamine play an important role in the formation of one-dimensional nanocrystalline binary chalcogenides, and hydrazine hydrate is crucial to the electron transfer in the room temperature reactions. These transition-metal nanocrystalline chalcogenides as prepared were analyzed by X-ray powder diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. The UV-Vis absorption properties of these nanocrystals were also measured.     

Kinetics of crystallization of Zr52Cu18Ni14Al10Ti6 metallic glass

Metallic glasses have received considerable attention in comparison to normal metallic materials due to their superior physical and mechanical properties. These systems possess large under cooled region, ∆T (∆T = T _x − T _g where, T _x is crystallization temperature and T _g is glass transition temperature) and hence increased thermal stability against crystallization. Due to this, the study of their crystallization kinetics is important and interesting. It is interesting because of the fact that, crystallization becomes multi-step process due to several components present in these systems. In this paper, we report the experimental investigations of crystallization of Zr₅₂Cu₁₈Ni₁₄Al₁₀Ti₆ glassy alloy system, which is among the best non-beryllium containing glasses, using differential scanning calorimetry (DSC). The crystallization, as expected, consists of multiple steps. Interestingly, the peak heights of these steps vary with heating rate. At lower heating rates, first peak is most prominent and subsequently diminishes with increase in heating rate with last peak prominence visible at highest heating rate. Both, iso-kinetic and iso-conversional methods of analysis of kinetics of crystallization have been used to evaluate the activation energy and Avrami exponents and consistent results are obtained.     

The role of the interface in a Ti‐based metallic glass matrix composite with in situ dendrite reinforcement

Many in situ metallic glass matrix (MGM) composites have been developed as promising engineering materials having distinguished properties because of sharing virtues of high strength of metallic glasses and large plasticity of crystal phase, for example, Ti₄₇Zr₁₉Be₁₅V₁₂Cu₇ MGM composites (the yield strength: 1600 MPa, the fracture strength: 3024 MPa and the total strain 32.6%). Although the toughening mechanisms in these materials have been investigated, the role of the interface bridging the ductile dendrite and the glass phase is still unclear. To this aim, specimens of the as‐received and after compression of this Ti‐based MGM composite were investigated to by using the transmission electron microscopy and the high‐resolution transmission electron microscopy. The results of the microstructure investigation indicated that the interface in the composite consists of a nanosized transform layer with an approximate width of 4 nm. During plastic deformation, the interface either suppresses plastic deformation caused by dislocations on the dendrite side or initiates nucleation of multiple shear bands throughout nanocrystallization on the glass phase side nearby the interface, which is favorable for the plastic deformation of the material. Copyright © 2014 John Wiley & Sons, Ltd.