Fatigue Softening of (Zr58Ni13.6Cu18Al10.4)99Nb1 Bulk Metallic Glass

The fatigue study was conducted on the (Zr₅₈Ni_13.6Cu₁₈Al_10.4)₉₉Nb₁ bulk metallic glass (BMG) under four-point bending with a maximum stress of 600 MPa. After the fatigue experiment, compression tests were performed with samples cut from three different sections, including sections a: within the inner pins, b: between inner and outer pins, and c: outside the outer pins. It is concluded that, as the fatigue damage increases, the compression flow stress decreases, the ductility increases, and the deformation becomes more homogeneous.     

Kinetic study on the non-isothermal crystallization of Gd53Al24Co20Zr3 bulk metallic glass

Gd-based bulk metallic glass has drawn strong attention because of its large magnetic entropy changes. Thermal stability of metallic glass is a very important issue for its application. In the paper, crystallization behavior of Gd53Al24Co20Zr3 bulk metallic glass was investigated using non-isothermal differential scanning calorimetric (DSC) technique. Attention was given to the analytic details. The crystallized volume fractions as a function of temperature were derived from the DSC signals, where heat capacity change between amorphous phase and crystalline phase was considered. The local activation energies at different crystallized volume fraction were estimated using Doyle-Ozawa and Agrawal methods. The results suggested that the Doyle-Ozawa equation was appropriate to get local activation energy due to its simplicity and accuracy. The local activation energy depended on the crystallized volume fraction. Function reflecting crystallization mechanism was also deduced. The crystallization mechanism of the Gd-based bulk metallic glass was discussed.     

Roles of In-Situ Forming Hard Particles in a Zr-Based Bulk-Metallic Glass during Monotonic and Cyclic Loading

Zr₆₇Ni₂₀Cu₅Al₈ (in at. pct) is a bulk-metallic glass (BMG) with in-situ forming hard particles. Some crystalline particles can be observed in the polished beam samples under optical microscopy (OM). The hardness measurements show that these crystalline particles are harder than the matrix of Zr₆₇Ni₂₀Cu₅Al₈. The energy-dispersive spectroscopy (EDS) analyses demonstrate that there is little difference in the compositions between the crystalline particles and the matrix. The Zr₆₇Ni₂₀Cu₅Al₈ BMG under compressive loading exhibits yield strength of 1580 MPa with an up to 7.7 pct fracture strain. The fatigue behavior of Zr₆₇Ni₂₀Cu₅Al₈ is investigated under four-point-bending loading. The fatigue results show that the fatigue limit of Zr₆₇Ni₂₀Cu₅Al₈ is approximately 361 MPa, based on the stress range. It is generally found that the fatigue cracks initiate from the hard particles. The influence of the hard inclusions on the fracture and fatigue behavior of Zr-based BMGs is discussed.     

Effect of metal doping into Ce0.5Zr0.5O2 on catalytic activity of MnOx/Ce0.5–xZr0.5–xM0.2xOy/Al2O3 for benzene combustion

The research investigated the effect of doping two metals separately or together into Ce0.5Zr0.5O2 on the catalytic activity of MnOx/Ce0.5-xZr0.5-xM0.2xOy/Al2O3 （M=Y, Mn, Y and Mn） for catalytic combustion of benzene. The prepared catalysts were characterized by X-ray diffraction （XRD）, surface area analysis, oxygen storage capacity （OSC）, and H2-temperature programmed reduction （H2-TPR）. Catalytic test was performed on a conventional fixed bed flow reactor. The characterization results revealed that Y and Mn ions entered into the ceria-zirconia mixed oxides framework, which improved the textural properties and greatly promoted the MnOx dispersion on the support surface. The complete conversion temperature of benzene on MnOx/Ce0.4Zr0.4Y0.1Mn0.1Oy/Al2O3 was 563 K, and the selectivity of carbon dioxides was 99%. This catalyst could be applied in a wide range of GHSV and wide concentration condition, showing great potential for application.     

Enhanced Mechanical Properties by Cyclic Compression in TiNb/Zr-Based Metallic Glassy Composite

A significant enhancement of yield strength and large plasticity was obtained in TiNb/Zr₅₅Cu₃₀Al₁₀Ni₅ composite by cyclic compression at the yield point. This phenomenon resulted from the cooperation of the metallic crystalline alloy TiNb and metallic glassy matrix Zr₅₅Cu₃₀Al₁₀Ni₅ in the composite. It was found that a large dislocation density of TiNb was produced during cyclic compression, which resulted in the increase of the strength. Meanwhile, the improvement of plasticity of the composite benefited from the propagation of excess shear bands in the glassy matrix, which were produced during the cyclic compression process. Hence, the collective effect of both resulted in the improved yield strength and large plasticity of the composite.     

Effects of crystal field on photoluminescence properties of Ca2Al2SiO7:Eu2+ phosphors

A series of single-phased Ca₂Al₂SiO₇:Eu²⁺ phosphors were synthesized by the solid-state reaction. Their structure and photolumi-nescence properties were investigated by the X-ray powder diffraction （XRD） and excitation and emission spectra in detail. The emission spectra of Ca₂Al₂SiO₇:Eu²⁺ phosphors consisted of blue and green band located at419 and542 nm, respectively. The relative intensities of the blue and green emission changed with Eu²⁺ concentration and were sensitive to the excitation wavelength. The unique photoluminescence property originated from the 4f⁷→4f⁶5d transition of Eu²+ at different energy levels, on which the effect of the crystal field strength was con-sidered to be tailed by adjusting the host composition.     

Effect of Metal Oxide Doping into Ce0.5Zr0.5O2 on Catalytic Activity of MnOx/γ-Al2O3/Ce0.45Zro.45M0.1Ox （M = Y, La, Mn） Honeycomb Catalysts

This article showed that the catalytic activity of MnOx/γ-Al2O3/Ce0.5Zr0.5O2 monolithic catalyst toward the catalytic combustion of ethanol in a fixed bed reactor could be greatly improved by doping three metal oxides into Ce0.5Zr0.5O2. The catalytic activity of MnOx/γ-Al2O3/Ce0.45Zr0.45M0.1 Ox （M = Y, La, Mn） is better than that of MnOx/γ-Al2O3/Ce0.5 Zr0.5O2. The order of activity of the catalysts is as follows： MnOx/γ-Al2O3/Ce0.45Zr0.45Y0.1Ox 〉 MnOc/γ-Al2O3/Ce0.45 Zr0.45La0.1Ox 〉 MnOx/γT-Al2O3/Ce0.45Zr0.45Mn0.1Ox 〉 MnOx/y-Al2O3/Ce0.5Zr0.5O2. The influence of the loading amount of manganese oxide in enhancing the catalytic activity of MnOx/γ-Al2O3/Ce0.45Zr0.45Y0.1 Ox was investigated. The results showed that when MnO2 loading amount was 10% （mass fraction）, the MnOx/Al2O3/Ce0.45Zr0.45Y0.1Ox catalyst recorded the highest activity.     

Tough Hypoeutectic Zr-Based Bulk Metallic Glasses

Significant softening of Zr-based bulk metallic glasses (BMGs) can be seen in a hypoeutectic Zr-enriched composition, which brings about very high toughness (for the Zr₅₅Cu₃₅Al₁₀ and Zr₆₀Cu₃₀Al₁₀ BMGs) and tensile plasticity at room temperature (for the Zr₇₀Ni₁₆Cu₆Al₈ BMG). The unique features of such BMGs include the formation of multiple shear bands and harmonic alternating movements that can immediately accommodate concentrated stresses and avoid accidental catastrophic fracture.     

Mapping the Strain Distributions in Deformed Bulk Metallic Glasses Using Hard X-Ray Diffraction

The deformation behavior of Cu₄₅ Zr_46.5 Al₇Ti_1.5 bulk metallic glass (BMG) under bending was investigated in-situ using high-energy X-ray synchrotron diffraction. Samples were bent using two different benders with radii of 10 and 20 mm. The components of the strain tensor were determined from the change of positions of the first maximum of the diffracted intensity in reciprocal space. The procedure of data treatment was improved by the introduction of direct beam off-center correction. Comparing results for the two different bending radii, we found that the zero stress region does not necessarily lay within the central part of the specimen. Bending with smaller radius resulted in symmetric strain distribution, whereas a larger bending radius revealed strong asymmetry. Furthermore, bending with a smaller radius (10 mm) shows steeper strain gradients as compared with the situation in which the larger bending radius (20 mm) was used. Using a smaller bending radius implies reaching higher tensile/compressive stresses and reveals the signs of the plastic deformation, which are demonstrated as a saturation of elastic strains.     

Deformation and Fracture Behavior of Metallic Glassy Alloys and Glassy-Crystal Composites

The present work demonstrates the deformation behavior of Zr-Cu-Ni-Al bulk glassy alloys and Zr-Ni-Cu-Al-Pd glassy foils as well as Ni-Cu-Ti-Zr bulk crystal-glassy composites. Fracture of Zr₆₀Cu₁₆Ni₁₄Al₁₀ and Zr_64.13Ni_10.12Cu_15.75Al₁₀ bulk glassy alloys is featured by nearly equal fraction areas of cleavage-like and vein-type relief. The observed pattern of alternating cleavage-like and vein-type patterns illustrates a result of dynamically self-organizing shear propagation at the final catastrophic stage. The deformation behavior of Zr_64.13Ni_10.12Cu_15.75Al₁₀ alloy has also been tested at LN₂ temperature. The strength of the sample decreases with temperature, and no clear serrated flow typical for bulk glassy samples tested at room temperature is observed in the case of the samples tested at LN₂ temperature. We also studied the deformation behavior of Zr-Ni-Cu-Al-Pd glassy foils thinned to electron transparency in situ in tension in a transmission electron microscope. We also present a Ni-Cu-Ti-Zr crystal-glassy composite material having a superior strength paired with a considerable ductility exceeding 10 pct. The metastable cP2 crystalline phase promotes a strain-induced martensitic transformation leading to pseudoelastic behavior as well as enhanced plasticity at room temperature. Underlying mechanisms of plastic deformation are discussed in terms of the interplay between the dislocation slip in the crystalline phase and the shear deformation in the glassy matrix.     

Influence of Ce0.35Zr0.55Y0.10 Solid Solution on Performance of Pt-Rh Three-Way Catalysts

Ce0.35Zr0.55Y0. 10 solid solution was prepared by co-precipitation technique and characterized by specific surface area measurements （BET） and X-ray diffraction （XRD）. Ce0.35Zr0.55Y0.10 was used to prepare low Pt-Rh threeway catalyst （TWC）, and its influence on the performance of TWC was investigated. The results revealed that Ce0.35 Zr0.55Y0.10 had a cubic structure similar to Ce0.50Zr0.50O2 and its specific surface area can maintain higher than Ce0.50 Zr0.50O2 after 1000 ℃ calcination for 5 h. Being hydrothermal aged at 1000 ℃ for 5 h, the catalyst containing Ce0.35 Zr0.55Y0.10 still exhibited higher conversion of C3H8, CO and NO and lower light-off temperature in comparison with Ce0.50Zr0.50O2 TWC.     

Oxidation and Crystallization Behavior of Quinary Zr-Based Bulk Metallic Glasses

Non-isothermal and isothermal oxidation behavior of four Zr-based bulk metallic glasses (Zr₅₈Cu₂₂Co₄Ag₄Al₁₂, Zr₅₈Cu₂₂Co₂Ag₆Al₁₂, Zr₅₈Cu₂₂Fe₄Ag₄Al₁₂, and Zr₅₈Cu₂₂Fe₂Ag₆Al₁₂ (compositions are in at.%)) has been studied in oxygen environment. Non-isothermal oxidation has been performed at different heating rates up to 1,173 K to understand the effect of progressive crystallization on the oxidation behavior. In addition, crystallization behavior of the glassy alloys has been studied, and activation energies have been calculated in an inert and oxygen environment. Partial replacement of iron with silver and cobalt has a distinct effect on the oxidation and crystallization behavior of the alloys. Oxidation of the glassy alloys starts with the dissolution of oxygen in the amorphous matrix followed by rapid oxidation after crystallization.     

Influence of Melt-Spinning Parameters on the Structure and Soft Magnetic Properties of (Fe0.65Co0.35)88Zr7B4Cu1 Alloy

Melt-spun ribbons of (Fe_0.65Co_0.35)₈₈Zr₇B₄Cu₁ alloy have been prepared at different wheel speeds, namely, 47, 39, 34, and 17 m/s, and subsequently annealed at 773 K (500 °C) under controlled atmosphere. Structural and soft magnetic properties have been evaluated using X-ray diffraction, differential scanning calorimetry, transmission electron microscopy, and vibrating sample magnetometer. The structure of as-spun ribbons changes from fully amorphous to partially amorphous/nanocrystalline to fully nanocrystalline (bcc α-Fe(Co) + Fe₂Zr) on decreasing the wheel speed. Annealing of amorphous ribbons leads to the precipitation of nanocrystalline bcc α-Fe(Co) phase. The Curie temperature (T _c ) of the amorphous phase is found to increase with decreasing wheel speed possibly due to the effect of exchange field penetration of nanocrystals present in the amorphous matrix. The saturation magnetization (4πM _s ) of as-spun ribbons having partially nanocrystalline bcc α-Fe(Co) phase is high as compared to the ribbons with completely amorphous phase, and it remains almost the same even after annealing. The lowest coercivity has been achieved in the ribbons that are fully amorphous, and the coercivity was found to increase with decreasing wheel speed.     

Deformation and failure of Zr<Subscript>57</Subscript>Nb<Subscript>5</Subscript>Al<Subscript>10</Subscript>Cu<Subscript>15.4</Subscript>Ni<Subscript>12.6</Subscript>/W particle composites under quasi-static and dynamic compression

We have investigated the mechanical behavior of a composite material consisting of a Zr₅₇Nb₅Al₁₀Cu_15.4Ni_12.6 metallic glass matrix with 60 vol pct tungsten particles under uniaxial compression over a range of strain rates from 10⁻⁴ to 10⁴ s⁻¹. In contrast to the behavior of single-phase metallic glasses, the failure strength of the composite increases with increasing strain rate. The composite shows substantially greater plastic deformation than the unreinforced glass under both quasi-static and dynamic loading. Under quasi-static loading, the composite specimens do not fail even at nominal plastic strains in excess of 30 pct. Under dynamic loading, fracture of the composite specimens is induced by shear bands at plastic strains of approximately 20 to 30 pct. We observed evidence of shear localization in the composite on two distinct length scales. Multiple shear bands with thicknesses less than 1 μm form under both quasi-static and dynamic loading. The large plastic deformation developed in the composite specimens is due to the ability of the tungsten particles both to initiate these shear bands and to restrict their propagation. In addition, the dynamic specimens also show shear bands with thicknesses on the order of 50 μm; the tungsten particles inside these shear bands are extensively deformed. We propose that thermal softening of the tungsten particles results in a lowered constraint for shear band development, leading to earlier failure under dynamic loading.     

NiO-Ce0.5Zr0.5O2 catalysts prepared by citric acid method for steam reforming of ethanol

NiO-Ce0.5Zr0.5O2 catalysts were prepared by citrate method and used for hydrogen production from steam reforming of ethanol （SRE）. The effect of nickel content and space velocity on the catalytic performance was investigated. The prepared catalysts were characterized with XRD and thermal analysis techniques. 20%NiO-Ce0.5Zr0.5O2catalyst was very active and selective for hydrogen production via SRE, in which ethanol conversion of 100% could be obtained with feed component of 20% （H2O＋EtOH） and 80% N2, water/ethanol of 3/1 in molar ratio at 350 ℃. Also, the catalyst showed good stability for anti-sintering and carbon-resistance. The XRD illuminated that both NiO and Ce0.5Zr0.5O2 crystal sizes were very small in NiO-Ce0.5Zr0.5O2 catalyst, and Ce0.5Zr0.5O2 solid solution was formed.     

The Effects of Fatigue on the Atomic Structure with Cyclic Loading in Zr50Cu40Al10 and Zr60Cu30Al10 Glasses

The potential damage effect from fatigue on Zr bulk metallic glass alloys of Zr₅₀Cu₄₀Al₁₀ at the eutectic point and Zr₆₀Cu₃₀Al₁₀ away from the eutectic point (in atomic percent) is examined via the local atomic structure, which was obtained from the pair density function analysis of the synchrotron X-ray radiation and neutron data. Samples cut from the same rods were subjected to 10⁴, 10⁵, and 10⁶ compression cycles ex situ, and the evidence for fatigue damage was investigated by comparing alloys before and after cyclic loading. Bond orientation was observed particularly in Zr₅₀Cu₄₀Al₁₀, suggesting that fatigue damage occurs even in the elastic range, below the yield point, and during cyclic loading. The initiation of fatigue changes is observed first within small localized atomic regions.     

Size Effect on Flow Behavior of a Zr55Al10Ni5Cu30 Bulk Metallic Glass in Supercooled Liquid State

Size effect on the flow behavior of Zr₅₅Al₁₀Ni₅Cu₃₀ bulk metallic glass in its supercooled liquid state was investigated by compression tests with specimen diameters varying from 1 to 3 mm. It was found that the smaller the specimen, the higher flow stress exhibits. Strain gradient theory considering friction effect is validated to be suitable to rationalize this size effect. The more geometrical-necessary flow sites needed to be created in smaller specimens, the higher stress it may result in. Considering the efficiency of power dissipation and instability condition, processing maps of different specimens were constructed. With the specimen size decreasing, the processing condition corresponding to low temperature or high strain rate becomes disadvantageous to the thermoplastic forming of Zr₅₅Al₁₀Ni₅Cu₃₀, which is closely related to the local stress concentration and strain gradient induced by friction.     

Microstructural Evolution and Mechanical Properties of Zr-Cu-Ni-Al Bulk Metallic Glasses by the Bridgman Solidification

The microstructural evolution was experimentally studied at a withdrawal velocity between 6 and 0.1?mm/s by a Bridgman technique in Zr_51.7Cu₃₀Ni_8.3Al₁₀. Our results indicate that the Zr_51.7Cu₃₀Ni_8.3Al₁₀ alloy can be considered as the ZrCu-Zr₂Cu pseudo-binary eutectic system, and the glass-forming ability (GFA) is correlated with the (L ?? ZrCu?+?Zr₂Cu) pseudo-binary eutectic reaction. This understanding has important implications and guidance for designing and fabricating new Zr-Cu-Ni-Al bulk metallic glasses (BMGs) with superior glass formation. Moreover, compressive tests were also performed on these samples. The results show that as the precipitation of crystal, plastic strain decreases. It indicates that the precipitated crystal cannot block the fast propagation of the localized shear bands and the macroscopically brittle failure.     

Effect of Nb Content on Mechanical Behavior and Structural Properties of W/(Zr55Cu30Al10Ni5)100−x Nb x Composite

In the present study, (Zr₅₅Cu₃₀Al₁₀Ni₅)_100−x Nb_(x=0,1,2,3) bulk metallic glass matrix/tungsten wire composites were fabricated by infiltration process. Structural studies were investigated by scanning electron microscopy and X-ray diffraction method. Also, mechanical behaviors of the materials were analyzed using quasi-static compressive tests. Results indicated that the best mechanical properties i.e., 2105 MPa compressive ultimate strength and 28 pct plastic strain before failure, were achieved in the composite sample with X = 2. It was also found that adding Nb to the matrix modified interface structure in W fiber/(Zr₅₅Cu₃₀Al₁₀Ni₅)₉₈Nb₂ since the stable diffusion band formation acts as a functionally graded layer. Finally, the observation of multiple shear bands formation in the matrix could confirm the excellent plastic deformation behavior of the composite.

     

Formation,Structure, and Crystallization Behavior of Cu-Based Bulk Glass-Forming Alloys

We studied Cu-Zr–based alloys having exceptionally high glass-forming ability (GFA) and investigated the influence of Ag and Al addition on their structure and crystallization behavior. Most of the bulk glassy alloys (BGAs) do not contain any crystals, while some samples studied by high-resolution transmission electron microscopy (HRTEM) were found to contain well-developed medium-range order zones and nanoparticles in a bulk form. The crystallization kinetics of Cu₅₅Zr₄₅, Cu₅₀Zr₅₀, Cu_55–x Zr₄₅Ag _x (x = 0, 10, 20), Cu₄₅Zr₄₅Al₅Ag₅, Cu₄₄Ag₁₅Zr₃₆Ti₅, and Cu₃₆Zr₄₈Al₈Ag₈ glassy alloys was analyzed. An influence of the cooling rate on the formation of glassy phase and thermal stability of the Cu-based glassy alloys on heating was also studied. The crystallization kinetics and phase composition of the ribbon-shape and bulk glassy samples of Cu₃₆Zr₄₈Al₈Ag₈ alloys were also analyzed. The results also indicate that the best glass-forming compositions are possibly located at slightly off-eutectic area, owing to the shift of the eutectic point due to the nonequilibrium processing conditions.