Centimeter-sized Ti-based bulk metallic glass with high specific strength

Based on the quaternary Ti₄₁Zr₂₅Be₂₉Al₅ glassy alloy with a critical diameter of 7 mm reported not long ago, an obvious enhancement of glass-forming ability (GFA) has been realized in this alloy by the addition of Cu element. A series of (Ti₄₁Zr₂₅Be₂₉Al₅)_100?xCu_x (x=0, 2, 5, 7, 9, 11 at%) glassy alloys have been developed and some of them can be cast into one-centimeter diameter fully glassy rods by copper mold suction casting. It has been found that Cu addition could stabilize the liquid phase and suppress the crystallization, resulting in improvement of the GFA of the alloy. The addition of Cu also increases the compressive strength of the alloy and the (Ti₄₁Zr₂₅Be₂₉Al₅)₉₁Cu₉ glassy alloy possesses a specific strength (defined as yield strength/density) of 4.13×10⁵ Nm/kg, which is much higher than most other reported centimeter-sized bulk metallic glasses. The present result suggests that the newly developed (Ti₄₁Zr₂₅Be₂₉Al₅)₉₁Cu₉ glassy alloy is a good candidate for structural applications because of its good glass-forming ability and mechanical properties.     

BaCe1-x Yx O3-δ质子导体的制备与性能

采用高温固相合成法制备出掺杂Y³⁺的BaCeO₃电解质BaCe_1-xY_xO_3-δ（x=0.10~0.30). XRD谱分析结果表明,样品均为正交钙钛矿结构;氧空位、 缺陷缔合和固深度均对样品的质子电导率与掺杂浓度有一定影响.     

Microstructural characterization and hydrogenation performance of Zr_xV_5Fe(x=3-9) alloys

Zr_xV_5 Fe(x=3,5,7,8,9) alloys were designed to investigate the influence of Zr addition on hydrogenation performance.The alloys were prepared by arc melting and then annealed at 1273 K for 168 h.The results showed that the alloys were composed of α-Zr and C15-ZrV2 phases.The cell volume of C15-ZrV_2 phase firstly increased and then decreased as the content of Zr increased,while the reversed trend was found for the cell volume of α-Zr phase,which was related to the stoichiometric ratio of elements.α-Zr phase distributed in C15-ZrV2 phase matrix in Zr_xV_5 Fe(x=5,7,8,9) alloys,among which Zr7 V5 Fe alloy showed the best distribution.The PCT curves of the alloys under 623 K,673 K and 723 K showed that the hydrogen absorption plateau pressure of the phases in different alloys decreased gradually with the increasing content of Zr.However C15-ZrV2 phase in Zr7 V5 Fe alloy had the lowest hydrogen absorption plateau pressure at room temperature,which was consistent with the change tendency of the corresponding cell volume.Moreover,the kinetic curves of hydrogen absorption at 623 K revealed that Zr7 V5 Fe alloy with the smallest average particle size and the largest phase boundary area showed the fastest hydrogen absorption kinetics.Compared with other four alloys(including St707 alloy),Zr_7 V_5 Fe alloy is more suitable for the use of getter.     

Revisiting Al-Ni-Zr bulk metallic glasses using the ＇cluster-resonance＇ model

Six series of alloys,namely,Ni3Zr6Alx,Ni3Zr7Alx,Ni4Zr9Alx,Ni3Zr8Alx,Ni3Zr9Alx and Ni3Zr10Alx (x=1,1.5,2,3) were designed in this work and the bulk metallic glass (BMG) formation of these compositions was investigated by copper mold suction casting. A centimeter-scale BMG sample was obtained for the Ni4Zr9Al2 (Al13.3Ni26.7Zr60 in atomic percent) composition. The thermal glass parameters for this BMG were determined to be ΔTx = 68 K,Trg = 0.579,and γm = 0.689. Using the ’cluster-resonance’ model for glass formation an optimal BMG composition was determined using the cluster formula [Ni3Zr9](Al2Ni1).     

Effect of Nb on the corrosion behavior of continuous bulk metallic glass-coated steel wire composites

(Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5)_100?xNb_x (at%, x=0 and 8) bulk metallic glasses (BMGs) were coated on the surface of Q195 steel wires by a continuous coating process. The potentiodynamic polarization tests of these BMGs were conducted in 3.5wt% NaCl aqueous solution. It is found that the addition of 8at% Nb into Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 alloy results in the improvement of corrosion resistance with the pitting potential of ?52 mV, the open circuit potential of ?446 mV, and the corrosion current density of 9.86×10?6 mA/cm2. This may be attributed to that Nb is beneficial to passivate and stabilize Zr and Ti.     

Mechanism of Ag and Al on improving the glass forming ability of CuZr-based alloys

By a mean field theoretical computation, the equilibrium distributions of additional Ag and Al in the crystalline phase of CuZr-based alloys were determined to occupy the two sublattices of the B2 structure randomly. With the molecular dynamics technique, the effects of Ag and Al on the enthalpy difference (ΔH) between the supercooled melt and the crystalline phase were evaluated. The improved glass forming ability of Cu₄₅Zr₄₅Al₁₀and Cu₄₅Zr₄₅Ag₁₀ can be attributed to their remarkably smaller ΔH than that of CuZr. The calculated diffusion coefficients are more sensitive to the atomic weight of the component atoms than to their interaction strength. As the component atom with the largest mass, the additional Ag increases the viscosity of the supercooled melt significantly and the experimentally stronger glass formation ability of Cu₄₅Zr₄₅Ag₁₀ than Cu₄₅Zr₄₅Al₁₀ can be well understood.     

Synthesis,structure and mechanical properties of Zr-Cu-based bulk metallic glass composites

The unusual glass-forming ability (GFA) of the Zr₄₈Cu₃₆Ag₈Al₈ alloy and the high ductility of the Zr₄₈Cu₃₆Ag₈Al₈ metallic glass-matrix composites containing Ta powder were reported. The bulk metallic glass rod with a diameter of 25 mm was successfully synthesized using copper mold casting for the Zr₄₈Cu₃₆Ag₈Al₈ alloy. High GFA of this alloy was found to be related to a large supercooled liquid region and a quaternary eutectic point with low melting temperature. The bulk metallic glass matrix composites were prepared by introducing extra Ta particles into the Zr₄₈Cu₃₆Ag₈Al₈ melt. The composites consist of Ta particles homogenously distributed in the Zr₄₈Cu₃₆Al₈Ag₈ metallic glass matrix. The optimum content of Ta powder is 10at% for the composite with the highest plasticity, which shows a plastic strain of 31%.     

Influence of yttrium on the structure and magnetostriction of Fe83Ga17 alloy

Polycrystalline Fe₈₃Ga₁₇ alloy rods with various amounts of yttrium were prepared by high vacuum induction melting. It is found that yttrium addition has a significant effect on the structure and magnetostriction of Fe₈₃Ga₁₇ alloy. The small addition of yttrium alters the solidification character and the grain shape of Fe₈₃Ga₁₇ alloy, and as a result, columnar grains with the ??100?? preferential direction are produced. Yttrium addition improves the magnetostrictive performance of the as-cast Fe₈₃Ga₁₇ alloy. The magnetostriction values of the as-cast alloy with 0.32at% and 0.64at% yttrium addition go up to 119×10^?6 and 137×10^?6 under 15 MPa compressive stress, respectively. The energy dispersive spectroscopy (EDS) result shows that almost all of the yttrium atoms exist in the Y₂Fe_17?x Ga _x phase. A small amount of this kind of secondary phase cannot obviously increase the saturate magnetic field.     

Formation and properties of high Fe-content Fe-(B-Si)-Zr bulk amorphous alloys

The present work is devoted to the development of Fe-(B-Si)-Zr amorphous alloys with high glass-forming ability and good magnetic properties. Using the cluster-plus-glue-atom model proposed for ideal amorphous structures, [FeFe₁₁B₃Si](Fe_1?xZr_x) was determined as the cluster formula of Fe-(B-Si)-Zr alloys. The glass formation and thermal stability of the serial alloys, namely, [FeFe₁₁B₃Si](Fe_1?xZr_x) (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.75, and 1.0), were studied by the combination of copper mold casting, X-ray diffraction, and differential thermal analysis techniques. The maxima of glass-forming ability and thermal stability were found to occur at the compositions of [FeFe₁₁B₃Si](Fe_0.6Zr_0.4) and [FeFe₁₁B₃Si](Fe_0.5Zr_0.5). The alloys can be cast into amorphous rods with 1.5 mm diameter, and upon reheating, the amorphous alloys exhibit a large undercooled liquid span of 37 K. The saturation magnetization of the [FeFe₁₁B₃Si](Fe_0.5Zr_0.5) amorphous alloy was measured to be 1.4 T.     

A Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous filler metal for improving the strength of Ti–6Al–4V alloy brazing joint

Ti_(50)Zr_(27)Cu_8Ni_4Co_3Fe_2Al_3Sn_3(at%) amorphous filler metal with low Cu and Ni contents in a melt-spun ribbon form was developed for improving mechanical properties of Ti–6Al–4V alloy brazing joint through decreasing brittle intermetallics in the braze zone. Investigation on the crystallization behavior of the multicomponent Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous alloy indicates the high stability of the supercooled liquid against crystallization that favors the formation of amorphous structure. The Ti–6Al–4V joint brazed with this Ti-based amorphous filler metal with low total content of Cu and Ni at 1203K for 900s mainly consists of α-Ti, β-Ti,minor Ti–Zr-rich phase and only a small amount of Ti_3Cu intermetallics, leading to the high shear strength of the joint of about 460 MPa. Multicomponent composition design of amorphous alloys is an effective way of tailoring filler metals for improving the joint strength.     

Structure and multiferroic properties of Y-doped BiFeO3 ceramics

Bismuth ferrite, BiFeO₃, is an important multiferroic material, which simultaneously exhibits ferroelectric ordering and antifer-romagnetic ordering in bulk form. Samples of Bi_1-xY_xFeO₃ (x=0, 0.05, 0.10, 0.15 and 0.20) were prepared by conventional solid state reaction. By X-ray diffraction and Raman scattering spectra, the crystal structures of the samples were identified as rhombo-hedral with R3c space group, in addition to a second phase at x≥0.05. Multiferroic properties of the samples were also measured. With the increasing of Y content, the relative dielectric constants of the samples increased gradually, while the loss tangents firstly decreased and then began to increase. Meanwhile, the saturation magnetization values were significantly enhanced, namely 0.1440, 0.7468, 1.9217, 3.3309 and 6.2774 emu/g at 300 K for x=0, 0.05, 0.10, 0.15 and 0.20, respectively.     

Preparation of Al<Subscript>72</Subscript>Ni<Subscript>8</Subscript>Ti<Subscript>8</Subscript>Zr<Subscript>6</Subscript>Nb<Subscript>3</Subscript>Y<Subscript>3</Subscript> amorphous powders and bulk materials

Amorphous Al₇₂Ni₈Ti₈Zr₆Nb₃Y₃ powders were successfully fabricated by mechanical alloying. The microstructure, glass-forming ability, and crystallization behavior of amorphous Al₇₂Ni₈Ti₈Zr₆Nb₃Y₃ powders were investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). The isothermal crystallization kinetics was analyzed by the Johnson–Mehl–Avrami equation. In the results, the supercooled liquid region of the amorphous alloy is as high as 81 K, as determined by non-isothermal DSC curves. The activation energy for crystallization is as high as 312.6 kJ·mol?1 obtained by Kissinger and Ozawa analyses. The values of Avrami exponent (n) imply that the crystallization is dominated by interface-controlled three-dimensional growth in the early stage and the end stage and by diffusion-controlled two- or three-dimensional growth in the middle stage. In addition, the amorphous Al₇₂Ni₈Ti₈Zr₆Nb₃Y₃ powders were sintered under 2 GPa at temperatures of 673 K and 723 K. The results show that the Vickers hardness of the compacted powders is as high as Hv 1215.     

块状金属玻璃Zr55Cu30Al10Ni5的微压痕尺寸效应

基于Drucker-Prager屈服准则,建立了适用于描述压敏材料的低阶应变梯度塑性(CMSG)理论. 通过ABAQUS自定义材料子程序(UMAT),构造了CMSG理论本构计算的有限元格式,并对块状金属玻璃Zr₅₅Cu₃₀Al₁₀Ni₅的圆锥压痕实验响应进行了数值模拟分析. 计算结果与实验数据相吻合,表明该理论可以很好地描述金属玻璃的弹塑性行为. 在此基础上,研究了不同压深下的载荷位移曲线和硬度,计算结果显示该材料的硬度随着压痕深度的增大而减小,表明基于Drucker-Prager屈服准则的CMSG理论可以预测金属玻璃Zr₅₅Cu₃₀Al₁₀Ni₅在微米尺度下表现出来的尺寸效应现象. 此外,通过分析不同摩擦因数下材料的载荷位移曲线,表明摩擦力对该材料微压痕响应的影响可以忽略不计.     

Correlation between the glass-forming ability and activation energy of crystallization for Zr75−x Ni25Al x metallic glasses

The thermal stability and the kinetics of glass transition and crystallization for Zr_75?x Ni₂₅Al _x (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 Al content increasing; the activation energy of crystallization increases with Al changing from 8at% to 15at%, and then decreases with Al further up to 24at%, which exhibits a good correlation to the thermal stability and the glass-forming ability (GFA). The Zr₆₀Ni₂₅Al₁₅ 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.     

Co80+xZr20-x合金的永磁性能

利用X射线衍射和磁性测量研究Co_80+xZr_20-x（x=0,1,2,3,4）合金、 快淬薄带的结构与磁性. 结果表明, 所有样品的比饱和磁化强度均较大, 且在实验范围内随退火温度的升高而增加; 经750℃热处理2 h后, Co₈₁Zr₁₉样品的比饱和磁化强度达到最大值128 (A·m2)/kg; Co₈₂Zr₁₈快淬样品在25 m/s速率下的矫顽力最大, 为60 kA/m, 根据该样品中Co5Zr相的含量较大可知, Co₅Zr相为Co-Zr合金的硬磁相; 由初始磁化曲线可知, 所有样品的矫顽力机制为成核模型.      

Preparation of Al-Cu-Fe-(Sn,Si) quasicrystalline bulks by laser multilayer cladding

(Al₆₅Cul₂₀Fe₁₅)_100-x Sn_x (x=0, 12, 20, 30) and Al₅₇Si₁₀Cu₁₈Fe₁₅ powders were cladded on a medium carbon steel (45# steel) substrate by laser multilayer cladding, respectively. The phases and properties of the produced quasicrystalline bulks were investigated. It was found that the main phases in the Al₆₅Cul₂₀Fe₁₅ sample were crystalline λ-Al₁₃Fe₄ and icosahedral quasicrystal together with a small volume fraction of θ-Al₂Cu phase. The volume fraction of icosahedral phase decreased as the Sn content in the (Al₆₅Cul₂₀Fe₁₅)_100-x Sn_x samples increased owing to the formation of β-CuSn phase. The increase of Sn content improved the brittleness of the quasicrystal samples. The morphology of the solidification microstructure in the Al₅₇Si₁₀Cu₁₈Fe₁₅ sample changed from elongated shape to spherical shape due to the addition of Si. The nanohardness of the laser multilayer cladded quasicrystal samples was equal to that of the as-cast sample prepared by vacuum quenching. In terms of hardness, the laser cladded Al₅₇Si₁₀Cu₁₈Fe₁₅ quasicrystalline alloy has the highest value among all the investigated samples.     

Sintering mechanism of Cu-9Al alloy prepared from elemental powders

The sintering behavior of Cu-9Al alloys prepared from die pressing of elemental powders was investigated. The experimental results and kinetic analysis showed the formation of three consecutive layers of Al₂Cu, Al₄Cu₉, and AlCu phases, with Al₂Cu appearing first in the initial solid phase sintering stage. A liquid phase formed in the intermediate stage, resulting from the eutectic reaction between Al and Al₂Cu phases at 500 °C, which is 47 °C lower than the equilibrium reaction temperature. Swelling occurred when the liquid phase infiltrated the gaps between the copper particles, leaving pores at the original sites of Al particles and Al₂Cu. In the final stage of sintering, the Al-rich phases (Al₂Cu and AlCu) transformed to Al-poor phases (Al₄Cu₉ and α-Cu) in the temperature range of 500–565 °C. Al₄Cu₉ and α-Cu then transformed to AlCu₃ (β) above the eutectoid reaction temperature (565 °C), whereas AlCu₃ transformed to α-Cu and eutectoid phases (α-Cu + Al₄Cu₉) during cooling. The pure copper transformed to AlCu₃, and the pore volume decreased at 1000 °C. The microstructure study helps manipulate precisely the sintering process of Cu-Al alloys and optimize the microstructure with a high dimensional accuracy.     

Phase analysis and thermal conductivity of in situ O′-sialon/β-Si3N4 composites

Typical O??-sialon-based ceramics, with a formula of Si_2?x Al _x O_1+x N_2?x , where x was set as 0.25, were fabricated by in-situ synthesis. Si₃N₄, Al₂O₃, and SiO₂ powders were used as raw materials, and MgO and Y₂O₃ were added as sintering additives. All the samples were sintered at different temperatures under a nitrogen pressure of 0.25?C0.30 MPa, and their microstructure, phase content, and thermal conductivity were evaluated. The effects of O??-sialon and ??-Si₃N₄ on the thermal conductivity were analyzed by numerical calculation in detail. In the case of the similar porosity, the thermal conductivity of O??-sialon-based ceramics decreased with the ratio of O??-sialon/??-Si₃N₄ increasing. When the ratio was 12, the thermal conductivity of O??-sialon ceramics sintered at 1360°C was 1.197 W·m^?1·K^?1.     

Effects of yttrium on the formation and magnetic properties of bulk metallic glassy (Fe,Co)-B-Si-Nb alloys

The bulk metallic glassy (BMG) rods of [(Fe_0.5Co_0.5)_0.72B_0.192Si_0.048Nb_0.04]_100-xY_x (x=0-6) and [(Fe_xCo_1-x)_0.72B_0.192Si_0.048Nb_0.04]₉₆Y₄ (x=0.5-0.8) were prepared by copper mold casting. The structure, thermal stability, and magnetic properties of the samples were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC), and vibrating sample magnetometer (VSM). Adding 1at% to 6at% of yttrium, the bulk glassy alloy rods of [(Fe_0.5Co_0.5)_0.72B_0.192Si_0.048Nb_0.04]_100-xY_x(x=0-6) with the diameter of 3 mm were not formed, and the sample with 4at% of yttrium showed less crystalline phase than others. When the Fe/Co atomic ratio was between 5:5 and 7:3, the bulk glassy alloy rods of [(Fe_1-xCo_x)_0.72B_0.192Si_0.048Nb_0.04]₉₆Y₄ (x=0.5-0.8) with the diameter of 2 mm were fabricated. In the (Fe, Co)-B-Si-Nb-Y BMGs, when the Fe content increased, the thermal stability, the supercooled liquid region, and the glass-forming ability (GFA) decreased, but the saturation magnetization (M_s) increased.     

Bulk Al-Al3Zr composite prepared by mechanical alloying and hot extrusion for high-temperature applications

Bulk Al/Al₃Zr composite was prepared by a combination of mechanical alloying (MA) and hot extrusion processes. Elemental Al and Zr powders were milled for up to 10 h and heat treated at 600℃ for 1 h to form stable Al₃Zr. The prepared Al₃Zr powder was then mixed with the pure Al powder to produce an Al-Al₃Zr composite. The composite powder was finally consolidated by hot extrusion at 550℃. The mechanical properties of consolidated samples were evaluated by hardness and tension tests at room and elevated temperatures. The results show that annealing of the 10-h-milled powder at 600℃ for 1 h led to the formation of a stable Al₃Zr phase. Differential scanning calorimetry (DSC) results confirmed that the formation of Al₃Zr began with the nucleation of a metastable phase, which subsequently transformed to the stable tetragonal Al₃Zr structure. The tension yield strength of the Al-10wt%Al₃Zr composite was determined to be 103 MPa, which is approximately twice that for pure Al (53 MPa). The yield stress of the Al/Al₃Zr composite at 300℃ is just 10% lower than that at room temperature, which demonstrates the strong potential for the prepared composite to be used in high-temperature structural applications.