Microstructure studies of Zr65Cu17.5Al7.5Ni10 and Zr65Cu15Al10Ni10 glass forming alloys: Phase morphologies and undercooled melt solidification

Zr₆₅Cu_17.5Al_7.5Ni₁₀ (at.%) and Zr₆₅Cu₁₅Al₁₀Ni₁₀ (at.%) glass forming alloy microstructures have been investigated by means of optical and electron microscopies. They are composed of a fine eutectic matrix with eutectic dendrites (EDs) that have peculiar morphologies. Al and Cu concentrations, in these alloys, favour primary dendrites and determine the ED morphologies and compositions. Their locations within the microstructures suggest a two-step solidification process of the two undercooled melts. The identified crystalline phases indicate the occurrence of solid state phase transformations in agreement with the structural defects observed in the grains. The crystalline phases can be classified into Zr-rich, Cu-rich, Ni-rich and Al-rich compounds resulting from competing diffusion between Cu, Ni, and Al in the melts.     

A mechanical spectroscopy study of the Zr69.5Cu12Ni11Al7.5 alloy

The vibrating reed technique has been used to investigate the Zr_69.5Cu₁₂Ni₁₁Al_7.5 glass forming alloy. The phase transformations of the material, as can be seen through the changes of the resonance frequency of the sample as a function of temperature, have been studied and the results have been compared with TEM and DSC measurements confirming the development, above T_g, of a metastable quasicrystalline state prior to crystallisation. Hydrogen-induced damping peaks were then observed in the different phases of the material with particular attention to the quasicrystalline state, where it seems that the microscopic reorientation mechanism responsible for the internal friction peaks should be similar to the one already known in the amorphous phase (hydrogen jumps between tetrahedral sites). Shortly after crystallisation, three damping peaks were observed, two of which are attributed to relaxation processes (Zener-type or intercrystalline Gorsky effect) taking place in the tetragonal CuZr₂ phase.     

Effect of cooling rate on crystallization of metallic Zr–Cu–Ni glass

X-ray diffraction (XRD) and differential scanning calorimetry (DSC) were employed to investigate the effect of cooling rate on crystallization behavior of metallic Zr₇₀Cu₂₀Ni₁₀ glass. It is found that all DSC traces of the metallic Zr₇₀Cu₂₀Ni₁₀ glasses under different cooling rates exhibit two exothermic peaks, indicating that the crystallization of metallic Zr₇₀Cu₂₀Ni₁₀ glass proceeds through a double-stage mode. In our previous studies, we have concluded that the first exothermic reaction mainly corresponds to the precipitation of the Zr₂Cu phase, and the second one is mainly due to the formation of nanoscale Zr₂Ni particles. It is observed that there exists a close relationship between the cooling rate and thermodynamic parameters of metallic Zr₇₀Cu₂₀Ni₁₀ glass, such as the onset crystallization temperature T_x, the first peak temperature T_p1 and the second one T_p2. The above three thermodynamic parameters reach a maximum when the surface velocity is 30 m/s. This effect is just similar to that of the Ni concentration, which has been discussed in our previous works. The activation energy for crystallization and the local Avrami exponent of metallic Zr–Cu–Ni glass under isothermal annealing conditions also exhibit a similar tendency with the cooling rate.     

Oxidation induced ductility enhancement of Zr based metallic glass ribbons in vicinity of glass transition temperature

Zr-based metallic glasses(MGs)possess a wide supercooled liquid region,which gives a wide processing window for superplastic forming to make microdevices with demanding size accuracy and surface finishing.The existence of oxygen may have an influence on the thermoplastic deformation process.Therefore,the effect of oxidation on the mechanical behavior of the MGs in the vicinity of glass transition temperature is of great significance for practical forming of MG components.In the present study,the effect of oxidation on tensile properties of Zr50Cu40Al10 metallic glass was investigated.The tested samples were characterized by XRD and SEM analysis.For the samples tested in air,the strength decreases 187 MPa,61 MPa and 59 MPa and the ductility increases 0.31,0.36,and 0.77 at 420℃,430℃,and 440℃,respectively,compared with those tested in flowing argon.ZrO₂ preferentially formed during the tensile testing at 420℃,and both ZrO₂ and Al₂O₃ oxides formed at 430℃.The dilution of Zr elements in the remaining amorphous matrix caused by preferential oxidation on the surface layer attributes to the decrease in strength and enhancement in ductility of the Zr₅₀Cu₄₀Al₁₀ metallic glasses.     

Microstructure and mechanical properties of mechanically alloyed and spark plasma sintered amorphous–nanocrystalline Al65Cu20Ti15 intermetallic matrix composite reinforced with TiO2 nanoparticles

Multiphase Al₆₅Cu₂₀Ti₁₅ intermetallic alloy matrix composite, dispersed with 10 wt.% of TiO₂ nanoparticles, has been processed by mechanical alloying, followed by spark plasma sintering under pressure in the temperature range of 623–873 K. Differential scanning calorimetry and X-ray diffraction suggest that equilibrium crystalline phases evolve from the amorphous or intermediate crystalline phases. Transmission electron microscopy shows that the composite sintered at 873 K has partially amorphous microstructure, with dispersion of equilibrium, crystalline, intermetallic precipitates of Al₅CuTi₂, Al₃Ti, and Al₂Cu of 25–50 nm size, besides the TiO₂. The composite sintered at 873 K exhibits little porosity, hardness of 5.6 GPa, indentation fracture toughness in the range of 3.1–4.2 MPa√m, and compressive strength of 1.1 GPa. Indentation crack deflection by TiO₂ particle aggregates causes increase in fracture resistance with crack length, and suggests R-curve type behaviour. The study provides guidelines for processing high strength amorphous–nanocrystalline intermetallic composites based on the Al–Cu–Ti ternary system.     

Avrami exponent and isothermal crystallization of Zr/Ti-based bulk metallic glasses

The isothermal crystallization kinetics of Zr/Ti-based bulk metallic glasses (BMGs) have been investigated by using Avrami exponent. It is a constant nucleation rate and a constant number of quenched-in nuclei that cause the linear John–Mehl–Avrami (JMA) modes in Avrami exponents of Zr₆₂Al₈Ni₁₃Cu₁₇ and Zr₆₅Al₈Ni₁₀Cu₁₇ BMGs, respectively. However, sub-T_g pre-annealing of Zr₆₂Al₈Ni₁₃Cu₁₇, and multiple-step phase transition in Ti₄₃Cu₄₃Zr₇Ni₇ and Ti₄₅Zr₅Cu₄₀Ni_7.5Sn_2.5 make their Avrami exponents deviate from the linear JMA mode. The difference in Avrami exponents maybe provides useful information for performing the microstructure control of BMG composites upon isothermal annealing.     

Effect of ball-milling and shot-peening on Zr55Al10Ni5Cu30 alloys

Effect of ball-milling and shot-peening on a metallic glass Zr₅₅Al₁₀Ni₅Cu₃₀, which possesses a large supercooled liquid region, has been investigated by means of differential scanning calorimetry, x-ray diffractometry and transmission electron microscopy. Metallic glassy ribbons, powders and plates were prepared by melt-spinning, gas-atomizing and mold-clamp casting techniques, respectively. No structural changes were observed in both the ribbon and powder specimens by ball-milling for around 100 h; however, the powder specimens were crystallized by Fe contamination when they were ball-milled for 540 h. No structural evolution was also observed when the plate specimens were subjected to shot-peening, while crystallized plate specimens were easily amorphized by mild and short period shot-peening. These results imply high phase stability of the Zr₅₅Al₁₀Ni₅Cu₃₀ metallic glass against deformation.     

脉冲磁场处理Fe52Co34Hf7B6Cu1非晶的低温真空退火效应

对Fe₅₂Co₃₄Hf₇B₆Cu₁非晶合金进行了低频磁脉冲处理,研究低温真空退火对磁脉冲处理Fe_52Co₃₄Hf₇B₆Cu₁非晶软磁性能的影响.结果表明,磁脉冲处理导致非晶合金发生纳米晶化,析出晶态相α-Fe（Co）,晶粒尺寸为5-10 nm,形成的纳米晶粒弥散分布于非晶基体的双相纳米合金中.对磁脉冲处理的试样进行低温真空退火,可以进一步优化纳米合金的软磁性能,在100℃退火可以得到最佳的软磁性能.     

Al25Nb20Ti30Zr25低密度高熵合金的组织和性能

通过Thermo-Calc软件计算、微观组织多尺度表征以及热模拟试验等研究了Al₂₅Nb₂₀Ti₃₀Zr₂₅合金的组织结构、高温组织稳定性和热加工性能。结果表明,Al₂₅Nb₂₀Ti₃₀Zr₂₅合金的铸锭组织主要由BCC基体相和Zr₅Al₃析出相组成,Zr₅Al₃相在BCC晶界连续析出,晶粒内部的Zr₅Al₃相呈块状分布,平均尺寸在750 nm左右;合金在750~1000 ℃保温24 h后,基体中的晶粒尺寸并未发生明显变化;随着温度的增加,Zr₅Al₃相含量小幅度降低,合金的高温组织稳定性较好。建立了合金的本构方程为$\dot{ε}$=4.5×10¹⁴×[sinh(0.0063σ_p)]^2.8exp(-419/RT),并绘制了合金的能量耗散系数图;在1050 ℃/1 s^-1变形条件下,能量耗散系数达到峰值0.69,在该变形条件下等温锻造出尺寸为$\phi$ 180 mm×20 mm完整无开裂的圆形块体材料。锻造消除了原始晶界处连续分布的Zr₅Al₃相,使其分解成短杆状均匀分布于合金基体中,BCC基体组织发生了动态回复和部分再结晶。     

Optimized Mechanical Properties,Corrosion Resistance and Bactericidal Ability of Ti-15Zr-xCu Biomedical Alloys During Aging Treatment

The effects of different aging conditions on the microstructure, strength, corrosion resistance, cytotoxicity and antibacterial ability of Ti-15Zr-xCu (3 ≤ x ≤ 7, wt%) (TZC) alloys were systematically investigated. Microstructural evolution and behavior were analyzed by X-ray diffraction (XRD) patterns and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), while potentiodynamic polarization technique was employed to characterize the corrosion response of the alloys after solution-treatment and aging (STA). High-temperature aging at 660 °C for 4 h (660-4) gave the best combination of properties by enabling significant precipitation of the Cu-rich Ti₂Cu and Zr₂Cu compounds, and mild formation of the Zr₇Cu₁₀ secondary phase. The high kinetics at this condition was beneficial to the complete precipitation and more homogeneous distribution of the intermetallic particles. These led to the inhibition of dislocation movements and allowed for significantly improved mechanical strengths with added ductility, availability of more Cu ions for the desired oligodynamic activity without evoking cytotoxicity, better corrosion resistance and very high antibacterial ability (over 99.5%), thus improving the overall properties of the TZC alloys for biomedical applications.     

表面活化Al2O3陶瓷与5005铝合金真空钎焊

采用Al-Si钎料对经过Ag-Cu-Ti粉末活性金属化处理的Al₂O₃陶瓷与5005铝合金进行了真空钎焊,研究了钎焊接头的典型界面组织,分析了钎焊温度对接头界面结构特征及力学性能的影响. 结果表明,接头典型界面结构为5005铝合金/α-Al+θ-Al₂Cu+ξ-Ag₂Al/ξ-Ag₂Al+θ-Al₂Cu+Al₃Ti/Ti₃Cu₃O/Al₂O₃陶瓷. 钎焊过程中,Al-Si钎料与活性元素Ti及铝合金母材发生冶金反应,实现对两侧母材的连接. 随着钎焊温度的升高,陶瓷侧Ti₃Cu₃O活化反应层的厚度逐渐变薄,溶解进钎缝中的Ag和Cu与Al反应加剧,生成ξ-Ag₂Al+θ-Al₂Cu金属间化合物的数量增多,铝合金的晶间渗入明显;随钎焊温度的升高,接头抗剪强度先增加后降低,当钎焊温度为610 ℃时,接头强度最高达到15 MPa.     

HRTEM study of crystallization of Zr–Cu–Ni metallic glass

Employing differential scanning calorimetry (DSC) and high-resolution transmission electron microscopy (HRTEM), the micromechanism for crystallization of Zr₇₀Cu₂₀Ni₁₀ metallic glass under isothermal annealing conditions has been investigated. It is found that the relationship between the annealing temperature and the peak position, incubation time and ending time in the isothermal annealing DSC traces of Zr₇₀Cu₂₀Ni₁₀ metallic glass obeys a first-order exponential function. However, the time–temperature transformation curves of Zr₇₀Cu₂₀Ni₁₀ metallic glass at different crystallized volume fractions can be well fitted by a second-order exponential function. It is observed that at the initial crystallization stage some ordered atomic clusters precipitate first, acting as nucleation sites and facilitating the subsequent crystallization process, and the crystal growth process mainly proceeds through the atomic depositing on the previously formed crystals. This behavior confirms that the new micromechanism for crystallization of amorphous alloys proposed by Lu and Wang can also be applied to the new series of zirconium based amorphous alloys.     

Novel Crystallization Behaviors of Zr-Based Metallic Glass Under Thermo-Mechanical Coupled Fatigue Loading Condition

Novel crystallization behaviors of Zr_(55)Cu_(30)Al_(10)Ni_5 bulk metallic glass are investigated.On the one hand,mixed oxides,including CuO,CuAlO_2,CuAl_2O_4 and ZrO_2,show sequential oxidation process determined by coupling effects of specific cyclic load and temperature.On the other hand,at a temperature(100 ℃)by far lower than Tg of 412 ℃,under cyclic loading condition,non-oxidized binary alloy CuZr_2 is precipitated;the thermo-mechanical coupled effects of temperature below Tg and fatigue accumulation on the non-oxidized crystallization behaviors are revealed.Meanwhile,at a constant temperature of 400℃, by comparing among the XRD patterns,respectively,obtained from tensile,creep and fatigue fractures,the dominating effect of cyclic load on the generation of non-oxidized CuZr_2 is verified.Furthermore,the crystallization behavior of amorphous phases under cyclic loading condition is observed through TEM micrograph and diffraction pattern at 100 ℃.     

Superplastic deformation and crystallization behavior of Cu54Ni6Zr22Ti18 metallic-glass sheet

Superplastic deformation and crystallization behavior of a Cu₅₄Ni₆Zr₂₂Ti₁₈ metallic glass were investigated. A maximum elongation of 650% was obtained at 733 K at 1 × 10⁻² s⁻¹ from the sheet fabricated by squeeze copper-mold casting method. At low strain rates, the strain-rate-sensitivity exponent value was close to 1, suggesting that Newtonian-like behavior governed the plastic flow. At a high strain rate around 10⁻² s⁻¹, a transition from Newtonian to non-Newtonian behavior took place with decrease in m value. Large strain hardening by crystallization occurred during the course of deformation. The strain hardening was found to be caused by crystallization according to the analyses of the relation of true stress vs. testing time, T-T-T diagram and DSC characteristics. The time periods up to the strain before strain hardening at 733 K for the Cu₅₄Ni₆Zr₂₂Ti₁₈ metallic glass were similar to that of the Zr₆₅Al₁₀Ni₁₀Cu₁₅ metallic glass at 696 K as 180–300 s (3–5 min). This coincidence could be explained by comparison of their T-T-T diagrams showing that the incubation times for crystallization of the Cu BMG at 733 K and for Zr BMG at 696 K are similar.     

Temperature memory effect of Ti50Ni30Cu20 (at.%) alloy

After the reverse thermal induced martensitic transformation process of shape memory alloy is arrested at a temperature between the reverse transformation start and finish temperatures (A_s and A_f), and then cooled to a temperature below M_f, a kinetic stop will occur in the next heat flow curve during the heating process. The kinetic stop is closely related to the arrested temperature. This phenomenon is called temperature memory effect (TME). TME of Ti₅₀Ni₃₀Cu₂₀ (at.%) shape memory alloy with phase transformation between B2 austenite and B19 martensite has been investigated by differential scanning calorimeter in this paper. The results indicate that TME of Ti₅₀Ni₃₀Cu₂₀ alloy only exists in the heating process.     

In Situ Scattering Studies of Crystallization Kinetics in a Phase-Separated Zr-Cu-Fe-Al Bulk Metallic Glass

Thermal stability and the crystallization kinetics of a phase-separated Zr-Cu-Fe-Al bulk metallic glass were investigated using in situ high-energy synchrotron X-ray and neutron diffraction, as well as small-angle synchrotron X-ray scattering. It was revealed that this glass with excellent glass-forming ability possesses a two-step crystallization behavior. The crystalline products and their evolution sequence are more complicated than a homogeneous Zr-Cu-Al glass with average glass-forming ability. The experimental results indicate that a finely distributed nanometer-sized cubic Zr₂Cu phase forms first and then transforms to a tetragonal Zr₂Cu phase, while the matrix transforms to an orthorhombic Zr₃Fe phase. The strength of the Zr-Cu-Fe-Al composite containing cubic Zr₂Cu phase and glass matrix increases, and the plasticity also improves compared to the as-cast Zr-Cu-Fe-Al bulk metallic glass. Our results suggest that the formation of multiple and complex crystalline products would be the characteristics of the Zr-Cu-Fe-Al glass with better glass-forming ability. Our study may shed light on the synthesis of bulk-sized glass-nanocrystals composites of high strength and good plasticity.     

Effect of amorphous–crystalline interfaces on the martensitic transformation in Ti50Ni25Cu25

A partially crystallized amorphous Ti₅₀Ni₂₅Cu₂₅ melt-spun ribbon showing spherical particles in martensite has been investigated. Microstructural observations support the hindering of the martensitic transformation as well as the production of additional autoaccommodated structures nearby the interface compared with the ones used inwards.     

New low thermal expansion ceramics: Sintering and thermal behavior of Ln1/3Zr2(PO4)3-based composites

Materials with the general formula M_xZr₂(PO₄)₃ are known to possess low coefficients of thermal expansion (CTE). The present work investigates the thermal properties of new composite materials issued from the decomposition at high temperature of Ln_1/3Zr₂(PO₄)₃ (Ln=La, Gd). The decomposition process was studied and showed that the resulting powder was a LnPO₄, Zr₂P₂O₉ and ZrO₂ mixture. Composite materials made of that mixture were sintered and characterized. The effect of sintering aids such as ZnO was considered. Final densities of the composites were about 90% of theoretical density and these materials presented low CTE in the 10⁻⁶ °C⁻¹ range.     

Stability evaluation of fluorite structure phases in ZrO2-MO2 (M=Th, U, Pu, Ce) systems by thermodynamic modelling

Thermodynamic modelling was demonstrated for ZrO₂-ThO₂ system based on the data for the ZrO₂-UO₂ and ZrO₂-CeO₂ systems in the literature. The calculated phase diagram for the ZrO₂-ThO₂ system showed a good agreement with the experimental data in the literature. Using the data obtained, together with the data for ZrO₂-UO₂, ZrO₂-PuO₂ and ZrO₂-CeO₂ systems, the stability of the fluorite structure phases in the ZrO₂-MO₂ (M=Th, U, Pu, Ce) systems was also studied with respect to the partial molar quantities. The effect of the ZrO₂ on the enthalpy in the MO₂ rich region increased as the cation size of the matrices decreased. The solubility limits of the ZrO₂ in the fluorite structure phase in this region also increased as the cation size of the matrix decreased. The effect of MO₂ on the partial molar Gibbs energy in the ZrO₂ rich region increased as the cation size of the MO₂ increased. It implies that the dissolution of the larger cation stabilises the fluorite structure of the ZrO₂ more.     

Types of mechanical relaxation by hydrogen in intermetallic compounds

Hydrogen in polycrystalline intermetallic compounds generally produces extremely broad damping spectra, indicating the presence of short-range as well as long-range relaxation mechanisms. These are discussed on the basis of vibrating-reed results on Zr₆₅Cu_27.5Al_7.5, Zr₆₅Cu_17.5Ni₁₀Al_7.5, and CuZr₂ alloys. A relaxation peak at 270 K observed in all three cases is interpreted as a Zener-type relaxation of hydrogen in the CuZr₂ lattice. The differences found at higher temperatures — a second relaxation peak in the ternary and quaternary alloys but an exponential increase of damping in CuZr₂ — are related to different grain sizes and can be attributed to an ‘intercrystalline Gorsky effect’ due to elastic anisotropy mismatch strains.