Strain rate response of a Zr-based composite fabricated by Bridgman solidification

Zr_58.5Ti_14.3Nb_5.2Cu_6.1Ni_4.9Be_11.0 bulk metallic glass matrix composites, containing β-Zr dendrites, were fabricated by Bridgman solidification at the withdrawal velocity of 1.0 mm/s through a temperature gradient of ～45 K/mm. Subjected to the increasing compressive strain rates, the monotonic increasing and decreasing were obtained for the maximum strength and the fracture strain, respectively. The results show that high strain rate may induce the insufficient time for the interaction between shear bands and the crystalline phase, and early fracture occurs as a result. The fractographs are consistent with the mechanical properties, and the failure mode of the present Zr-based composites is in agreement with the frame of the ellipse criterion.     

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.     

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.     

Limitation of the Johnson-Mehl-Avrami equation for the kinetic analysis of crystallization in a Ti-based amorphous alloy

The primary crystallization of the Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ amorphous alloy was studied by isochronal differential scanning calorimetry (DSC). The activation energy was determined by the Kissinger-Akahira-Sunose method. Trying to analyze the crystallization kinetics of the Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ amorphous alloy by two different methods, it was found that the crystallization kinetics did not obey the Johnson-Mehl-Avrami equation. A modified method in consideration of the impingement effect was proposed to perform kinetic analysis of the isochronal crystallization of this alloy. The kinetic parameters were then obtained by the linear fitting method based on the modified kinetic equation. The results show that the isochronal crystallization kinetics of the amorphous Ti₄₀Zr₂₅Ni₈Cu₉Be₁₈ alloy is heating rate dependent, and the discrepancy between the Johnson-Mehl-Avrami method and the modified method increases with the increase of heating rate.     

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.     

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%.     

Fabrication of bulk glassy Zr41Ti14Ni8Cu12.5Be22.5Fe2 alloy by water quenching

A glassy Zr₄₁Ti₁₄Ni₈Cu_12.5Be_22.5Fe₂ rod with a diameter of 9 mm was successfully produced by water quenching. The effects of iron addition on thermal stability and hardness of Zr₄₁Ti₁₄Ni₈Cu_12.5Be_22.5Fe₂ bulk amorphous alloy were investigated by XR D, DSC and microhardness test. It is found that the full annealing would enhance the strength of the alloy significantly. The cause of the increase in hardness was analyzed and the formation mechanisms of the bulk amorphous alloy are discussed.     

Mechanical, deformation and fracture behaviors of bulk metallic glass composites reinforced by spherical B2 particles

Ti_(45)Cu_(40)Ni_7Zr_5Sn_(2.5)Si_(0.5) alloys were prepared under various cooling rate conditions during solidification.The alloys exhibited different volume fractions of B2 particles with 0～40 vol%in an amorphous matrix.Monolithic bulk metallic glass of 1 mm diameter showed no macroscopic plasticity and exhibited the typical vein patterns in a maximum shear stress plane on the fracture surface.However,a bulk metallic glass composite containing the B2 particles revealed obvious plasticity(～5.6%)with a remarkable work-hardening behavior that resulted from a stress-induced martensitic transformation of the B2 particles.Moreover,the composite displayed the complicated fracture morphologies containing of three types of fracture features.Through detailed investigations on the microstructural evolution,mechanical,deformation and fracture characteristics,the influence of B2 particle on overall behavior of the TiCu-based bulk metallic glass composites was elucidated.     

Bulk metallic glass rings prepared by a modified water quenching method

Bulk metallic glass rings have the potential applications as annular gasket and active solder in special fields. The bulk metallic glass ring of Zr_1.2Ti_13.8Cu_12.5Ni_10.0Be_22.5 with the outer diameter, the inner diameter, and the thickness of 38, 36, and 5 mm, respectively, was prepared by using a special shaped quartz tube water quenching method. The mechanical properties along the whole cross section were investigated by a nanoindentation method, and no evident variation of the Young's modulus and hardness was found, further indicating the single amorphous structure. Amorphous ring and tube-shape parts with different dimensions can be produced by this method.     

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.     

<Emphasis Type="Italic">In situ</Emphasis> synthesis of TiC reinforced Cu<Subscript>47</Subscript>Ti<Subscript>34</Subscript>Zr<Subscript>11</Subscript>Ni<Subscript>8</Subscript> bulk metallic glass composites

In situ synthesized TiC particles and β-Ti dendrites reinforced Cu47Ti34Zr11Ni8 bulk metallic glass (BMG) composite ingots were prepared by the suction casting method.The ingots with diameters from 1 up to 4mm were successfully obtained. It was shown that introducing TiC micro-sized particles into the amorphous matrix did not disturb the glass forming ability (GFA) of the matrix,while the yield strength and ductility could be well improved.The phase constitution, microstructure and elements distribution in the composites were studied by OM, XRD, SEM and EDS.It was shown that the in situ synthesized TiC particles acting as heterogeneous nucleation sites promoted the precipitation of β-Ti dendrites, resulting in the formation of the TiC particles and β-Ti dendrites co-reinforced BMG composites. The compressive tests were employed to probe the yield strength and ductility of BMG composites.     

Eutectic reaction and cored dendritic morphology in yttrium doped Zr-based amorphous alloys

The microalloying effect of yttrium on the crystallization behaviors of (Zr_0.525Al_0.10Ti_0.05Cu_0.179Ni_0.146)_100-x Y_x, and (Zr_0.55Al_0.15-Ni_0.10Cu_0.20)_100-x Y_x (x=0, 0.4, and 1, thus the two alloy systems were denoted as Zr52.5, Zr52.5Y0.4, Zr52.5Y1, and Zr55, Zr55Y0.4, Zr55Y1, respectively) was studied. Transmission electron microscopy (TEM) results suggested that the crystalline phases were different in the two Zr-based alloys and with different yttrium contents. ZrNi-phase and Al₃Zr₅ phase precipitations can be well explained by the mechanisms of nucleation and growth. Al₃Zr₅ phase is mainly formed by a peritectic-like reaction, while ZrNi-phase by a eutectic reaction. The contents of elements Y, Al, and Ti may dominate the reaction types. The orientation relationship between Y₂O₃ particles and Al₃Zr₅ phase is also discussed.     

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.     

Hydrogen storage properties of (Ti0.85Zr0.15)1.05Mn1.2Cr0.6V0.1M0.1 (M=Ni, Fe, Cu) alloys easily activated at room temperature

The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)M_(0.1)(M=Ni, Fe, Cu) alloys with a single C14-type Laves phase have been fabricated by arc melting. They are able to be easily activated by one hydrogen absorption and desorption cycle under 4 MPa hydrogen pressure and vacuum at room temperature. Partial substitution of M for Mn results in the increase of hydrogenation and dehydrogenation capacities in an order of Ni Fe Cu. M elements increase the absorption and desorption plateau pressure in an order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1). The(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1) alloy has reversible hydrogen capacities of 1.81 wt% at 273 K and 1.58 wt% at 318 K with formation enthalpy(ΔH_(ab)) of-20.66 kJ mol~(-1) and decomposition enthalpy(ΔH_(de)) of 27.37 kJ mol~(-1). The differences in the hydrogen storage properties can be attributed to the increase of the interstitial size for hydrogen accommodation caused by the increase of unit cell volumes in the order of(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Ni_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Fe_(0.1)(Ti_(0.85)Zr_(0.15))_(1.05)Mn_(1.2)Cr_(0.6)V_(0.1)Cu_(0.1).     

Effect of proton irradiation on structure relaxation of Zr<Subscript>41.5</Subscript>Ti<Subscript>14.9</Subscript>Cu<Subscript>12.6</Subscript>Ni<Subscript>10.5</Subscript>Be<Subscript>20.4</Subscript> bulk metallic glass

Effects of proton irradiation on structure re-laxation of Zr_(41.5)Ti_(14.9)Cu_(12.6)Ni_(10.5)Be_(20.4) bulk metallic glass areinvestigated by means of X-ray diffraction, differential scan-ning calorimetric and electronic resistance measurements.The results show that, at 203 K, the structure ofZr_(41.5)Ti_(14.9)Cu_(12.6)Ni_(10.5)Be_(20.4) bulk metal glass is relaxed obvi-ously by proton irradiation with the energy and the dosebeing of 160 keV and 1.65×10~(16) ions/cm~2, respectively. How-ever, Zr_(41 .5)Ti_(14.9)Cu_(12.6)Ni_(10.5)Be_(20.4) bulk metallic glass becomesmore steady amorphous state under two conditions, one isthat the energy and the dose are 160 keV and 1.1×10~(15)ions/cm~2, respectively. Another is that the energy and thedose are 120 keV and 6.5×10~(15) ions/cm~2, respectively.     

Effects of gravity field on glass forming ability in ZrTiCuNiBe alloy

The solidification and glass forming ability of Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk glassy forming alloy is investigated by Bridgman unidirectional solidification at different growth velocities under different gravity field orientations. Large differences in glass formation, undercooling and crystallization morphology on different solidification conditions have been found and discussed from the point of view of gravity induced convection. The results are useful for understanding the nucleation and growth in the melt and glass formation mechanism in the alloy.     

Effects of density difference of constituent elements on glass formation in TiCu-based bulk metallic glasses

Glass formation is generally favored by a large atomic size mismatch among constituent elements,which usually leads to large density differences among them as well.During melting,elemental segregation occurs due to Stokes’ law and then inevitably affects glass formation.In this paper,such effects on glass-forming ability in a TiCu-based alloy system have been demonstrated.In the bulk glassforming composition Ti43Cu42Hf14Si1,macroscopic segregation of Si was observed in the as-melted ingots and silicon was completely depleted in the as-cast rods.In another Ti33Cu47Ni8Zr11Si1 alloy,nevertheless,the effects of density differences among the constituent elements were less severe.It was also confrmed that using proper pre-alloys could be an effective way in alleviating the side effects of the elemental segregation.     

Influence of pulsing current on the glass transition and crystallizing kinetics of a Zr base bulk amorphous alloy

Based on the thermal analysis, the influence of pulsing current on the glass transition and crystallizing kinetics of Zr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy has been studied. The obtained results show that after the Zr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy was pretreated by high-density pulsing current at low temperature, its glass transition temperature Tg, the initial crystallizing temperature Tx and the corresponding exothermic peak of crystallization Tpi were reduced. But the temperature range of supercooled liquid △T=Tx-Tg is almost the same. The calculated results with Kissinger equation show that the activation energy of glass transition of the alloy pretreated is reduced significantly, while the activation energy of crystallization is basically unchanged. The influence of pulsing current on the glass transition and crystallization of theZr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy is believed to be related with the structure relaxation of the glass caused by the current.     

Transitions of amorphouscrystalline-amorphous in bulk metallic glass under HP and HT

In-situ SR-XRD measurements revealed that the crystallization process in Zr₄₁.2Ti₁₃.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass is significantly different from that in traditional glasses. Subsequent heating at 10 GPa converts the sample from amorphous phase into the metastable fcc phase and then leads to the fcc phase back to the amorphous phase, indicating that there exists ‘reversible’ phase transition phenomena in the material under high pressure and high temperature.     

Work toughening effect in Zr_（41）Ti_（14）Cu_（12.5）Ni_（10）Be_（22.5） bulk metallic glass

Work hardening is a well-known phenomenon occurring in crystalline metals during deformation,which has been widely used to increase the strength of metals although their ductility is usually reduced simultaneously. Here we report that the plastic strain of Zr41Ti14Cu12.5Ni10Be22.5 (at.%) bulk metallic glasses has been increased from 0.3% for the as-cast sample to 2.5%-8.0% for samples that have experienced pre-deformation under constrained conditions. The pre-deformed glassy alloys possess more free volume and abundant introduced shear bands,which are believed to promote the activation of shear bands in post-deformation and result in an increase in plasticity. The orientation of the pre-introduced shear bands relative to the loading direction will affect the deformation behavior of pre-deformed samples. The present results show that pre-deformation of this glassy alloy will result in work toughening. This work toughening effect can be removed by isothermal annealing at a sub-Tg (glass transition) temperature,which causes annihilation of free volume and healing of shear bands.