Low-temperature brazing of titanium by the application of a Zr–Ti–Ni–Cu–Bebulk metallic glass (BMG) alloy as a filler

Titanium (Ti) was successfully brazed at low temperatures below 800 °C by employing a Zr_41.2Ti_13.8Ni_10.0Cu_12.5Be_22.5 (at.%) bulk metallic glass (BMG) alloy as a filler. Through the use of this alloy filler, the detrimental segregation of Zr–Cu–Ni filler elements was completely eliminated by heating to well below 800 °C, so the resultant joint was quite homogeneous with a coarse acicular structure. The disappearance of the Zr–Cu–Ni segregated region was rate-controlled by the diffusion of the filler elements in the Ti base metal. Remarkably, the mechanical property and corrosion resistance of the homogeneous joint brazed at 800 °C for 10 min were mostly comparable to those of bulk Ti.     

On the amorphous and nanocrystalline Zr–Cu and Zr–Ti co-sputtered thin films

In the current study, we examined and compared the mixing and vitrification behavior of the Zr–Cu and Zr–Ti binary systems in the form of co-sputtered thin films with or without post-annealing. The co-sputtered Zr–Cu films are all amorphous under various co-sputtering conditions, suggesting the high vitrification tendency. The amorphous Zr–Cu thin film will start to crystallize into nano-crystalline Zr₂Cu and Zr₇Cu₁₀ phases upon long exposure at temperatures above 350 °C. On the other hand, it is difficult to form amorphous film with the Zr–Ti system, except at a low sputtering power of 30–50 W. The low powers enable the co-sputtered Zr–Ti thin film to exhibit the diffuse hump in the X-ray diffraction. Examination by high resolution transmission electron microscopy reveals numerous fine nano-crystalline phases around 2 nm in the amorphous matrix. Upon exposure at 700 °C, the Zr–Ti films transform into crystalline hexagonal close-packed α and body-centered cubic β phases.     

Formation and thermal stability of new Zr–Cu-based bulk glassy alloys with unusual glass-forming ability

The simultaneous addition of Al and Ag to Zr–Cu binary alloys increased in the stabilization of supercooled liquid, the reduced glass transition temperature and γ value, leading to greatly enhance the glass-forming ability (GFA). The Zr–Cu–Ag–Al glassy alloy samples with diameters above 15 mm were obtained in the wide composition range of 42–50 at% Zr, 32–42 at% Cu, 5–10 at% Ag, and 5–12 at% Al. The best GFA was obtained for Zr₄₈Cu₃₆Ag₈Al₈ alloy, and the glassy samples with diameters up to 25 mm were fabricated by an injection copper mold casting. The Zr₄₈Cu₃₆Ag₈Al₈ glassy alloy exhibited high tensile and compressive fracture strength of over 1800 MPa.     

Similar and dissimilar friction welding of Zr–Cu–Al bulk glassy alloys

The friction welding of three kinds of Zr–Cu–Al bulk glassy alloys (BGAs) which show eutectic or hypoeutectic compositions to similar and dissimilar BGAs and crystalline metals has been tried. The shape and volume of the protrusion formed at the weld interface were investigated. In order to characterize the friction welded interface, micrographic observation and X-ray diffraction analysis on the weld cross-section were carried out. A successful joining of Zr–Cu–Al bulk glassy alloys to similar and dissimilar BGAs was achieved without occurrence of crystallizations at the weld interface through the precise control of friction conditions. In addition, the joining of Zr₅₀Cu₄₀Al₁₀ BGA to crystalline alloys was tried, but it was only successful for specific material combinations. The residual strength after welding of dissimilar BGAs was evaluated by the four-point bending test.     

Strong bonding of infrared brazed α2-Ti3Al and Ti–6Al–4V using Ti–Cu–Ni fillers

Infrared dissimilar brazing of α₂-Ti₃Al and Ti–6Al–4V using Ti–15Cu–25Ni and Ti–15Cu–15Ni filler metals has been performed in this study. The brazed joint consists primarily of Ti-rich and Ti₂Ni phases, and there is no interfacial phase among the braze alloy, α₂-Ti₃Al and Ti–6Al–4V substrates. The existence of the Ti₂Ni intermetallic compound is detrimental to the bonding strength of the joint. The amount of Ti₂Ni decreases with increasing brazing temperature and/or time due to the depletion of Ni content from the braze alloy into the Ti–6Al–4V substrate during brazing. The shear strength of the brazed joint free of the blocky Ti₂Ni phase is comparable with that of the α₂-Ti₃Al substrate, and strong bonding can thus be obtained.     

Hydrogenation of Zr–Cu–Al–Ni–Pd metallic glasses by electrochemical means

Amorphous materials of Zr–Cu–Ni–Al systems have shown attractive electrochemical hydrogen absorption properties. A comparison between Zr₆₀Cu₁₅Al₁₀Ni₁₀Pd₅ and Zr₆₅Cu_17.5Al_7.5Ni₁₀ reveals that the palladium (Pd) increases the hydrogen absorption capacity. Charging melt-spun Zr₆₀Cu₁₅Al₁₀Ni₁₀Pd₅ ribbons electrochemically to different hydrogen-to-metal (H/M) ratios and following the effusion of hydrogen by thermal desorption analysis (TDA) reveals hydrogen desorption from interstitial sites of high energy levels at temperatures below 630 K. Zirconium hydrides are formed above 630 K. At higher temperatures partial desorption of hydrogen occurs. The thermal stability observed with differential scanning calorimetry (DSC) of the amorphous phase has been significantly deteriorated by hydrogen absorption. After hydrogenation, the crystallization behaviour shows suppression of the characteristic quasicrystalline phase and depends on the hydrogen content. Therefore, at low hydrogen concentrations H/M = 0.3, Cu and/or Cu-rich phases are primarily formed while at high hydrogen concentrations H/M ≥ 0.9 Zr-hydride phase(s) are mainly formed.     

Effects of electrochemical hydrogenation of Zr-based alloys with high glass-forming ability

Zr–(Ti)–Cu–Al–Ni metallic glasses exhibit a high thermal stability corresponding to a wide undercooled liquid region. Depending on their composition, the formation of metastable intermediate phases, e.g. a quasicrystalline phase is possible. The combination of early and late transition metals makes these alloys very interesting regarding their interaction with hydrogen. Amorphous Zr₅₅Cu₃₀Al₁₀Ni₅, Zr₆₅Cu_17.5Al_7.5Ni₁₀ and Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ ribbons were prepared by melt spinning and their microstructure and thermal behaviour was checked by X-ray diffraction, transmission electron microscopy and differential scanning calorimetry. The cathodic reactivity of alloy samples at different microstructural states and after pre-etching in 1 vol.-% HF was investigated in 0.1 M NaOH by applying potentiodynamic polarisation techniques. Galvanostatically hydrogenated samples were characterised by XRD, DSC, TEM and thermal desorption analysis (TDA). For amorphous Zr₅₉Ti₃Cu₂₀Al₁₀Ni₈ samples an increase in electrochemical surface capacity by two orders of magnitude is observed after pre-etching. Compared to the quasicrystalline and crystalline alloy, the hydrogen reduction takes place at significantly lower overpotentials. Zr-based alloys cathodically absorb hydrogen up to H/M=1.65 while keeping the amorphous structure. Already small amounts of hydrogen cause a significant decrease of the thermal stability and changes in the crystallisation sequence. The hydrogen desorption is a two-stage process: (T<623 K) hydrogen desorption from high interstitial-site energy levels and (T>623 K) zirconium hydride formation and subsequent transformation under hydrogen effusion. Hydrogen suppresses the oxygen-triggered formation of metastable phases upon heating and supports primary copper segregation. At very high H/M ratios, severe zirconium hydride formation causes the crystallisation of new compounds.     

Unusual devitrification behaviour in rapidly solidified Ti45Zr38Ni17 alloy

In this study, Ti₄₅Zr₃₈Ni₁₇ ribbons have been elaborated using planar flow casting method (v_quenching = 10⁶ K s⁻¹). The rapidly quenched samples, displaying a dispersion of nanoscaled β phase particles in an amorphous matrix, have been extensively characterised using transmission electron microscopy (TEM) and X-ray diffraction (XRD). Devitrification behaviour, investigated by four-probe resistivity measurements and differential scanning calorimetry as well as high resolution TEM analysis, revealed the formation of nanometric quasicrystals (QC) during the first exothermic phase transformation as well as the precipitation of omega domains inside β particles. On the basis of these data, it has been noticed that nanoscaled β metastable particles had adopted the same temperature dependence as β metastable bulk. Furthermore, particular orientation relationships have been observed for QCs in the vicinity of β particles which have suggested probable influence of crystalline structure on the QCs growth, although the presence of such peculiar materials after annealing treatment could be mainly explained by an icosahedral short-range order prevailing in Ti–Zr–Ni melt and favouring their nucleation.     

Formation, properties and microstructure of amorphous/crystalline composite Ag20Cu30Ti50 alloy using miscibility gap

The aim of the work was to produce the amorphous/crystalline composite with uniform distribution of fine crystalline soft phase. Silver–copper–titanium Ag₂₀Cu₃₀Ti₅₀ alloy was prepared using 99.95 wt% Ag, 99.95 wt% Cu, 99.95 wt% Ti that were arc-melted in argon atmosphere. Then the alloy was melt spun on a copper wheel with linear velocity of 33 m/s. Investigation of the microstructure for both arc-melt massive sample and melt-spun ribbons was performed with use of scanning electron microscope (SEM) with EDS, light microscope (LM) and X-ray diffraction. The thermal stability was evaluated by differential scanning calorimetry (DSC). The properties such as Young modulus and Vickers hardness number before and after crystallization of the amorphous matrix were measured with use of nanoindenter. The microstructure was investigated by transmission electron microscope (TEM). It was found, that the alloy has a tendency for separation within the liquid state due to the miscibility gap which resulted in segregation into Ti–Cu–Ag matrix and Ag-base spherical particles after arc-melting. During rapid cooling through the melt spinning the Ag₂₀Cu₃₀Ti₅₀ alloy formed an amorphous/crystalline composite of fcc silver-rich spherical particles within the amorphous Ti–Cu–Ag matrix.     

Property improvement of copper films with zirconium additive for ULSI interconnects

Thermal stability of Cu–Zr/Zr–Si/Si connect system was evaluated by a standard four-point probe (FPP) method, X-ray diffraction (XRD) and Auger electron spectroscopy (AES) analyses. And the Cu/Zr–Si/Si connect system was used as control experiment. XRD spectra for the Cu–Zr/Zr–Si/Si and Cu/Zr–Si/Si stacked films after annealing showed that the Cu–Zr/Zr–Si/Si specimen was stable up to 650 °C. However, the peaks of Cu silicide (Cu₃Si) appeared for Cu/Zr–Si/Si specimen after annealing at 650 °C. The formation of high resistivity Cu₃Si corresponding to the drastic increase in sheet resistance of copper film. The results observed by AES were consistent with those obtained from XRD measurements and demonstrated that Cu–Zr/Zr–Si/Si system had more thermal stability than that of the Cu/Zr–Si/Si system. The thermal stability of Cu–Zr/Zr–Si/Si specimen was obviously improved when Zr was introduced into Cu film.     

The 473 K isothermal section of the Cu–Ti–Sn ternary system

The phase relationships of the Cu–Ti–Sn ternary system at 473 K have been investigated mainly by means of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), optical microscopy (OM) and differential thermal analysis (DTA). The isothermal section consists of 17 single-phase regions, 33 two-phase regions and 17 three-phase regions. The existence of 12 binary compounds and 2 ternary compounds, namely Cu₄Ti, Cu₃Ti₂, Cu₄Ti₃, CuTi, CuTi₂, Cu₃Sn, Cu₆Sn₅, Ti₃Sn, Ti₂Sn, Ti₅Sn₃, Ti₆Sn₅, Ti₂Sn₃, CuTi₅Sn₃ and CuTiSn, are confirmed in the Cu–Ti–Sn ternary system at 473 K. No new ternary compound is found. The maximum solid solubility of Cu in Ti₆Sn₅ was approximately 10 at.% Cu.     

Synthesis and characterization of amorphous Zr-based alloys with Ta and W additions

A reference Zr₅₇Cu₂₀Al₁₀Ni₈Ti₅ bulk metallic glass as well as a number of alloys obtained by addition of refractory elements Ta or W (combined with Sn) to the main Zr–Cu–Al–Ni system were elaborated by mould casting, twin roll casting and planar flow casting. The chemical compositions were chosen according to empirical rules, and as combinations of the binary eutectics for strongly interacting elements, taking into account the corresponding enthalpies of mixing. Optical microscopy, X-ray diffractometry, differential thermal analysis, differential scanning calorimetry, scanning electron microscopy and tensile mechanical testing were used to characterize the fully and partially obtained amorphous materials. Correlation of glass forming ability, thermodynamic parameters, crystallization behaviour and mechanical properties with chemical composition and production technology is discussed.     

Oxygen impurity and microalloying effect in a Zr-based bulk metallic glass alloy

A Zr-base bulk metallic glass (BMG) alloy with the base composition Zr–10 at.%Al–5% Ti–17.9% Cu–14.6% Ni (BAM-11) was used to study the effects of oxygen impurities and microalloying on the microstructure and mechanical properties. Oxygen impurity at a level of 3000 appm dramatically reduced the glass forming ability and embrittled BAM-11 at room temperature. The embrittlement was due to the formation of oxygen-induced Zr₄Ni₂O nuclei that triggered near complete crystallization of the metallic glass. Microalloying with 0.1 at.%B+0.2%Si+0.1%Pb was effective in suppressing the crystalline phase formation and alleviating the detrimental effect of oxygen. Microstructural analyses indicate that the beneficial effect of the optimum dopants was mainly due to stabilization of the glass-phase matrix even though it contained high levels of oxygen. Thus, microalloying is effective in reducing the production cost and is very useful for manufacturing good-quality Zr-based BMGs from impure charge materials.     

Formation of amorphous phase in the binary Cu−Zr alloy system

The aim of this work is to elucidate the formation of the amorphous phase in the Cu−Zr binary alloy system. It was found that 1 mm diameter rods with a fully amorphous structure can be prepared in a relatively wide range of compositions. In contrast, the formation of 2 mm diameter rods was achieved only for the Cu₆₄Zr₃₆ alloy and in the range of Cu₅₃Zr₄₇−Cu₅₀Zr₅₀, which are compositions near the energetically stable Cu₂Zr and CuZr intermetallic compounds. The difference between the calculated Gibbs free energy of the amorphous phase and the intermetallic compounds gives insight into the range of glass formation. In addition, the formation of the energetically stable phases can be kinetically by-passed owing to the crystallization of several competing phases.     

Formation and properties of the Zr75−xAlxNi10Cu10Ti5 bulk metallic glasses

Zr-based bulk metallic glasses (BMGs) exhibit interesting mechanical properties since they combine high fracture stress, elastic strain (up to 2%), significant fracture toughness and good corrosion resistance. Quaternary systems with general composition Zr–Ni–Cu–Ti show wide composition ranges in which BMG can be obtained. The addition of the another element to the quaternary alloys often increases the glass forming ability (GFA). The aim of this work was to study the influence of aluminium content on the GFA and on the mechanical properties of the Zr–Ni–Cu–Ti alloys. Multicomponent Zr_75−xAl_xNi₁₀Cu₁₀Ti₅ (x = 15, 20 at%) alloys were produced by melt spinning method obtaining ribbons, and by casting technique into a copper mould, manufacturing rod shape samples with maximum diameter of 2 mm. Supercooled liquid region depends on chemical composition and exceeds 45 °C. Vickers microhardness of studied alloys is comparable to the highest ones for other Zr-based BMG.     

The oxidation behavior of Cu–Zr–Ti–base bulk metallic glasses in air at 350–500 °C

The oxidation behavior of two Cu-base bulk metallic glasses (BMGs), having compositions Cu–30Zr–10Ti and Cu–20Zr–10Ti–10Hf (in at.%), was studied over the temperature range of 350–500 °C in dry air. In general, the oxidation kinetics of both BMGs followed the parabolic rate law, with the oxidation rates increasing with increasing temperature. The addition of Hf slightly reduced the oxidation rates at 350–400 °C, while the opposite results observed at higher temperatures. It was found that the oxidation rates of both BMGs were significantly higher than those of polycrystalline pure-Cu. The scales formed on both BMG alloys were strongly composition dependent, consisting of mostly CuO/Cu₂O and minor amounts of cubic-ZrO₂ and ZrTiO₄ for the ternary BMG, and of CuO, cubic-ZrO₂, and Zr₅Ti₇O₂₄ for the quaternary BMG. The formation of ternary oxides (ZrTiO₄ and Zr₅Ti₇O₂₄) was inferred to be responsible for the fast oxidation rates of the BMGs.     

Enhancement of the glass forming ability of Cu−Zr−Al alloys by Ag addition

The thermal stability and glass forming ability of Cu_50-xZr₄₃Al₇Ag_x (x=0, 1, 3, 5, and 7) bulk metallic glass alloys have been investigated. The glass forming ability in the Cu−Zr−Al−Ag alloys increased proportionally to the Ag content and show good correlations with thermal parameters such as ΔT_x(=T_x-T_g), T_rg(=T_g/T₁) and γ(=T_x/(T_g+T₁)). For the Cu₄₃Zr₄₃Al₇Ag₇ alloy, fully amorphous rods of 8 mm diameter were successfully fabricated by copper mold casting. Mechanical tests on this composition revealed also remarkable properties with compressive strength around 2000 MPa and large ductility.     

Microstructure and dry sliding wear resistance of laser clad TiC reinforced Ti–Ni–Si intermetallic composite coating

Wear resistant TiC reinforced Ti–Ni–Si intermetallic composite coating with a microstructure consisting of TiC uniformly distributed in Ti₂Ni₃Si–NiTi–Ti₂Ni multi-phase intermetallic matrix was fabricated on a substrate of TA15 titanium alloy by the laser cladding process using TiC/Ti–Ni–Si alloy powders as the precursor materials. Microstructure of the coating was characterized by optical microscope (OM), scanning electron microscope (SEM), X-ray diffraction (XRD) and X-ray energy dispersive spectrometer (EDS). Dry sliding wear resistance of the laser clad TiC reinforced Ti–Ni–Si intermetallic composite coating was evaluated at room temperature. Results indicated that the TiC/(Ti₂Ni₃Si–NiTi–Ti₂Ni) intermetallic composite coating exhibited excellent abrasive and adhesive wear resistance.     

Peculiarities of ball-milling induced crystalline–amorphous transformation in Cu–Zr–Al–Ni–Ti alloys

An amorphization process in (Cu₄₉Zr_45−xAl_6+x)_100−y−zNi_yTi_z (x = 1, y, z = 0; 5; 10) induced by ball-milling is reported in the present work. The aim was investigation of the effect of Ni and Ti addition to Cu₄₉Zr₄₅Al₆ and Cu₄₉Zr₄₄Al₇ based alloys as well as type of initial phases on the amorphization processes. Also the milling time sufficient for obtaining fully amorphous state was determined. The entire milling process lasted 25 h. Drastic structural changes were observed in each alloy after first 5 h of milling. In most cases, after 15 h of milling the powders had fully amorphous structure according to XRD except for those ones, where TEM revealed a few nanosized crystalline particles in the amorphous matrix. In (Cu₄₉Zr₄₅Al₆)₈₀Ni₁₀Ti₁₀ alloy the amorphization process took place after 12 h of milling and the amorphous state was stable up to 25 h of milling. In the case of (Cu₄₉Zr₄₄Al₇)₈₀Ni₁₀Ti₁₀ alloy the powders have fully amorphous structure between 12 h and 15 h of milling.     

Influence of Superheat on Microstructure and Mechanical Properties of Ductile Cu47.5Zr47.5Al5 Bulk Metallic Glass-Matrix Composite

Generally bulk metallic glasses (BMGs) posses very less ductility and toughness at room temperature. Over the recent past years to improve up on these properties in many alloy system BMG composites have been developed. It was also reported that Cu_47.5Zr_47.5Al₅ BMG composite shows a very high strength together with an extensive work hardening-like behavior of large ductility around 18%. In this study, the influence of superheat on microstructure and the resulting mechanical properties in Cu_47.5Zr_47.5Al₅ bulk metallic glass-matrix composite alloy has been studied. The Cu_47.5Zr_47.5Al₅ melt solidifies into a composite microstructure consisting of crystalline precipitates embedded in an amorphous matrix. The crystalline phase consists of B2 CuZr (cubic primitive with CsCl structure) with a small amount of monoclinic CuZr martensitic structure embedded in an amorphous matrix. The volume fraction of crystalline phases varies with melting current as well as position along the length of the as-cast rod, depending on the local cooling condition. The volume fraction and the distribution of the crystalline precipitates are heterogeneous in the amorphous matrix. Room temperature uniaxial compression tests revealed high yield strength ranging from 796 to 1900 MPa depending upon the volume fraction of the crystalline phases present. The presence of the dendritic B2 CuZr significantly improved the ductility. The BMG composites show a pronounced plastic strain up to 14% for the higher volume fraction of crystalline phase.