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.     

Microstructure identification of devitrified Cu–Ti–Zr–Ni bulk amorphous alloy

The microstructures of devitrified Cu–Ti–Zr–Ni bulk amorphous alloy were identified by X-ray diffractometry (XRD) and transmission electron microscope (TEM). XRD and TEM examinations show that the deep eutectic structures of the tested alloy consist of CuTi₂–Cu₁₀Zr₇, Cu₃Ti–CuZr, Cu₃Ti–Cu₁₀Zr₇–CuZr low-order eutectics. Moreover, short-range ordering clusters in the melt with configuration similar to that of Cu₁₀Zr₇ compound may contribute to the glass forming ability of bulk amorphous Cu–Ti–Zr–Ni alloy.     

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 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.     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

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 corrosion behavior of Cu–Al and Cu–Al–Be shape-memory alloys in 0.5 M H2SO4 solution

The corrosion behavior of Cu–Al and Cu–Al–Be (0.55–1.0 wt%) shape-memory alloys in 0.5 M H₂SO₄ solution at 25 °C was studied by means of anodic polarization, cyclic voltammetry, and alternative current impedance measurements. The results of anodic polarization test show that anodic dissolution rates of alloys decreased slightly with increasing the concentrations of aluminum or beryllium. Severe intergranular corrosion of Cu–Al alloy was observed after alternative current impedance measurement performed at the anodic potential of 0.6 V. However, the addition of a small amount of beryllium was effective to prevent the intergranular corrosion. The effect of beryllium addition on the prevention of intergranular corrosion is possibly attributed to the diffusion of beryllium atoms into grain boundaries, which in turn deactivates the grain boundaries.     

In situ XRD studies on Al–Ni and Al–Ni–Sr alloys prepared by rapid solidification

In this paper the structure and stability of Al–17 wt.%Ni(Al–17Ni) and Al–17 wt.%Ni–2 wt.%Sr alloys prepared by rapid solidification was investigated by means of XRD techniques. Our work demonstrates that both alloys are crystalline and composed of fcc (Al–Ni) solid solution and orthorhombic Al₃Ni phases. The ternary alloy shows in addition the presence of small amount of tetragonal Al₄Sr phase. In situ XRD experiment demonstrates the stability of the solute solution up to 650 °C, Al₃Ni above 750 °C while Al₄Sr overcomes melting of the major phases at 800 °C. High-temperature structure analysis proved strong bindings between Al and Ni atoms in Al₃Ni phase, corroborating its covalent nature, linear and faster increase of the fcc volume with annealing temperature. The linear correlation between constituting atoms decreases with increase of the temperature.The work also documents the applicability of pair distribution function (PDF) analysis to the study of multiphase crystalline systems.     

In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti–6Al–4V in simulated body fluid at 25 °C and 37 °C

The corrosion resistance of Ti and Ti–6Al–4V was investigated through electrochemical impedance spectroscopy, EIS, potentiodynamic polarisation curves and UV–Vis spectrophotometry. The tests were done in Hank solution at 25 °C and 37 °C. The EIS measurements were done at the open circuit potential at specific immersion times. An increase of the resistance as a function of the immersion time was observed, for Ti (at 25 °C and 37 °C), and for Ti–6Al–4V (at 25 °C), which was interpreted as the formation and growth of a passive film on the metallic surfaces.     

Constitution of the high-Al region of Al–Cu–Rh

Phase equilibria between 540 and 1010 °C were studied in Al–Cu–Rh alloys containing more than 50 at.% Al. Congruent equiatomic AlRh dissolves more than 40 at.% Cu and extends up to 58 at.% Al at the high-Cu part of its compositional range. High-temperature cubic C-Al₅Rh₂ (C-phase) dissolves up to 13 at.% Cu, “Al₃Rh” (₆-phase) up to 15 at.% Cu and Al₉Rh₂ up to 1.5 at.% Cu. The solubility of the third element in other binary Al–Rh and Al–Cu phases is below 0.5 at.%. Close to the high-Cu limit of the C-phase region the fcc C₂-phase structurally related to the C-phase is formed. Stable decagonal phase (D₁-phase) is formed below 1005 °C in a compositional range extending from Al₆₅Cu₁₆Rh₁₉ to Al₆₂Cu₂₃Rh₁₅, which shifts to higher Cu concentrations with decreasing temperature. An additional ternary phase forming around the Al₇₀Cu₂₀Rh₁₀ composition below 660 °C was revealed. Partial 1010, 990, 900, 800, 700, 600 and 540 °C isothermal sections were determined.     

Vacuum brazing of TiAl-based intermetallics with Ti–Zr–Cu–Ni–Co amorphous alloy as filler metal

An amorphous Ti41.7–Zr26.7–Cu14.7–Ni13.8–Co3.1 (wt%) ribbon fabricated by melt spinning was used as filler to vacuum braze Ti–48Al–2Nb–2Cr (at%) intermetallics. The influences of brazing temperature and time on the microstructure and strength of the joints were investigated. It is found that intermetallic phases of Ti₃Al and γ-Ti₂Cu/Ti₂Ni form in the brazed joints. The tensile strength of the joint first increases and then decreases with the increase of the brazing temperature in the range of 900–1050 °C and the brazing time varying from 3 to 15 min. The maximum tensile strength at room temperature is 316 MPa when the joint is brazed at 950 °C for 5 min. Cleavage facets are widely observed on all of the fracture surfaces of the brazed joints. The fracture path varies with the brazing condition and cracks prefer to initiate at locations with relatively high content of γ-Ti₂Cu/Ti₂Ni phases and propagate through them.     

Determination of phase equilibria in the Co-rich Co–Al–W ternary system with a diffusion-couple technique

Phase equilibria in the Co-rich Co–Al–W ternary system were determined with a unique diffusion-couple technique in which Co–27Al and Co–15W binary alloys (at. %) were first coupled for interdiffusion and then heat-treated for precipitation. After a diffusion process at 1300 °C for 20 h, concentration gradients of Al and W were formed in the γ-Co(A1) matrix in the vicinity of the coupled interface. After a heat treatment at 900 °C for 500 h the γ′-Co₃(Al,W)(L1₂) phase was formed with a coarsened shape in contact with the γ, CoAl(B2) and Co₃W(D0₁₉) phases. Additionally, it appeared with a submicron cuboidal shape within the γ matrix. After 2000 h, however, the coarsened γ′ phase became infrequent and the three phases of γ, CoAl and Co₃W came into frequent contact with each other. These results clearly demonstrate that the γ′ phase is metastable and the three phases of γ, CoAl and Co₃W are thermodynamically in equilibrium at 900 °C in the Co–Al–W ternary system.     

Nanocrystalline spherical iron–nickel (Fe–Ni) alloy particles prepared by ultrasonic spray pyrolysis and hydrogen reduction (USP-HR)

FeCl₂ and NiCl₂ were used for synthesis of nanocrystalline spherical Fe–Ni alloy particles by ultrasonic spray pyrolysis and hydrogen reduction (USP-HR). Spherical ultrafine Fe–Ni particles were obtained by USP of aqueous solutions of iron–nickel chloride followed by thermal decomposition of generated aerosols in hydrogen atmosphere. Particle sizes of the produced Fe–Ni particles can be controlled by the change of the concentration of an initial solution. The effect of the precursor solution in the range of 0.05, 0.1, 0.2 and 0.4 M on the morphology and crystallite size of the Fe–Ni alloy particles are investigated under the conditions of 1.5 h running time, 900 °C reduction temperature, and 1.0 L/min H₂ volumetric flow rate. X-ray diffraction (XRD) studies and Scherrer crystallite size calculations show that the crystalline size was nearly 28 nm. Energy dispersive spectroscopy (EDS) was performed to determine the chemical composition of the particles. Transmission electron microscope (TEM) was used to confirm the crystalline size, that was determined using XRD results. Scanning electron microscopy (SEM) observations reveal that the precursor solution strongly influences the particle size of the synthesized Fe–Ni alloy particles. Spherical nanocrystalline Fe–Ni alloy particles in the range of 80 and 878 nm were obtained at 900 °C.     

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.     

Multi-stage transformation in annealed Ni-rich Ti49Ni41Cu10 shape memory alloy

Multi-stage transformation (MST) in 500 °C annealed Ni-rich Ti₄₉Ni₄₁Cu₁₀ shape memory alloy (SMA) is investigated by differential scanning calorimetry (DSC), dynamic mechanical analyzer (DMA), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The as solution-treated alloy undergoes B2 ↔ B19 ↔ B19′ two-stage transformations. Ti(Ni,Cu)₂ precipitates are formed in 500 °C annealed specimens. Alloy annealed at 500 °C for 6–24 h exhibits MST. This MST is confirmed by DMA tests and is composed of B2₁ ↔ B19₁ ↔ B19′₁ and B2₂ ↔ B19₂ ↔ B19′₂ transformations corresponding to the regions near and far from Ti(Ni,Cu)₂ precipitates, respectively. Experimental results show that the more the annealing time, the more the B2₁ ↔ B19₁ ↔ B19′₁ transformations and finally only B2₁ ↔ B19₁ ↔ B19′₁ transformations retain with the transformation temperatures close to those of Ti₅₀Ni₄₀Cu₁₀ SMA.     

Effect of brazing temperature and brazing time on the microstructure and tensile strength of TiAl-based alloy joints with Ti-Zr-Cu-Ni amorphous alloy as filler metal

An amorphous Ti-37.5Zr-15Cu-15Ni (wt.%) ribbon fabricated by vacuum arc remelting and rapid solidification was used as filler metal to vacuum braze TiAl alloy (Ti-45Al-2Mn-2Nb-1B (at.%)). The effects of brazing temperature and time on the microstructure and strength of the joints were investigated in details. The typical brazed joint major consisted of three zones and the brazed joints mainly consisted of α_2-Ti₃Al phase, α-Ti phase and (Ti, Zr)₂(Cu, Ni) phase. When the brazing temperature varied from 910 °C to 1010 °C for 30 min, the tensile strength of the joint first increased and then decreased. With increasing the brazing time, the tensile strength of the joint increased. The maximum room temperature tensile strength was 468 MPa when the specimen was brazed at 930 °C for 60 min. All the fracture surfaces assumed typical brittle cleavage fracture characteristic. The fracture path varied with the brazing parameter and cracks preferred to initiate at (Ti, Zr)₂(Cu, Ni) phase and propagation path were mainly determined by the content and distribution of α-Ti phase and (Ti, Zr)₂(Cu, Ni) phase.     

Cu + TiB2 composite filler for brazing Al2O3 and Ti-6Al-4V alloy

Al₂O₃ and Ti-6Al-4V alloy were brazed using Cu + TiB₂ composite filler, which manufactured by mechanical milling of Cu and TiB₂ powders. Typical interface microstructure of joint was Al₂O₃/Ti₄(Cu,Al)₂O/Ti₂Cu + Ti₃Al + Ti₂(Cu,Al)/Ti₂(Cu,Al) + AlCu₂Ti/Ti₂Cu + AlCu₂Ti + Ti₃Al + Ti₂(Cu,Al) + TiB/Ti(s.s) + Ti₂Cu/Ti-6Al-4V alloy. Based on temperature- and time-dependent compositional change, the formation of intermetallics in joint was basically divided into four stages: formation of interfacial Ti₄(Cu,Al)₂O in Al₂O₃ side, formation of Ti₂Cu, Ti₃Al, TiB, Ti₂Cu, and AlCu₂Ti in layers II and IV, formation of Ti₂(Cu,Al) and AlCu₂Ti in layer III, formation of Ti + Ti₂Cu hypereutectoid organization adjacent to Ti-6Al-4V alloy. TiB in situ synthesized in joint not only acted as low thermal expansion coefficient reinforcement to improve the mechanical properties at room temperature, but also as skeleton ceramic of joint to increase high temperature mechanical properties of Al₂O₃/Ti-6Al-4V alloy joint increasing. When the joint containing 30 vol.% TiB brazed at 930 °C and 10 min of holding time, the maximum room temperature shear strength of joint was 96.76 MPa, and the high temperature shear strength of joint was 115.16 MPa at 800 °C.     

Reinforcement of Al–Fe–Ni alloys with the in situ formation of composite materials

One of the most effective methods for the improvement of the mechanical properties of metals is their reinforcement with non-metallic materials. In the present work powder of K₂TiF₆ and KBF₄ was added in an Al–Fe–Ni alloy while the alloy was in liquid form at 1060 °C with a 5 wt.% mixture of powders and with simultaneous stirring for 30 min. The liquid was squeeze-casted at 150 bar. The as-cast specimens were examined with electron microscopy and X-ray diffraction. SEM analysis revealed that the as-formed material is composed by needle-like crystallites along with a dentritic form and an interdendritic phase. The composition of the needle-like crystallites may presumably be expressed by the formula (Fe-Ni)Al₃. The rest of the matrix consists of almost pure Al grown dentritically, while the interdendritic phase contains Fe and Ni dissolved in Al. EDS analysis also proved the existence of spots with high Ti concentration, which probably refer to the Ti–B compounds. Finally TEM verified the presence of nanocrystals in the matrix.     

Influence of thermal cycling on shear strength of Cu–Sn3.5AgIn–Cu joints with various content of indium

This work presents an investigation on the influence of thermal cycling of Cu–Sn3.5AgIn–Cu joints for various content of indium. Solders Sn–3.5Ag containing 0, 6.5 and 9 mass% In were prepared by rapid quenching of appropriate alloys. Joints Cu–solder–Cu were prepared in furnace at 280 °C and 1800 s. Thermal cycling was in the interval room temperature (RT)–150 °C up to 1000 cycles and in the interval RT–180 °C for 500 cycles. The shear strength of the joints with indium-free solder decreases with increasing number of cycles. On the contrary shear strength of joints with indium containing solders increases with increasing number of cycles. It is related with the thickness of Cu₆Sn₅ phase which makes the interface between Cu substrate and solder. In the first case the thickness of this phase is growing with increasing number of cycles, in the second case the amount of this phase is reducing with increasing the number of cycles due to the support of dissolution of copper from Cu₆Sn₅ phase into the Sn–Ag–In solder by indium. X-ray diffraction analysis of original solders as well as of uncycled and 1000 times cycled joints made with all three kinds of solders is given.     

Oxidation behavior at 300–1000 °C of a (Mo,W)Si2-based composite containing boride

The oxidation behavior of a (Mo,W)Si₂ composite with boride addition was examined at 300–1000 °C for 24 h in dry O₂. The oxidation kinetics was studied using a thermobalance, and the oxide scales were analyzed using a combination of electron microscopy (SEM/EDX, FIB, BIB) and XRD. Accelerated oxidation was found to occur between 500 °C and 675 °C, with a peak mass gain at 625 °C. The rapid oxidation is attributed to the vaporization of molybdenum oxide that leaves a porous and poorly protective silica layer behind. At higher temperature (700–1000 °C) a protective scale forms, consisting of a dense SiO₂/B₂O₃ glass.