Influence factors and microstructure evolution during preparation of nanocrystalline (Ti, W, Mo, V)(C, N)–Ni composite powders

Nanocrystalline (Ti, W, Mo, V)(C, N)–Ni composite powders with crystalline size of about 35 nm were synthesized at 1300 °C from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation techniques. Influence of main technological parameters was investigated by X-ray diffraction, and microstructure of the milled powders and reaction products was studied by scanning electron microscopy. The results show that the phase evolution of TiO₂ follows TiO₂ → Ti₃O₅ → Ti(C, N), and (Ti, W, Mo, V)(C, N)–Ni composite powders with higher nitrogen content and smaller crystalline size can be produced by introducing high nitrogen pressure. By contrast with high nitrogen pressure, high synthesizing temperature and long isothermal time can contribute to dissolution of W, Mo and V atoms into Ti(C, N). In addition, synthesizing temperature has a significant effect on the microstructure evolution of (Ti, W, Mo, V)(C, N)–Ni composite powders.     

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.     

A contribution to the Al–Ni–Cr phase diagram

The Al–Ni–Cr phase diagram was specified at 1000 °C and partially at 900 °C. The results concerning the region below 60 at.% Al agreed qualitatively with the literature data. The binary Al–Cr phases μ and γ dissolve up to 1 and 3 at.% Ni, respectively, and Al₃Ni₂ up to 2.5 at.% Cr. Two ternary phases were revealed: hexagonal ζ (a ≈ 1.77, c ≈ 1.24 nm) in a wide range between Al₈₁Ni₃Cr₁₆, Al_76.5Ni₃Cr_20.5, Al_76.5Ni₉Cr_14.5 and Al_71.5Ni₉Cr_19.5, and high-temperature orthorhombic (a ≈ 1.26, b ≈ 3.48, c ≈ 2.02 nm) around Al_76.5Ni_2.0Cr_21.5.     

Synthesis of (Ti,W, Mo,V)(C,N) nanocomposite powder from novel precursors

(Ti, W, Mo, V)(C, N) nanocomposite powders with globular-like particle of ∼10–100 nm were synthesized by a novel method, namely carbothermal reduction–nitridation (CRN) of complex oxide–carbon mixture, which was made initially from salt solution containing titanium, tungsten, molybdenum, vanadium and carbon elements by air drying and subsequent calcining at 300 °C for 0.5 h. Phase composition of reaction products was discussed by X-ray diffraction (XRD), and microstructure of the calcined powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that the synthesizing temperature of (Ti, W, Mo, V)(C, N) powders was reduced greatly by the novel precursor method. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N) is at only 1200 °C for 2 h. The lowering of synthesizing temperature is mainly due to the homogeneous chemical composition of the complex oxide–carbon mixture and its unusual honeycombed structure.     

Effect of (Ti,W, Mo,V)(C,N) powder size on microstructure and properties of (Ti,W, Mo,V)(C,N)-based cermets

Three kinds of (Ti, 15 W, 5Mo, 0.2 V)(C, N) powders with different particle size were prepared from a mixture of oxides and carbon powders by carbothermal reduction-nitridation method. (Ti, W, Mo, V)(C, N)-based cermets were obtained by mixing Co, Ni, WC, MoC₂ and (Ti, 15 W, 5Mo, 0.2 V)(C, N) powders, and then processed via a conventional P/M technique. The influence of (Ti, 15 W, 5Mo, 0.2 V)(C, N) particle size on the microstructure and mechanical properties of (Ti, 15 W, 5Mo, 0.2 V)(C, N)-5WC-10MoC₂-7Co-8Ni cermets has been studied. When the particle size of (Ti, W, Mo, V)(C, N) is 0.2–0.5 μm, (Ti, 15 W, 5Mo, 0.2 V)(C, N)-based cermets can be characterized by weak core/rim structure. With the particle size of (Ti, W, Mo, V)(C, N) increasing to 1–1.5 μm, the microstructure of (Ti, 15 W, 5Mo, 0.2 V)(C, N)-based cermets develops into composite structure that consists of typical core/rim and no core/rim. Accordingly, typical core/rim structure is obtained in the case of the particle size of 3–5 μm. With the coarsening of raw (Ti, 15 W, 5Mo, 0.2 V)(C, N) powders, the fracture toughness of (Ti, 15 W, 5Mo, 0.2 V)(C, N) cermets is greatly improved, but the hardness continues to decline. (Ti, 15 W, 5Mo, 0.2 V)(C, N) cermets with composite structure have higher bend strength of 2165 MPa.     

The Yb–Zn–In system at 400 °C: Partial isothermal section with 0–33.3 at.% Yb

The phase relations in the ternary system Yb–Zn–In have been established for the partial isothermal section in the 0–33.3 at.% ytterbium concentration range at 400 °C, by researching of more than forty alloys. X-ray powder diffraction (XRPD), optical microscopy (OM) and scanning electron microscopy (SEM), complemented with energy dispersive X-ray spectroscopy (EDS), were used to study the microstructures, identify the phases and characterize their crystal structures and compositions. The phase equilibria of this Yb–Zn–In partial section at 400 °C are characterized by the presence of three extended homogeneity ranges, indium solubility in Yb₁₃Zn₅₈ and YbZn₂ and of zinc solubility in YbIn₂, and the existence of one ternary intermetallic compound, YbZn_1−xIn_1+x, x = 0.3. This new compound crystallizes in the UHg₂ structure type (space group P6/mmm), with a = 4.7933(5) Å, c = 3.6954(5) Å. The studied partial isothermal section has eight ternary phase fields at 400 °C.     

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.     

A convenient thermal reduction–nitridation route to nanocrystalline molybdenum nitride (Mo2N)

Nanocrystalline molybdenum nitride (γ-Mo₂N) was synthesized via a thermal reduction–nitridation route by the reaction of metallic sodium with anhydrous molybdenum pentachloride and ammonium chloride in an autoclave at 550 °C. X-ray powder diffraction pattern indicated that the product was cubic Mo₂N, and the cell constant was a = 4.161 Å. Scanning electron microscopy image showed that it consisted of particles with an average size of about 30 nm. The product was also studied by BET and TGA. It had good thermal stability and oxidation resistance below 400 °C in air.     

Phase equilibria on the ternary Mg–Mn–Ce system at the Mg-rich corner

Three isopleths at the Mg-rich corner of Mg–Mn–Ce ternary system were investigated via thermal analysis, SEM/EPMA and XRD. A ternary eutectic reaction was observed at 1 wt.% Mn and 23 wt.% Ce and 592 °C. A solid-solution type ternary intermetallic compound, (Mg,Mn)₁₂Ce, was observed with 0.5 at% solid solubility of Mn in the tetragonal Mg₁₂Ce. With the aid of thermodynamic modeling and experiments, a revised phase diagram for the binary Mg–Ce system and the isopleths of 0.6, 1.8 and 2.5 wt.% Mn were proposed up to 25 wt.% Ce.     

Effects of C particle size on the ignition and combustion characteristics of the SHS reaction in the 20 wt.% Ni–Ti–C system

C particle size plays an important role in the ignition and combustion characteristics of the SHS reaction in the 20 wt.% Ni–Ti–C system. When coarse C particles (38 and 75 μm) are used, the SHS reactions consist of two different combustion stages with different brightness intensity of the combustion wave; XRD results indicate that the first and second combustion stages mainly correspond to the formation of Ni–Ti compounds and TiC ceramics, respectively. However, the final reaction is incomplete with a few Ni–Ti compounds and unreacted C. In contrast, when the fine C particle (1 μm) is used, the SHS reaction consists of only one combustion stage with high brightness intensity of the combustion wave; XRD result indicates that final products consist of TiC and Ni, without any intermediate phase. With the decrease of C particle size, the wave velocities increase, and the ignition time becomes shorter. In addition, the morphology of TiC particulate changes to near-spherical, as C particle size decreases.     

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.     

Differential thermal analysis (DTA) on the reaction mechanism in Fe–Ti–B4C system

Differential thermal analysis (DTA) was undertaken to determine the reaction mechanism in the Fe–Ti–B₄C system under argon. When the mixtures were heated to about 786 °C, Fe₂B and C appeared as a result of Fe reacting with B₄C. As the temperature continued to increase, FeTi formed by an interdiffusion between Fe and Ti. When the mixtures were heated to 1089 °C, FeTi reacted with Ti, leading to the formation of a Fe–Ti melt, into which the displaced C and B from B₄C dissolve, forming a Fe–Ti–C–B melt. Finally, when the concentration of C and B attained a certain value, Ti reacted with C and B, yielding TiC and TiB₂ in the melt, and simultaneously considerable heat released.     

Phase equilibria and chemical vapor transport in the system Mo–Ta–As

The phase diagram Mo–Ta–As was studied in two partial isothermal sections at 1050 °C (in the As-rich corner) and at 1400 °C (As-poor alloys) using powder X-ray diffraction and electron probe microanalysis. A complete solid solution was found to exist between isostructural Mo₅As₄ and Ta₅As₄ and the ternary solubility of Mo in Ta₃As at 1400 °C was determined. A ternary phase Mo_xTa_1−xAs with MnP-type structure was found to exist in the As-rich part of the system. Lattice parameters were investigated as a function of composition for (Mo,Ta)₅As₄ and for Mo_xTa_1−xAs. Additional experiments of chemical vapor transport (CVT) from 1000 °C to 900 °C using different ternary source compositions and I₂ and Br₂ (PtBr₂) as transport agents were performed. Only Ta compounds were found in the sink and no ternary transport was observed.     

The phase equilibria of the Al–Ce–Ni system at 500 °C

The phase equilibria at 500 °C in the Al–Ce–Ni system in the composition region of 0–33.3 at.% Ce are investigated using XRD and SEM/EDX techniques applied to equilibrated alloys. The previously reported ternary phases and the variation of the lattice parameters versus the composition for different solid solution phases are investigated. It is confirmed that τ₂(Al₂CeNi) exists at 500 °C, while τ₃(Al₅Ce₂Ni₅) does not exist at 500 °C. A new compound τ₉ with composition of about Al₃₅Ce_16.5Ni_48.5 is found. The solubility of Ni in Al₁₁Ce₃ and αAl₃Ce is generally about 1 at.%, while the solubility of Ni in Al₂Ce is measured to be 2.7 at.%. The solubility of Ce in Al₃Ni, Al₃Ni₂, AlNi and AlNi₃ is all less than 1 at.%. The solubility of Al in CeNi₅, Ce₂Ni₇ and CeNi₃ is measured to be 30.4, 4.8 and 9.2 at.%, respectively, while there is no detectable solubility for Al in CeNi₂. A revised isothermal section at 500 °C in the Al–Ce–Ni system has been presented.     

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.     

Phase equilibria in the Ni–Cr–Ti system at 850°C

The isothermal cross-section through the ternary phase diagram Ni–Cr–Ti at 850°C was constructed by means of diffusion couples and equilibrated alloys. No ternary phases exist in the system at this temperature. The topology of the isotherm is largely determined by the presence of the TiCr₂-Laves phases which are in equilibrium with the binary Ti–Ni intermetallics. About 10 at.% of Ni can be dissolved in the hexagonal β-TiCr₂ at 850°C, and the solubility of nickel in cubic α-TiCr₂ is approximately 4 at.%. A small amount of nickel or chromium increases the stability of the b.c.c. β-Ti structure. At this temperature the β-Ti(Ni)-based solid solution can dissolve up to 18 at.% of Cr.     

Effect of secondary carbides addition on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-based cermets

(Ti, W, Mo, V)(C, N)-based cermets were prepared by mixing Mo₂C, WC and TaC with ultrafine (Ti, W, Mo, V)(C, N) powders, and then processed via a conventional P/M technique. The effect of Mo₂C, WC and TaC on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co systems was investigated. The Mo₂C content was varied from 0 to 10 wt.% and additive WC or TaC was added at a level of 5 wt.% with Mo₂C addition. The results show that the densification of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co cermets was improved significantly by the addition of Mo₂C. With the increase of Mo₂C content, there is a coarsening tendency in the microstructure of (Ti, 20W, 15Mo, 0.2V)(C, N)-8Ni-7Co system, but the refinement for (Ti, 15W, 5Mo, 0.2V)(C, N)-8Ni-7Co. TaC addition decreases the density of (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-8Ni-7Co cermet and thus weakens its bending strength. (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-5WC-8Ni-7Co cermet has optimal mechanical properties: bending strength of 1999 MPa, hardness (H_v) of 1677 MPa and toughness of 9.95 MPa m^1/2 respectively by adding WC, which is due to its ultrafine and weak core/rim structure.     

Effect of composition and milling parameters on the critical ball milling of Ti–Si–B powders

The absence of brittle phases and elevated temperature during ball milling of a powder mixture containing a large amount of ductile component can contribute to reach an excessive agglomeration denoting a critical ball milling (CBM) behavior. This work reports in the effect of composition and milling parameters on the CBM behavior of Ti–Si–B powders. High-purity elemental Ti–Si–B powder mixtures were processed in a planetary ball mill in order to prepare the Ti₆Si₂B compound and two-phase Ti + Ti₆Si₂B alloys. TiH₂ chips instead of titanium powder were used as a starting material. To avoid elevated temperature in the vials during ball milling of Ti–Si–B powders the process was interrupted after each 10 min followed by air-cooling. Following, the milled powders were hot-pressed at 900 °C for 1 h. Samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS). Short milling times followed by air-cooling contributed to obtain a large amount of powders higher than 75% in the vials. Only Ti and TiH₂ peaks were observed in XRD patterns of Ti–Si–B and TiH₂–Si–B, respectively, suggesting that extended solid solutions were achieved. The large amount of Ti₆Si₂B and Ti + Ti₆Si₂B structures were formed during hot pressing from the mechanically alloyed Ti–Si–B and TiH₂–Si–B powders.     

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.     

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.