Vacuum brazing of TZM alloy to ZrC particle reinforced W composite using Ti-28Ni eutectic brazing alloy

Reliable brazing of TZM alloy and ZrC particle reinforced (ZrC_p) W composite was achieved in this study by using Ti-28Ni eutectic brazing alloy. The typical interfacial microstructure of TZM/Ti-28Ni/ZrC_p-W brazed joint consisted of a Ti solid solution (Ti(s, s)) layer, a continuous Ti₂Ni layer and a diffusion layer mainly composed of W particles and (Ti, Zr)C particles. With an increase of brazing temperature, more ZrC particles and W particles entered the molten brazing alloy, which broadened the brazing seam and diminished the Ti₂Ni layer, resulting in the disappearance of the Ti₂Ni layer eventually. Meanwhile, more Ti(s, s) stripes were observed on the TZM side. The presence of continuous Ti₂Ni intermetallic phase and Ti(s, s) stripes structure in joints deteriorated the joining properties, which resulted in the formation of brittle fracture under shear test. In addition, the fracture path was related to the brazing temperature, and cracks initiate and propagate in the continuous Ti₂Ni layer at lower temperatures. However, the fracture path tended to be located at the TZM substrate close to the interface between TZM and the brazing seam when the brazing temperature exceeded 1040 °C. The optimal room temperature shear strength reached 120.5 MPa when brazed at 1040 °C for 10 min and the fracture surface exhibited cleavage fracture characteristics, and the shear strength at high temperature of 800 °C for the specimens with highest shear strength at room temperature reached 77.5 MPa.     

Deformation behavior of a two-phase Mo–Si–B alloy

Mo–Si–B alloys are being considered as possible candidates for high-temperature applications beyond the capabilities of Ni-based superalloys. In this paper, the high-temperature (1000–1400 °C) compression response over a range of quasi-static strain rates, as well as the monotonic and cyclic crack growth behaviors (as a function of temperature from 20 °C to 1400 °C) of a two-phase Mo–Si–B alloy containing a Mo solid solution matrix (Mo(Si,B)) with ∼38 vol% of the T2 phase (Mo₅SiB₂) is discussed. Analysis of the compression results confirmed that deformation in the temperature–strain-rate space evaluated is matrix-dominated, yielding an activation energy of ∼415–445 kJ/mol. Fracture toughness of the Mo–Si–B alloy varies from ∼8 MPa√m at room temperature to ∼25 MPa√m at 1400 °C, the increase in toughness with temperature being steepest between 1200 °C and 1400 °C. S–N response at room temperature is shallow whereas at 1200 °C, a definitive fatigue response is observed. Fatigue crack growth studies using R = 0.1 confirm the Paris slope for the two alloys to be high at room temperature (∼20–30) but decreases with increasing temperature to ∼3 at 1400 °C. The crack growth rate (da/dN) for a fixed value of ΔK in the Paris regime in the 900–1400 °C range, increases with increasing temperature.     

Reaction spark plasma sintering of niobium diboride

Niobium diboride (NbB₂) is synthesized and consolidated by the spark plasma sintering technique. Elemental reactants such as niobium (Nb) and boron (B) were subjected to two stage heat treatment, initially at 1200 °C for synthesis and followed by densification at the temperatures in the range of 1700 °C to 1900 °C. High dense NbB₂ (~ 97.7%ρ_th) is obtained at 1900 °C after 15 min holding period. Load application during heat treatment stage is found to improve the sinterability of the niobium diboride compacts. Hardness, elastic modulus and indentation fracture toughness of the high dense NbB₂ are measured as 20.25 GPa, 539 GPa and 4 MPa m^1/2 respectively.     

Two-step hot pressing of bimodal micron/nano-ZrB2 ceramic with improved mechanical properties and thermal shock resistance

The densification and grain growth behaviors for micron- and nano-sized ZrB₂ particles were investigated. The densification on-set temperature (T_d-micron) and grain growth on-set temperature (T_g-micron) for micron-sized ZrB₂ particles were about 1500 °C and 1800 °C, respectively. And the densification on-set temperature (T_d-nano) and grain growth on-set temperature (T_g-nano) for nano-sized ZrB₂ particles were about 1300 °C and 1500 °C, respectively. A bimodal micron/nano-ZrB₂ ceramic was therefore prepared using a novel two-step hot pressing. A high relative density of 99.2%, an improved flexural strength of 580.2 ± 35.8 MPa and an improved fracture toughness of 7.2 ± 0.4 MPa·m^1/2 were obtained. The measured critical thermal shock temperature difference (ΔT_c) for this bimodal micron/nano-ZrB₂ ceramic was as high as 433 °C.     

Influence of QLT treatment on microstructure and mechanical properties of a high nickel steel

After direct quenching from 870 °C, the samples were subjected to secondary quenching (L) at different intercritical temperatures within the two-phase region and various tempering temperatures (T). Optical microscopy and scanning electron microscopy were employed to analyse the distributions of phases and grain sizes, and transmission electron microscopy was used to reveal the morphology of martensite and retained austenite. Charpy impact specimens of the steel after different heat treatment were tested. Results show that QLT treatment gives the best impact toughness values compared with the rolling condition and conventional quenching and tempering process, and the optimum QLT heat treatment parameters are determined as Q: 870 °C, L: 770 °C, and T: 580 °C.     

Synthesis and hydrogen reduction of nano-sized copper tungstate powders produced by a hydrothermal method

The pure nano-sized copper tungstate (CuWO₄) powders were prepared by hydrothermal method and consequent annealing at 500 °C for 120 min. The thermogravimetric analysis was used to study dehydration processes, and the scanning electron microscopy (SEM) indicated that CuWO₄ particles were mostly spherical in the size range from 60 to 90 nm. Hydrogen reduction at 800 °C for 60 min converted the CuWO₄ to W–Cu composite powders. The hydrogen reduction results showed that nano-sized CuWO₄ particles calcining at 500 °C for 120 min indicated finer microstructure than the other calcination temperatures of 0 °C, 400 °C, 620 °C, 650 °C and 700 °C. W–Cu particles were observed finest and homogeneous in the size range from 90 to 150 nm by SEM images. Homogeneous distribution of W and Cu particles was clearly demonstrated by elemental mapping. Encapsulation of Cu phase by the W phase was observed by EDS and TEM. From FFT and HRTEM images, the orientation relationship of (01-1)_Cu ∥(01-1)_W and a semicoherent interface between W and Cu phases could be observed. A good correlation between the HRTEM image and the calculated lattice misfit (δ) was obtained.     

Investigation the effect of B4C addition on properties of TZM alloy prepared by spark plasma sintering

TZM alloy is one of the most important molybdenum (Mo) based alloy which has a nominal composition containing 0.5–0.8 wt.% titanium (Ti), 0.08–0.1 wt.% zirconium (Zr) and 0.016–0.02 wt.% carbon (C). It is a possible candidate for high temperature applications in a variety of industries. However, the rapid oxidation of TZM alloys at high temperature in air is considered to be one of the drawback. In this study, TZM alloys with additions of 0–5 wt.% B₄C were prepared by spark plasma sintering (SPS) at 1420 °C utilizing 40 MPa pressure for 5 min under vacuum. The effects of B₄C addition on oxidation, densification behavior, microstructure, and mechanical properties were investigated. The TZM alloy with 5 wt.% B₄C have exhibited an approximately 66% reduction in mass loss under normal atmospheric conditions in oxidation tests made at 1000 °C for 60 min. And an increase from 1.9 GPa to 7.8 GPa has been determined in hardness of the alloy.     

Effect of sintering temperature on the structure and properties of polycrystalline cubic boron nitride prepared by SPS

The polycrystalline cubic boron nitride (PcBN) with Si₃N₄–AlN–Al₂O₃–Y₂O₃ ceramic system as binding agents was prepared by spark plasma sintering (SPS). The starting materials Si₃N₄, AlN, Al₂O₃, Y₂O₃, and cBN in the ratio of 22:14:10:4:50 were heated to a sintering temperature between 1250 °C and 1450 °C at a heating rate of 300 °C/min, with a holding time of 5 min in nitrogen atmosphere. The microstructure, phase constitution, microhardness and fracture toughness of the prepared PcBN were then studied. It was shown that the Si₃N₄–AlN–Al₂O₃–Y₂O₃–cBN polycrystalline materials were densified in a very short sintering time resulting in materials with relative densities of more than 95%. When the sintering temperature increased, the microhardness and fracture toughness of prepared PcBN were also increased. The microhardness of PcBN prepared at 1250–1450 °C was between 28.0 ± 0.5 GPa and 48.0 ± 0.9 GPa, and its fracture toughness K_IC was from 7.5 ± 0.2 MPa m^1/2 to 11.5 ± 0.3 MPa m^1/2. Microstructure study showed that the ceramic-binding agents bonded with cubic boron nitride particles firmly. Our work demonstrated that spark plasma sintering technology could become a novel method for the preparation of PcBN cutting materials.     

A thermo-gravimetric and microstructural study of the oxidation of Nbss/Nb5Si3-based in situ composites with Sn addition

The effect of Sn addition on the oxidation of the Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf–5Sn (at.%) alloy (JG6) in the as cast (AC) and heat treated (HT) conditions was studied at 800 °C and 1200 °C in static air using thermo-gravimetry and microstructural analysis. The oxidation kinetics, morphology and microstructure of the oxide scale and the microstructure of the bulk of the oxidised alloy were investigated. Oxidation occurred by inward oxygen anion diffusion. The oxidation of JG6 at 800 °C and 1200 °C is compared with the oxidation of Sn-free Nb–Ti–Si–Cr–Al–Mo–Hf alloys and is found to have been improved by the addition of Sn. At 800 °C pest oxidation, which was exhibited by the heat treated Nb–24Ti–18Si–5Al–5Cr–2Mo–5Hf alloy (JG4-HT), was eliminated by alloying with 5 at.% Sn. The elimination of pesting at 800 °C is attributed to the nature of the Nb solid solution in the alloy which consists of Sn-rich, Si-rich and Ti lean solid solution usually surrounded by Sn-poor, Si-poor and Ti-rich solid solution. The oxide scales that formed at 1200 °C on JG6 did not separate from the base metal and consisted of Nb₂O₅, TiO₂, SiO₂, HfO₂ and TiNb₂O₇. TiN, instead of TiO₂, and the (Nb,Ti)₅(Sn_1−xSi_x)₃ phase, which is considered as a ternary phase based on Nb₅Sn₂Si, are formed in the diffusion zone of the alloys JG6-AC and JG6-HT after oxidation at 1200 °C. The formation of these phases in the oxidised alloys JG6-AC and JG6-HT controlled the penetration of oxygen into the base material. The better oxidation performance of JG6-AC compared to JG6-HT at 1200 °C is attributed to the formation of Nb₃Sn in the former. It is suggested that the presence of the Sn-poor, Si-poor and Ti-rich Nb_ss in the microstructure is a key to the formation of the Nb₃Sn phase at the scale/diffusion zone interface in the JG6-AC oxidised at 1200 °C.     

Oxidation behavior of an Zr53Ni23.5Al23.5 bulk metallic glass at 400–600 °C

The oxidation behavior of the Zr₅₃Ni_23.5Al_23.5 bulk metallic glass (BMG) and its crystalline counterpart was investigated over the temperature range of 400–600 °C in dry air and pure oxygen. In general, the oxidation kinetics of BMG followed the single- or two-stage parabolic rate law at T ≤ 500 °C, with rate constants (K_p values) generally increased with temperature. Conversely, three-stage parabolic kinetics were observed for BMG at T ≥ 550 °C, with K_p values decreased with increasing temperature. The oxidation rate constants for the BMG alloy are slightly higher than those for crystalline alloy at T ≤ 500 °C. In addition, K_p values of BMG were nearly independent of partial pressure of oxygen, implying a typical scaling behavior with a n-type semiconductivity. The scales formed on the BMG is temperature-dependent, consisting mainly of tetragonal-ZrO₂ (t-ZrO₂) and minor amounts of Al₂O₃ at T ≤ 475 °C. At higher temperatures (T ≥ 500 °C), some monoclinic-ZrO₂ (m-ZrO₂) were also detected, and its amounts increased with increasing temperature. The BMG substrate began to form the crystalline Zr₂Ni, Zr₂Al, and ZrNiAl phases beneath the scales after oxidation at T ≥ 450 °C.     

Mullite/molybdenum ceramic–metal composites

Dense (>98 th%) homogeneous mullite/Mo (32 vol.%) composites with two different Mo average grain sizes (1.4 and 3 μm) have been obtained at 1650°C in vacuum and in reducing condition. Depending on the Mo grain size and processing atmosphere, the K_IC ranges from 4 to 7 MPa m^1/2 and σ_f from 370 to 530 MPa. The MoO₂–2SiO₂·3Al₂O₃–Mo system was found to be compatible in solid state, and a solid solution of ≈4 wt% of MoO₂ in mullite at 1650°C was detected. A solid state dewetting of MoO₂ from the surface of the Mo particle takes place during sintering. It was found that the absence of MoO₂ in the mullite/Mo composites by processing in reducing conditions increases the strength of the metal/ceramic interface and the plasticity of the Mo metal particles, thus strengthening the composite by a crack bridging mechanism. As a result, the K_IC and the σ_f values of the ceramic–metal composite were found to be ≈4 times and ≈2 times higher than the ones corresponding to the mullite matrix.     

Effect of Al2O3 ceramic binder on mechanical and microstructure properties of spark plasma sintered WC-Co cermets

This study investigates how the partial replacement of Co with Al₂O₃ ceramic binder has an effect on the sintering behaviour, microstructure, and final mechanical properties of WC-Co cermets via spark plasma sintering. To examine this, three batches (WC-6 wt%Co, WC-3 wt%Co-3 wt%Al₂O_3, and WC-6 wt%Al₂O₃) were mixed through high energy ball mill, and sintering was carried out at temperatures of 1350 °C and 1600 °C. The results showed nearly full dense WC-Co cermets at different temperatures. It was shown that WC-6 wt%Al₂O₃, in comparison to reference WC-6 wt%Co cermet, not only led to the rise in sintering temperature from 1350 °C to 1600 °C, but also reduced its strength and toughness. But replacing some part of Co with alumina (WC-3 wt%Co-3 wt%Al₂O₃) exhibited the combination of high strength (1095 MPa), hardness (17.62 GPa), and fracture toughness (19.46 MPa·m^1/2).     

Investigation on the preparation and machinability of the B4C/BN nanocomposites by hot-pressing process

The machinable B₄C/BN nanocomposites were fabricated by the hot-pressing process using the B₄C/BN nanocomposite powders at 1850 °C for 1 h under the pressure of 30 MPa. The nanocomposite powders with the microstructure of micro-sized B₄C particles coated with amorphous nano-sized BN particles were prepared by the chemical reaction of H₃BO₃ and CO(NH₂)₂ on the surface of B₄C particles at high temperature. Then the amorphous BN transformed into the hexagonal-BN (h-BN) after the hot-pressing process at 1850 °C. The microstructure investigations of the B₄C/BN nanocomposites sintered samples showed that the nano-sized h-BN particles were homogenously distributed within the matrix grains as well as at the matrix grains boundaries. With the increasing content of h-BN, the relative density of the B₄C/BN nanocomposites decreased gradually. The fracture strength and fracture toughness of the B₄C/BN nanocomposites decreased gradually, the fracture strength and fracture toughness of the B₄C/BN nanocomposites with the h-BN content of 10 wt.% and 20 wt.% achieved high values. The Vickers hardness of the B₄C/BN nanocomposites decreased remarkably with the increasing content of h-BN, while the drilling rates and machinability of the B₄C/BN nanocomposites increased significantly. The B₄C/BN nanocomposites with the h-BN content more than 20 wt.% exhibited excellent machinability.     

Preparation of Eu-activated strontium orthosilicate (Sr1.95SiO4:Eu0.05) phosphor by a sol–gel method and its luminescent properties

Eu²⁺-activated Sr₂SiO₄ phosphor was successfully synthesized by a sol–gel method using sodium silicate and SrO as the starting materials. The wavelength of the emission peak and the emission intensity of the phosphor powders were influenced by the pre-treating temperature. The maximum emission intensity of the phosphor was found as pre-treated at 1200 °C in air and then heated at 1300 °C in the reducing atmosphere (10% H₂ + 90% He). As the pre-treating temperature was <1200 °C, the composition of the phosphor powder was not uniform, which leads to decrease of the emission intensity, whereas >1200 °C, the decrease of the emission intensity may be caused from the reversible phase transformation of Sr₃SiO₅ → Sr₂SiO₄ at 1300 °C, which also shows the red-shift behavior.     

Mechanical properties at the nanometer scale of GDC and YSZ used as electrolytes for solid oxide fuel cells

The Young’s modulus (E), hardness (H) and fracture toughness (K_IC) of various compositions of gadolinia doped-ceria (GDC, Gd_xCe_1?xO_2?x/2, 0.1 ? x ? 0.2) and yttria-stabilized zirconia (YSZ, Y_0.08Zr_0.92O_1.96) electrolytes were investigated by nanoindentation. All samples were produced by the sol–gel method, formed by uniaxial pressure and sintered at 1400 °C. In order to determine the mechanical properties, a Berkovich diamond tip was employed at applied loads of 5, 10, 30, 100 and 500 mN. The results were interpreted by the Oliver–Pharr method and values of K_IC were determined using the method of Palmqvist cracks. The residual imprints were observed by field emission scanning electron microscopy. The results obtained showed that the H, E and K_IC of GDC decreased with increasing gadolinia concentration, due to the oxygen vacancies generated by the dopant addition. As a result, the mechanical properties of GDC were significantly lower than those of YSZ electrolyte.     

Wetting of (0001) α-Al2O3 single crystals by molten Al

The wetting behavior of (0 0 0 1) α-Al₂O₃ by molten Al was studied over a wide temperature range between 700 and 1500 °C. The increase in the contact angle with time at temperatures lower than 1200 °C is attributed to the surface structural reconstruction of the (0 0 0 1) α-Al₂O₃. High-temperature annealing of the substrate does not have a significant influence on the wettability.     

Oxidation behavior and phase transition of ZrB2–SiCw–ZrO2f ceramic

The oxidation behavior and phase transition of ZrB₂–SiC_w–ZrO_2f ceramic had been investigated by in situ high-temperature XRD, XPS, SEM, EDS and TEM measurements. The initial oxidation temperature of most ZrB₂ was 1000 °C and no significant oxidation of SiC was found up to 1200 °C. The oxidation products formed at lower temperatures would penetrate into the pores and flaws on the surface, which was beneficial to crack healing. In order to improve the oxidation resistance of this system, it should be focused on decreasing the oxygen diffusivity and the volume expansion caused by phase transition.     

Anisothermal solid-state reactions of Ni/Al nanometric multilayers

The structural evolution of Ni/Al multilayer thin films with temperature was studied by differential scanning calorimetry (DSC), scanning electron microscopy (SEM), transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM) and X-ray diffraction (XRD). Thin films with nanometric Ni and Al alternated layers were deposited by d.c. magnetron sputtering. In our experiments, we used a bilayer thickness of 5, 14 and 30 nm and a total film thickness ranging from 2 to 2.7 μm. The XRD patterns of the as-deposited sample revealed only peaks of Al and Ni. DSC experiments were performed on freestanding films, from room temperature to 700 °C at 10 and 40 °C/min. Two exothermic reactions were detected in the DSC curves of the film with a 30 nm bilayer thickness, with peak temperatures at 230 and 330 °C. The films with 5 and 14 nm bilayer thickness presented only one exothermic peak at 190 and 250 °C, respectively. To identify the intermetallic reaction products, DSC samples were examined by XRD. NiAl formation corresponds to one single DSC peak, for films with short bilayer thicknesses (5 and 14 nm). The films with 30 nm bilayer thickness were heated at 250 °C (T = T_{1st peak}), 300 °C (T_{1st peak} < T < T_{2nd peak}), 450 °C (T > T_{2nd peak}) and 700 °C. The XRD results indicated that at 250 °C the phase formed was NiAl₃, whilst NiAl₃ and Ni₂Al₃ phases were identified at 300 °C. For the 450 °C sample, only NiAl was detected. Further heating to 700 °C promotes the growth of NiAl grains.     

The oxidation behavior of high Cr and Al containing Nb-Si-Ti-Hf-Al-Cr alloys at 1200 and 1250 °C

The oxidation behavior of two alloys containing different content of Al and Cr from the Nb-Si-Ti-Hf-Al-Cr system has been evaluated at 1200 and 1250 °C. The alloy compositions in atomic percent are Nb-24Ti-16Si-2Hf-2Al-10Cr (B1), and Nb-24Ti-16Si-2Hf-6Al-17Cr (B2). The oxidation kinetic of B1 alloy at 1200 and 1250 °C followed a mixed parabolic-linear law, while the oxidation kinetic of B2 alloy at 1200 and 1250 °C followed a parabolic law. The weight gain of B2 alloy was 18.9 mg/cm² after oxidation at 1200 °C for 100 h, which was a seventh of the value of that of B1 alloy. Besides, oxidation became more severe as temperature increased to 1250 °C. The oxide scales of B2 alloy consisted of CrNbO₄, TiNb₂O₇ and SiO₂, which were relatively compact and protective. In addition, the oxidation mechanism of Nb-Si based alloys were also discussed.     

Carbothermal synthesis of ZrC powders using a combustion synthesis precursor

ZrC powders were synthesized by carbothermal reduction of a combustion synthesized precursor derived from zirconium nitrate, urea, and glucose mixed solution. The results showed that the obtained precursor was comprised of polyporous blocky particles. The precursor powders were subsequently calcined under argon at 1200–1600 °C for 3 h. The transformation of ZrO₂ to ZrC, by adopting this route, occurred at 1300 °C. The preparation of ZrC experienced an intermediate phase of ZrOxCy. ZrC powders synthesized at 1500 °C are characterized by the spherical shape, small particle size (120–180 nm in diameter), low oxygen content (1.4 wt.%) and non-aggregated particles.