Tensile creep of Mo–Si–B alloys

Multiphase Mo–Si–B alloys containing a Mo solid solution matrix and brittle Mo₃Si and Mo₅SiB₂ (T2) intermetallic phases are candidates for ultra-high-temperature applications_. The elevated temperature uniaxial tensile response at a nominal strain rate of 10^?4 s^–1 and the tensile creep response at constant load between 1000 °C and 1300 °C of a (i) single phase solid solution (Mo–3.0Si–1.3B in at.%), (ii) two-phase alloy containing ～35 vol.% T2 phase (Mo–6Si–8B in at.%) and (iii) three-phase alloy with ～50 vol.% T2 + Mo₃Si phases (Mo–8.6Si–8.7B in at.%) were evaluated. The results confirm that Si in solid solution significantly enhances both the yield strength and the creep resistance of these materials. A Larson–Miller plot of the creep data showed improved creep resistance of the two- and three-phase alloys in comparison with Ni-based superalloys. The extent of Si dissolved in the solid solution phase varied in these three alloys and Si appeared to segregate to dislocations and grain boundaries. A stress exponent of ～5 for the solid solution alloy and ～7 at 1200 °C for the two multiphase alloys suggested dislocation climb to be the controlling mechanism. Grain boundary precipitation of the T2 phase during creep deformation was observed and the precipitation kinetics appear to be affected by the test temperature and applied stress.     

Refinement of primary Si in Cu–50Si alloys with novel Al–Zr–P master alloy

In this article, a novel Al-6Zr-2P master alloy with ZrP particles was successfully synthesized, and the refining performance of this novel master alloy for the primary Si in Cu-50Si alloys was also investigated. By means of the fracture plane observation, it is found that the ZrP phase would precipitate first in the solidification process, and then, the ZrAl 3 phase grows around them. Furthermore, it is observed that the refining effect can be remarkably improved by changing the addition sequence of the raw materials. After the melting of commercial Cu, the 2.0 wt% Al-6Zr-2P master alloy and crystalline Si were added in sequence, and the mean size of the primary Si in Cu-50Si alloy can be significantly refined from 255.7 to 75.3 lm. Meanwhile, the refining mechanism was discussed in detail.     

Effects of fluidised bed quenching on heat treating characteristics of cast Al–Si–Mg and Al–Si–Mg–Cu alloys

Abstract

The quench sensitivity of Al–Si–Mg (D357 unmodified and Sr modified), and Al–Si–Mg–-Cu (354 and 319 Sr modified) cast alloys was investigated using a fluidised bed (FB). The average cooling rate of castings in the fluidised bed is lower than those quenched in water; the cooling rate first increases to a certain maximum and then decreases during quenching. The change in the cooling rate during quenching in water was more drastic, where the cooling rate varied from 0 to ?80 K s^?1 in less than 8 s, as compared with those quenched in FB, where the cooling rate varied from 0 to ?14 K s^?1 in 18 s. The FB quenching resulted in the formation of several metastable phases in Al–Si–Mg–Cu alloys; in contrast, no such transformation was observed during water quenching. The T4 yield strength of the FB quenched alloys was greater than water quenched alloys owing to the formation of a greater volume fraction of metastable phases in the FB quenched alloys. The tensile properties of T6 treated alloys show that Al–Si–Mg alloys (both unmodified and Sr modified) are more quench sensitive than Al–Si–Mg–Cu alloys. The high quench sensitivity of the Al–Si–Mg alloys is because GP zones are not formed, whereas GP zones are formed during quenching of the Al–Si–Mg–Cu alloys as predicted by time temperature transformation and continuous cooling transformation) diagrams.     

Microstructural design of hardfacing Ni–Cr–B–Si–C alloys

This work reports the procedure for selection of alloying elements to refine the microstructure of hardfacing Ni–Cr–B–Si–C alloys by providing in situ formed nucleation agents. It is concluded that the refining element should be able to spontaneously produce precipitates at high temperatures with little solubility in their Cr-rich counterparts. After exploring the theoretical backgrounds on how to select the refining element, Nb and Zr were selected and the phase formation reactions of Zr- or Nb-modified Ni–Cr–B–Si–C alloys were calculated using Thermo-Calc® simulations. Detailed microstructural analyses of the rapidly solidified samples deposited from the modified alloys showed that addition of Nb in specific quantities induces a significant microstructural refinement in the original Ni–Cr–B–Si–C alloy without deteriorating its high hardness. The Nb-modified alloy could be used to further investigate the viability of microstructural refinement as an effective toughening mechanism for Ni–Cr–B–Si–C and similar alloy systems.     

Phase equilibria in the system Al–Co–Si

The Al–Co–Si system was studied for three isothermal sections at 600 °C (equilibria with Si), 800 °C (alloys up to 50 at.% Co) and 900 °C (alloys with more than 50 at.% Co). A total number of seven ternary compounds were characterized in the ternary system and the homogeneity ranges of the various ternary solid solutions of binary Co–Al and Co–Si compounds were studied. X-ray powder diffraction and optical microscopy was used for initial sample characterization and electron probe microanalysis of the annealed samples was used to determine the phase compositions within the ternary system. Lattice parameters have been determined for all ternary compounds and the change of lattice parameters with the composition is given for the solid solution phases.     

Environmental Resistance of Mo–Si–B Alloys and Coatings

For high temperature application beyond the range of Ni-base superalloys, multiphase Mo–Si–B alloys with compositions, that yield the ternary intermetallic Mo₅SiB₂ (T₂) phase as a key microstructure constituent together with the Mo and Mo₃Si phases, offer an attractive balance of high melting temperature, oxidation resistance and mechanical properties. The investigation of reaction kinetics involving the T₂ phase enables the analysis of oxidation in terms of diffusion pathways and the design of effective coatings. From this basis kinetic biasing is used together with pack cementation to develop multilayered coatings and in situ diffusion barriers with self-healing characteristics for enhanced oxidation resistance. While a combustion environment contains water vapor that can accelerate attack of silica based coatings, the current pack cementation coatings provide oxidation resistance in water vapor up to at least 1500 °C. An exposure to hot ionized gas species generated in an arc jet confirms the robust coating performance in extreme environments.     

Effect of Si on the reversibility of stress-induced martensite in Fe–Mn–Si shape memory alloys

Fe–Mn–Si is a well-characterized ternary shape memory alloy. Research on this alloy has consistently shown that the addition of 5–6 wt.% Si is desirable to enhance the reversibility of stress-induced martensite vis-à-vis shape memory. This paper examines the effect of Si on the morphology and the crystallography of the martensite in the Fe–Mn–Si system. It is concluded that the addition of Si increases the c/a ratio of the martensite, reduces the transformation volume change and decreases the atomic spacing difference between the parallel close-packed directions in the austenite–martensite interface (habit) plane. It is proposed that, in addition to austenite strengthening, Si enhances reversibility by reducing the volume change and the interfacial atomic mismatch between the martensite and the austenite. Although shape memory is improved, transformation reversibility remains limited by the necessary misfit dislocations that accommodate the atomic spacing differences in the interface.     

Phase composition and structure of aluminum Al–Cu–Si–Sn–Pb alloys

The structure and phase composition of cast and heat treated Al–Cu–Si–Sn–Pb alloys containing 6 wt % Sn, 2 wt % Pb, 0–4 wt % Cu, 0–10 wt % Si have been studied using calculations and experimental methods. Polythermal and isothermal sections are reported, which indicate the existence of two liquid phases. It was found that the low-melting phase is inhomogeneous and consists of individual leadand tin-based particles.     

Studying recovery processes in a strain-hardened Al–Mg–Mn–Fe–Si alloy

The material of a shell structure subjected to 20-year use under ambient conditions has been studied. The structure and mechanical characteristics of a strain-hardened AMg6 alloy, as well as the effect of subsequent holdings of this alloy for 10–3000 h at temperatures of 50, 70, 80, 100, 130, 150, 180, and 220°C, on changes in its dislocation structure and mechanical characteristics have been investigated. It has been shown that, in the structures under study, the AMg6 alloy has a cellular structure with a high density of dislocations and the ultimate strength σ_u = 445.5 ± 2.5 MPa, the proof stress σ_0.2 = 326.5 ± 3.5 MPa, and the relative elongation δ = 11.7 ± 0.5%. Polygonization in the alloy occurs at a temperature of 220°C and the initial stage of the recovery process corresponds to a temperature range of 50–100°С in which the softening process can be divided into two stages, i.e., stage (1) of active softening due to the interaction of point defects with each other and stage (2) of the stabilization of the characteristics of the alloy.     

Thermodynamic modeling of the Nb–Si system

Optimized coefficients of the Gibbs free energy expression for each stable phase of the binary Nb–Si have been obtained, using the Thermo-Calc program for this purpose. The Nb₃Si, αNb₅Si₃, NbSi₂ and Diamond (Si) have been modeled as stoichiometric phases and the liquid L, BCC (Nb) and the βNb₅Si₃ phases as solutions, with the excess term described using the Redlich–Kister formalism. The Si solubility in the βNb₅Si₃ phase has been modeled according to two possibilities: (i) Si substituting for Nb and (ii) vacancies in the Nb positions. The calculated diagrams compare well with the experimental information taken from the literature.     

Kinetics of Oxidation of Fe–6Si

Surface oxidation of Fe–6Si during annealing in low-pressure air (～10⁴ Pa) in the temperature range 500–550 °C was investigated using resistivity measurements, Mössbauer spectroscopy, X-ray diffraction and scanning-electron microscopy (SEM). The time dependence of the resistivity exhibits an increase in two steps, which indicates changes in the structure and/or phase composition of the alloy. Structure and phase investigations show that the first step can be explained as formation of hematite (α-Fe₂O₃) and the second step is due to transformation of the hematite to magnetite (Fe₃O₄). The kinetics of the transformations were derived from the resistivity data. The activation energies (estimated from Arrhenius plots) of 194 kJ/mol and 165 kJ/mol were obtained for the formation of hematite and transformation of hematite to magnetite, respectively.     

Non-equilibrium solidification of undercooled Co–Si melts

The effect of melt undercooling on solidification modes of peritectic Co–Si alloys has been studied by electromagnetic levitation. For Co_82.5Si_17.5, Co₈₁Si₁₉ and Co₇₅Si₂₅ alloys there are transitions towards direct crystallization of peritectic ε-Co and a metastable Co₃Si phase, respectively. For Co₇₃Si₂₇ a morphology change of the equilibrium α-Co₂Si phase was observed.     

Extrusion and selected engineering properties of Mo–Si–B intermetallics

In this study, an extrusion process has been developed to produce defect free, high-density rods of Mo–Si–B material. An initial powder composition (53.5 vol.%, 91 wt.%) of 66 vol.% Mo₅Si₃B_x (T1)–16 vol.% MoB–18 vol.% MoSi₂ was mixed with a paraffin-wax based binder (46.5 vol.%, 9 wt.%) and extruded using a twin-screw extruder. Following binder removal by a combination process of wicking and thermal degradation, the material was sintered at 1800°C. The bulk density of the sintered material was 90–92% of theoretical. Thorough binder removal was evidenced by low impurity levels: 258±6 ppm carbon and 772±10 ppm oxygen. The material demonstrated excellent high temperature oxidation resistance. The calculated parabolic rate constant is 1.1×10⁻² mg²/cm⁴/h at 1600°C. The extruded material was also successfully tested as a resistance heating element. These materials show promise for the development of heating elements with enhanced performance compared to current MoSi₂-based heating elements.     

A comparative study on corrosion of Mg–Al–Si alloys

Corrosion behavior of various Mg–Al–Si alloys (AS11, AS21, AS41, AS61 and AS91 series), cast under the same cooling conditions and controlled alloying composition, was investigated systematically. Optical microscopy and scanning electron microscopy were used for microstructural examinations. The corrosion behavior was evaluated by immersion tests and potentiodynamic polarization measurements in 3.5% NaCl solution. The results from both immersion tests and the potentiodynamic polarization measurements showed that marginal improvement in corrosion resistance was observed with 2.0% Al (mass fraction) containing alloy (AS21) whereas Al addition above 2.0% (AS41, AS61 and AS91) deteriorated the corrosion resistance which was attributed to β phase, acting as cathode, and the interruption of continuity of the oxide film on the surface of the alloys owing to coarsened β and Mg₂Si phases.     

Influence of vibrational entropy on structural stability of Nb–Si and Mo–Si systems at elevated temperatures

The heats of formation of stable and metastable phases of the Nb–Si and Mo–Si systems were studied using density functional theory (DFT). The high-temperature behavior of the competing phases was studied by performing additional phonon calculations. Our theoretical results rationalize the major differences observed in the behavior of the Nb–Si and Mo–Si systems: Nb₃Si is only stable at temperatures above 2043 K, whereas Mo₃Si is always stable; Nb₅Si₃ and MoSi₂ undergo phase changes at elevated temperatures, in contrast to Mo₅Si₃ and NbSi₂. These differences are qualitatively explained by including the vibrational entropy to the free energies within the harmonic approximation. In particular, the softer shear moduli of the Nb₅Si₃ and MoSi₂ βphases cause their stabilities over the α phases at elevated temperature.     

Wetting of porous titanium carbonitride by Al–Mg–Si alloys

Wetting of porous TiC_0.17N_0.83 by six alloys from the Al–Mg–Si system (pure Al, pure Mg, Al–15 at.% Mg, Al–10 at.% Si, Mg–5 at.% Si, and Al–10 at.% Mg–10 at.% Si) in an argon atmosphere was studied using the sessile drop experiment. The contact angle of the liquid drops on TiC_0.17N_0.83 substrates was measured as a function of temperature. Aluminium, Al–10 at.% Si, and Al–10 at.% Mg–10 at.% Si did not wet TiC_0.17N_0.83 in the studied temperature range. Magnesium always wetted TiC_0.17N_0.83 with a minimum contact angle of ≈44° at 900°C, and alloying with Mg significantly lowered the contact angle of Al on TiCN. Alloying with Si deteriorated the wetting of TiCN by Mg. A comparative study between the systems was conducted, based on the results and on data available in the literature. The improvement of the wetting of TiCN by Al due to alloying with Mg can be explained by the segregation of Mg to the interface with TiCN, where it lowers the interface energy. The addition of Si to pure Mg or to Al–Mg results in an increase in the contact angle on TiCN.     

Enhanced Oxidation Resistance of Mo–Si–B–Ti Alloys by Pack Cementation

As new high-temperature structural materials, Mo–Si–B alloys satisfy several requirements such as oxidation and creep resistance. Recently, novel Ti-rich Mo–Si–B alloys have shown an increased creep resistance compared to Ti-free alloys. However, due to the formation of a duplex SiO₂–TiO₂ oxide layer, which allows for fast ingress of oxygen, the oxidation resistance is poor. To improve the oxidation resistance, a borosilicate-based coating was applied to a Mo–12.5Si–8.5B–27.5Ti (in at.%) alloy. After co-deposition of Si and B by pack cementation at 1000 °C in Ar, a conditioning anneal at 1400 °C is used to develop an outer borosilicate layer followed by an inner MoSi₂ and Mo₅Si₃ layer. During both isothermal and cyclic oxidation after an initial mass loss during the first hours of exposure, a steady state is reached for times up to 1000 h at temperatures ranging from 800 to 1200 °C, demonstrating a significantly enhanced oxidation resistance.