Phase relations in an Fe-Cr-S system at temperatures of 1073 and 1173 K in the sulfur pressure range from 100 to 10−5 Pa

Phase relations and stability fields in the Fe-Cr-S system were investigated at 1073 and 1173 K in the sulfur pressure range 10⁰–10^–5 Pa. The sulfides, produced by the sulfidation-annealing process of Fe-Cr alloys followed by rapid quenching, were characterized using X-ray diffraction powder analysis at room temperature. The Cr₃S₄ in the Cr-S system extends beyond the FeCr₂S₄ stoichiometry in the Fe-Cr-S ternary system at intermediate sulfur pressures. The spinel-monoclinic transition of the FeCr₂S₄ was observed at sulfur pressures of 10^–3–10^–3.5Pa at 1073 K and at 10⁰–10^–0.5 Pa at 1173 K. The free energy change for formation of the spinel, FeCr₂S₄, from a monoclinic (Cr, Fe)₃S_4–y, hexagonal (Fe, Cr)_1–xS, and sulfur vapor is given by the relation G = –1523 + 1.09 T (kJ/mol). The phase-transition mechanism of FeCr₂S₄ is discussed on the basis of an enhancement of the cation coordination numbers from 4-6-6 for the spinel to 6-6-6 for the monoclinic, when the sulfur partial pressure decreases.Emeritus Professor.     

Phase Diagram of the Ni–Cr–S System at 873 K between 10−4 and 10−8 Pa

The phase diagram of the Ni–Cr–S system was determined at 873 Kby sulfidation of thin Ni-Cr alloy sheets (22, 50, 66.6, and 80 at.% Cr) at10^–4.0, 10^–5.5, 10^–7.0,and 10^–8.0 Pa in H₂S–H₂ gasmixtures. X-ray diffraction analysis identified two sulfides,NixCr_3–xS₄ (03S₂,while concentration profiles were measured by electron-probe microanalysis(EPMA). The compositions of the terminal sulfides and alloys in equilibriumwere determined at sulfur pressures below 10^–5.5 Pa, whereasat 10^–4.0 Pa they were obtained from the Cr₃S₄and Ni₃S₂ phases at their interface. The proposedphase diagram shows that the solubility limit of Cr into Ni₃S₂is only a few atomic percent Cr, while the Ni content in Cr₃S₄decreases rapidly with decreasing sulfur pressures from 14 at.% Ni, a metalratio N_Ni/(N_Ni+N_Cr) of 0.32, at 10^–4.0Pa to a negligible value at sulfur pressures below 10^–8.0 Pa.     

Sulfidation properties of TiAl–2 at.% X (X=V,Fe, Co,Cu, Nb,Mo, Ag and W) alloys at 1173 K and 1.3 Pa sulfur pressure in an H2S–H2 gas mixture

TiAl–2 at. % X (X=V, Fe, Co, Cu, Nb, Mo, Ag and W) alloys were sulfidized at 1173 K for 86.4 ks at a 1.3 Pa sulfur pressure in an H₂–H₂S gas mixture. The structure, phases, and compositions of the external sulfide scale and alloy surface layer were measured using EPMA and X-RD. The TiAl–2Ag and –2Cu alloys sulfidized faster than TiAl, and the alloy surface layer was thicker than that of TiAl. Sulfidation amounts of the TiAl–2X (X=V, Co, Fe, Mo, W and Nb) alloys were almost the same as that of TiAl, while the thickness of the alloy surface layer decreased in the order: V>Co>Fe>Mo>[Cr (by Narita T, Izumu T, Yatagai M, Yoshioka T. Intermetallics, 2000;8:371)]>W>Nb. The sulfide scale was composed of multi-layer structures: an outermost (rich in Ti-sulfides), an outer (rich in Al₂S₃), an inner (a mixture of Ti-sulfides and Al₂S₃), and an innermost (rich in Ti-sulfides) layer. The alloy surface layer also had a multi-layer structure, and was classified into four groups: group 1 for TiAl–2V and –2Co alloys as well as TiAl binary alloy where the surface layer consists of alloy substrate/TiAl₂/TiAl₃/sulfide scale, group 2 for TiAl–2Nb, –2Mo, and –2W (and also– 2Cr) alloys with alloy substrate/TiAl₂/TiAl₃/(Nb, Mo, W or Cr)–Al alloy/sulfide scale, group 3 for TiAl–2Cu and –2Ag alloys with alloy substrate/TiAl₂/Ti (Al, Ag or Cu)₃ with an L1₂ structure/TiAl₃/sulfide scale, and group 4 for TiAl–2Fe alloy with alloy substrate/TiAl₂/Ti(Al,Fe)₃ with an L1₂ structure/TiAl₃/FeAl₃/sulfide scale. Diffusion paths for these four groups were shown in a tentative Ti–Al–X ternary phase diagram.     

4 K crystallographic and electronic structures of (TMTTF)2X salts (X−: PF6−, AsF6−

The 4 K crystallographic and electronic structures of (TMTTF)₂PF₆ and (TMTTF)₂AsF₆ are presented. The structural investigation was performed by neutron diffraction. Thermal expansion and structural data are compared to those of the Se analogues. The tight-binding band electronic structures are based on calculations of the transfer integrals within the dimer splitting approximation. The results are discussed and compared to the room-temperature values. The trasfer integrals of the two salts, which are very similar at 300 K, tend to differ markedly at low temperature. The observed differences in the transfer integrals are related to the changes of the orientation of two neighbouring organic chains. The variations of the electronic parameters appear to depend on the anion.     

Effect of strain rate difference between inside and outside groove in M−K model on prediction of forming limit curve of Ti6Al4V at elevated temperatures

The influence of initial groove angle on strain rate inside and outside groove of Ti6Al4V alloy was investigated. Based on the evolution of strain rate inside and outside groove, the effect of strain rate difference on the evolution of normal stress and effective stress inside and outside groove was also analyzed. The results show that when linear loading path changes from uniaxial tension to equi-biaxial tension, the initial groove angle plays a weaker role in the evolution of strain rate in the M−K model. Due to the constraint of force equilibrium between inside and outside groove, the strain rate difference makes the normal stress inside groove firstly decrease and then increase during calculation, which makes the prediction algorithm of forming limit convergent at elevated temperature. The decrease of normal stress inside groove is mainly caused by high temperature softening effect and the rotation of groove, while the increase of normal stress inside groove is mainly due to strain rate hardening effect.     

Sulfidation Properties of Ni–20Cr and Ni–13.5Co–20Cr Alloys at 873 K under Low Sulfur Pressures in H2S-H2 Atmospheres

The sulfidation properties of Ni–20Cr and Ni–13.5Co–20Cralloys as well as a nickel-base superalloy AISI685 were investigated at873 K in H₂S–H₂ gas mixtures with sulfur partial pressures of10^–4, 10^–5.5, and 10^–7Pa by mass-gain measurements,electron-probe microanalysis (EPMA), and X-ray diffraction (XRD)analysis. Sulfidation obeyed the parabolic rate law, and the parabolic rateconstants decreased in the order Ni–20Cr, Ni–13.5Co–20Cr,and AISI685 at each sulfur pressure. With decreasing sulfur pressure, therate constants first decreased slowly and then rapidly at a 10–7 Pasulfur pressure. At both 10^–4 and 10^–5.5 Pa sulfur pressures,Ni–20Cr formed a surface scale with a duplex structure of inner(Cr₃S₄) and outer (Ni₃S₂) layers, while Ni–13.5Co–20Cr formeda triplex structure of inner (Cr₃S₄), intermediate(Ni,Co)Cr₂S₄, and outer[Ni₃S₂+(Co,Ni)₉S₈] layers. Thesurface scale formed on AISI685 was verycomplex, comprising at least four layers, a fibrous (Co,Ni)₉S₈ top surface,outer [Ni₃S₂+(Co,Ni)₉S₈], and intermediate [(Cr,Ti)₃S₄] layers, as well asan inner layer containing Cr, Ti, Mo, Al, and S. At the 10^–7 Pa sulfurpressure, which is lower than the dissociation pressure of Ni₃S₂, bothNi–20Cr and Ni–13.5Co–20Cr formed a surface scale ofCr₃S₄ covered by a thin NiCr₂S₄ layer, accompanied by copious internalsulfidation of Cr₃S₄ and/or CrS. On AISI685 there was a surface scale of(Cr,Ti)₃S₄ accompanied by the usual internal sulfidation. It is discussedthat diffusion of cations in the inner Cr₃S₄ layer is the rate-determiningstep for the growth of the multilayer structures. At the 10^–7 Pasulfur pressure, diffusion of Cr and S contribute to form a thin surfacescale and internal sulfidation, respectively.     

AMts alloy cracking resistance,strength, strain,and energy characteristics at strain rates of 10−3–103 sec−1

The literature gives little information on the effects of strain rate on the mechanical properties of alloys. The cracking resistance criterion K has been determined for low-strength aluminum alloy AMts on small specimens, together with a series of standard and nonstandard strength, strain, and energy characteristics for plastic-strain rates of 10^–3–10³ sec^–1. A dynamically loaded structure such as the central tube in a spiral explosive magnetic generator should be made of AMts alloy in the heat-treated state.All-Russian Experimental Physics Research Institute, Arzamas-16. Translated from Metallovedenie i Termicheskaya Obrabotka Metallov, No. 8, pp. 31–35, August, 1994.     

The Accumulation and Annealing of Radiation-Induced Defects and the Effect of Hydrogen on the Physicomechanical Properties of the V−4Ti−4Cr and V−10Ti−5Cr Vanadium-Based Alloys under Low-Temperature (at 77 K) Neutron Irradiation

The processes of the accumulation and annealing of radiation-induced defects that occur under low-temperature (at 77 K) irradiation (with an energy E > 0.1 MeV) of V?4Ti?4Cr and V?10Ti?5Cr bcc alloys both nonmodified and modified with hydrogen isotopes in a concentration of 200 ppm, as well as the effect of these processes on the physicomechanical properties of these alloys, have been studied. It has been found that the saturation of these alloys with hydrogen leads to slight changes in their strength and ductility characteristics. The irradiation of the alloys at the temperature of 77 K results in a substantial increase in their yield stress and ultimate strength, as well as a decrease in their ductility. In the course of the postradiation annealing of the alloys at a temperature of 130 K, the stage related to the migration of interstitial atoms is observed. At temperatures of 290–320 K, the recovery stage occurs due to the formation of vacancy clusters. The stage that occurs at a temperature of 470 K can be attributed to the formation of impurity-vacancy clusters. Possible mechanisms of the radiation-induced strengthening of the alloys during irradiation and subsequent annealing have been discussed.     

Influence of Al Addition on Oxidation Behavior of Cu–Ni–Cr Alloys at 973–1073 K in 1.01 × 10<Superscript>2</Superscript> kPa Pure Oxygen

The oxidation behavior of Cu–20Ni–15Cr–2.5Al and Cu–20Ni–20Cr–2.5Al alloys was studied at 973–1073 K in 1.01 × 10² kPa pure oxygen. The oxidation kinetics exhibited large deviations from the parabolic rate law and were comprised of three or four quasi-parabolic stages. Oxidation rates of the present alloys were much lower than those previously reported for a Cu–20Ni–20Cr alloy. Cu–20Ni–15Cr–2.5Al alloy formed a continuous scale of chromia in contact with the alloy, while at other locations, the scale formed deep protrusions into alloy along β phases. Cu–20Ni–20Cr–2.5Al alloy formed a continuous scale of chromia with a small quantity of light and unoxidized precipitates of α phase, especially at 1073 K. There was a thin layer depleted in Cr beneath the continuous scales of chromia. The addition of 2.5 at.% Al to Cu–Ni–Cr alloy made the diffusion of reactive component Cr become much faster and facilitated the formation of a continuous external scale of chromia for a lower Cr content.     

Oxidation behavior of sulfidation processed TiAl–2 at.%X (X=Si,Mn, Ni,Ge, Y,Zr, La,and Ta) alloys at 1173 K in air

The oxidation behavior of sulfidation processed TiAl–2 at.%X (X=Si, Mn, Ni, Ge, Y, Zr, La, and Ta) alloys was investigated at 1173 K in air for up to 630 ks under a heat-cycle condition between 1173 K and room temperature. During the sulfidation processing the TiAl–2 at.%Ta alloy formed Ta-aluminides on the TiAl₃ layer, while the alloys containing Mn, Ni, Y, and Zr formed a TiAl₃ (TiAl₂ included) layer including a small amount of the third element, like the TiAl binary alloy. The cross-sectional microstructure of the TiAl–2 at.%Ta alloy shows the sequence: oxide scale/TiAlTa/TiAl₂/alloy substrate; and the cross sections of the alloys containing Mn, Ni, Y, and Zr are: oxide scale/Ti₃Al/alloy substrate. The TiAl–2 at.%Ta alloy showed some scale exfoliation at the initial stage of oxidation, but very little exfoliation after long oxidation times, whereas alloys containing other third elements such as Si and Ge showed little exfoliation at the first several cycles and then tended to exfoliate significantly, resulting in very rapid oxidation. The TiAlTa/TiAl₂ layers formed by the reaction between the Ta-aluminide and TiAl₃ improve the oxidation properties of the TiAl–2 at.%Ta alloy.