A Derivation of a Quadratic Activity Coefficient <Emphasis Type=Italic>vs</Emphasis> Composition Relationship in a Quaternary System, <Emphasis Type=Italic>A-B-C-D</Emphasis>

In the literature, no direct derivation exists of the quadratic activity coefficient vs composition relationships for a quaternary system with high solute concentrations. Such relations for a ternary system (1-2-3) were derived by Darken by extending the results of a binary system (1-2), introducing a new concept of “hypothetical system” (2-3). To present a better scheme to find the activity coefficient-composition relations for multicomponent systems, derivations are made for a quaternary system A-B-C-D in the current work. Using a MacLaurin series expansion, the (Raoultian) activity coefficient, ln γ _i , of each component is equated with a quadratic expression of mole fractions (x), involving the activity coefficient at zero concentration ( g_i⁰ ) left( {gamma_{i}^{0} } right) and nine interaction coefficients (ε). Subsequently, with the help of a Gibbs–Duhem equation, followed by a comparison of coefficients, most preceding 9 × 4, i.e., 36 interaction coefficients are eliminated, leaving behind only three self- and three ternary interaction coefficients, which are enough to express the activity coefficient vs composition relationships for the solutes B, C, and D, as well as for the solvent A. Setting the mole fraction x _D  = 0, the preceding expressions establish the same relations as proposed by Darken for the ternary system A-B-C. The derivation also clarifies how the quadratic concentration terms accompany the first-order interaction coefficients, not the second-order ones. Applications of the derived relations to determine simultaneously the activity coefficients g_i⁰ gamma_{i}^{0} and the interaction coefficients ε in a new way in some iron- and steelmaking systems are presented. A new data on interaction coefficients in liquid iron at 1873 K (1600 °C), e_textV^textV = - 6. 1, varepsilon_{text{V}}^{text{V}} = - 6. 1, has been generated through such an application.     

Anomalous Mixing State in Room-Temperature Ionic Liquid-Water Mixtures: <Emphasis Type=Italic>N,N</Emphasis>-diethyl-<Emphasis Type=Italic>N</Emphasis>-methyl-<Emphasis Type=Italic>N</Emphasis>-(2-methoxyethyl) Ammonium Tetrafluoroborate

The mixing states of room-temperature ionic liquid (RTIL) H₂O mixtures (x = 0.0 mol pct to 99.5 mol pct H₂O) were investigated using wide-angle X-ray scattering (WAXS), small-angle X-ray scattering (SAXS), and optical absorption in an ultraviolet and visible (UV-vis) region. The RTIL is N, N-diethyl-N-methyl-N-(2-methoxyethyl) ammonium tetrafluoroborate, [DEME][BF₄]. In a “prepeak” region of the WAXS, the scattered intensities increased at 85 mol pct to 95 mol pct. A medium-range order (MRO) in the liquid structure as observed in network-forming materials developed markedly. In the SAXS experiments, we can detect nanoscale fluctuations relating to polar and nonpolar regions. At 65 mol pct to 85 mol pct, the SAXS intensity increased unexpectedly. Furthermore, entirely different optical absorption spectra in the UV-vis region were observed as a macroscopic property from 90 mol pct to 95 mol pct. We suppose that these anomalies relate to the MRO of the liquid structure. All anomalies probably are induced by an intrinsic property in [DEME][BF₄]-H₂O mixtures.     

Thermal conductivity of NdCl<Subscript>3</Subscript>-<Emphasis Type=Italic>M</Emphasis>Cl (<Emphasis Type=Italic>M</Emphasis> = Na,K, Cs) melts

The thermal conductivities of individual NdCl₃, the K₃NdCl₆ chemical compound, an equimolar 0.5NdCl₃-0.5NaCl mixture, and eutectic 0.5NdCl₃-0.5KCl and 0.45NdCl₃-0.55CsCl mixtures are measured. For all melts, the concentration and temperature dependences of the thermal conductivity are found.     

<Emphasis Type=Italic>L</Emphasis><Subscript>3</Subscript>-XANES spectroscopy of the valence-unstable cerium in intermetallic compounds with 3<Emphasis Type=Italic>d</Emphasis> metals

The effective valence of cerium is studied by L ₃-XANES spectroscopy using synchrotron radiation in the following valence-unstable systems with different types of magnetic ordering: a CeNi matrix doped with neodymium, praseodymium, and gadolinium ions in the temperature range 5–300 K and the Ce₂Fe1_{7 − x} Mn _x intermetallic compound. The obtained dependences are discussed in terms of generally accepted models of states with an intermediate valence of rare-earth ions. Possible correlations between the effective valence of cerium and the magnetic properties of the substances are taken into account.     

Ultrasound velocity and adiabatic compressibility of GdCl<Subscript>3</Subscript>-<Emphasis Type=Italic>M</Emphasis>Cl (<Emphasis Type=Italic>M</Emphasis> = Na,Cs) melts

The ultrasound velocity in GdCl₃ + MCl (M = Na, Cs) chloride melts is measured over wide temperature and composition ranges, and their adiabatic compressibility is calculated. A correlation is established between the relative deviations of these properties from their values in hypothetic ideal salt mixtures and the reciprocal alkali-metal cation radii. The role of lanthanide compression in the propagation of sound vibrations in the chlorides of cerium group REMs is revealed.     

Ultrasound velocity and adiabatic compressibility of LaCl<Subscript>3</Subscript> + <Emphasis Type=Italic>M</Emphasis>Cl (<Emphasis Type=Italic>M</Emphasis> = Li,Na, K,Rb, and Cs) melts

The ultrasound velocity in binary LaCl₃ + MCl (M = Li, Na, K, Rb, and Cs) melts is measured, and their adiabatic compressibility is calculated as a function of temperature and composition. A relation is established between the relative deviations of these properties from their values for hypothetic ideal salt mixtures, on the one hand, and the ionic potentials of the alkali-metal cations, on the other.     

First <Emphasis Type=Italic>In Situ</Emphasis> Lattice Strains Measurements Under Load at VULCAN

The engineering materials diffractometer, VULCAN, at the Spallation Neutron Source began commissioning on June 26, 2009. This instrument is designed for materials science and engineering studies. In situ lattice strain measurements of a model metallic material under monotonic tensile load have been performed on VULCAN. The tensile load was applied under two different strain rates, and neutron diffraction measurements were carried out in both high-intensity and high-resolution modes. These experiments demonstrated VULCAN’s in situ study capability of deformation behaviors even during the early phases of commissioning.     

<Emphasis Type=Italic>In-Situ</Emphasis> Observations of Martensitic Transformation in Blast-Resistant Steel

A hybrid in-situ characterization system, which couples the laser scanning confocal microscopy (LSCM) with the time-resolved X-ray diffraction (TRXRD) measurement with synchrotron radiation, was used to characterize the microstructure evolution during heat-affected zone (HAZ) thermal cycling of high-strength and blast-resistant steel. The combined technique has a time resolution of 0.3 seconds that allows for high-fidelity measurements of transformation kinetics, lattice parameters, and morphological features. The measurements showed a significant reduction in the martensite start transformation temperature with a decrease in the prior austenite grain size. In addition, the LSCM images confirmed the concurrent refinement of martensite packet size with smaller austenite grain sizes. This is consistent with dilatometric observations. The austenite grain size also influenced the rate of transformation (df _m /dT); however, the measurements from the hybrid (surface) and dilatometric (volume) measurements were inconsistent. Challenges and future directions of adopting this technique for comprehensive tracking of microstructure evolution in steels are discussed.     

<Emphasis Type="Italic">In Situ</Emphasis> Observation of Calcium Aluminate Inclusions Dissolution into Steelmaking Slag

The dissolution rate of calcium aluminate inclusions in CaO-SiO₂-Al₂O₃ slags has been studied using confocal scanning laser microscopy (CSLM) at elevated temperatures: 1773 K, 1823 K, and 1873 K (1500 °C, 1550 °C, and 1600 °C). The inclusion particles used in this experimental work were produced in our laboratory and their production technique is explained in detail. Even though the particles had irregular shapes, there was no rotation observed. Further, the total dissolution time decreased with increasing temperature and decreasing SiO₂ content in the slag. The rate limiting steps are discussed in terms of shrinking core models and diffusion into a stagnant fluid model. It is shown that the rate limiting step for dissolution is mass transfer in the slag at 1823 K and 1873 K (1550 °C and 1600 °C). Further investigations are required to determine the dissolution mechanism at 1773 K (1500 °C). The calculated diffusion coefficients were inversely proportional to the slag viscosity and the obtained values for the systems studied ranged between 5.64 × 10^?12 and 5.8 × 10^?10 m²/s.     

<Emphasis Type=Italic>In Situ</Emphasis> Studies of Intercritically Austempered Ductile Iron Using Neutron Diffraction

Intercritically austempered ductile irons hold promise for applications requiring fatigue durability, excellent castability, low production energy requirements, reduced greenhouse gas emissions, and excellent machinability. In the present study, four different ductile iron alloys, containing manganese and nickel as the primary austenite-stabilizing elements, were heat treated to obtain different quantities of austenite in the final microstructure. This article reports the microstructures and phases present in these alloys. Furthermore, lattice strains and diffraction elastic constants in various crystallographic directions and the transformation characteristics of the austenite were determined as a function of applied stress using in situ loading during neutron diffraction at the second generation Neutron Residual Stress Facility at the High Flux Isotope Reactor at Oak Ridge National Laboratory.     

Texture Evolution and Phase Transformation in Titanium Investigated by <Emphasis Type=Italic>In-Situ</Emphasis> Neutron Diffraction

Time-of-flight neutron diffraction was used to study in-situ texture evolution and the α → β phase transformation in cold-drawn titanium upon continuous heating. The texture changes in the α phase at elevated temperatures upon recrystallization are presented. For the first time, a transient β texture was observed during the α → β transformation, as indicated by the initial rise and the final drop of the {110} _β reflection intensity. This unusual observation is explained in terms of competitive growth between inter- and intragranular β allotriomorphs.     

Fiber <Emphasis Type=Italic>vs</Emphasis> Rolling Texture: Stress State Dependence for Cold-Drawn Wire

The texture of the cold-drawn copper wire was investigated along the radius using electron backscatter diffraction. The complex fiber texture of the central region of the wire was considered as the rolling texture consisting of a set of preferred orientations. The texture of the periphery region was revealed to be similar to the shear texture. The orientation-dependent properties of the wire were proven to be determined by the texture of the near-surface layers.     

<Emphasis Type=Italic>In-Situ</Emphasis> Neutron Scattering Measurement of Stress-Strain Behavior of a Bulk Metallic Glass

Bulk metallic glasses (BMGs) are an emerging class of materials whose unique properties make them excellent choices for many applications. As with crystalline metals, the processing and forming techniques used to produce BMG components necessarily result in residual stresses. However, traditional diffraction stress analysis is difficult to apply to BMG components, because they lack the long-range order necessary to produce sharp diffraction patterns, and thus, the internal strains for BMG have not been examined until recently. In this work, in-situ neutron scattering was used to measure the local elastic internal strain distribution in a Zr₅₇Nb₅Cu_15.4Ni_12.6Al₁₀ BMG as a function of applied stress. Various techniques were used to evaluate the internal strain. The strain was determined in real space, by measuring changes in the atomic pair distribution function (PDF). These results can be used to help understand the elastic deformation of BMGs as well be to evaluate current models of BMG deformation. This article is based on a presentation given in the symposium entitled “Bulk Metallic Glasses IV,” which occurred February 25–March 1, 2007 during the TMS Annual Meeting in Orlando, Florida under the auspices of the TMS/ASM Mechanical Behavior of Materials Committee.     

<Emphasis Type=Italic>In Situ</Emphasis> Observation of Strain Evolution in Cp-Ti Over Multiple Length Scales

The strain evolution in polycrystalline CP-Ti strip under tension was studied in situ and at two length scales using Synchrotron X-ray diffraction. To establish the bulk material behavior, experiments were performed at the Australian Synchrotron facility. Because of the relatively large grain size, discontinuous “spotty” Debye ring patterns were observed, and a peak fitting algorithm was developed to determine the individual spot positions with the necessary precision for strain determination. The crystallographic directional dependence of strain anisotropy during the loading cycle was determined. Strain anisotropy and yielding of individual crystallographic planes prior to the macroscopic yield point were further clarified by in situ loading experiments performed at the Advanced Light Source (ALS). The deviatoric strain accumulation and plastic response were mapped on a grain-by-grain basis. The onset of microscopic yielding in the grains was identified and correlated with the relative orientation of the grains with respect to the loading direction.     

Development of methods for estimating the <Emphasis Type=Italic>Z</Emphasis> properties of thick rolled products

The main stages of developing the methods for estimating the mechanical properties of rolled plates across the plate thickness (Z properties) and the corresponding standards are described in a chronological manner. The application of experimental fracture mechanics methods for estimating the sensitivity of building steels to laminated fracture is discussed. The effects of the structure dispersity, the steel purity in non-metallic inclusions, and the reduction on the Z properties of rolled products are described.     

<Emphasis Type=Italic>In Situ</Emphasis> Neutron-Diffraction Studies on the Creep Behavior of a Ferritic Superalloy

Precipitate strengthening effects toward the improved creep behavior have been investigated in a ferritic superalloy with B2-type (Ni,Fe)Al precipitates. In situ neutron diffraction has been employed to study the evolution of the average phase strains, (hkl) plane-specific lattice strains, interphase lattice misfit, and grain-orientation texture during creep deformation of the ferritic superalloy at 973 K (700 °C). The creep mechanisms and particle-dislocation interactions have been studied from the macroscopic creep behavior. At a low stress level of 107 MPa, the dislocation-climb-controlled power-law creep is dominant in the matrix phase, and the load partition between the matrix and the precipitate phases remains constant. However, intergranular stresses develop progressively during the primary creep regime with the load transferred to 200 and 310 oriented grains along the axial loading direction. At a high stress level of 150 MPa, deformation is governed by the thermally activated dislocation glide (power-law breakdown) accompanied by the accelerated texture evolution. Furthermore, an increase in stress level also leads to load transfer from the plastically deformed matrix to the elastically deformed precipitates in the axial direction, along with an increase in the lattice misfit between the matrix and the precipitate phases.     

<Emphasis Type=Italic>In-Situ</Emphasis> Neutron Diffraction Study of the Bauschinger Effect in B2 Structured CoZr

A combination of in-situ neutron diffraction and elastoplastic self-consistent (EPSC) modeling have been used to elucidate the role played by intergranular stresses in the Bauschinger effect in B2 structured CoZr at room temperature and 423 K (150 °C). It is shown that, when insufficient slip modes are present to accommodate arbitrary strains, the large intergranular stresses built up due to inhomogeneous plastic deformation are responsible for the observed Bauschinger effect. Upon the onset of secondary deformation mechanism(s), the stresses are more uniformly distributed among the grains and the influence of intergranular stresses on the Bauschinger effect diminishes. On the other hand, it is speculated that the contribution of intragranular (dislocation-based) stresses is responsible for the persistent Bauschinger effect past the transition point. Similar results are obtained at both room temperature and 423 K (150 °C), and while the yield strength decreases with temperature, the high-temperature stress-strain curve progressively becomes harder than the room temperature one. In light of this, the previously characterized yield strength anomaly in CoZr has been re-examined.     

<Emphasis Type=Italic>In-Situ</Emphasis> Microtomographic Characterization of Single-Cavity Growth During High-Temperature Creep of Leaded Brass

Synchrotron microtomography was used for in-situ characterization of high-temperature creep damage in leaded brass. Applying image registration to subsequent tomographic reconstructions, the volumetric growth rate of single cavities with equivalent radii between 2 and 4.3 μm was assessed. We conclude from the volume dependence of the growth rates that both the viscous flow and grain boundary (GB) diffusion mechanisms influence void growth. We show that void growth in leaded brass is retarded by negative stress triaxiality, which develops in the matrix during heating the specimen to the deformation temperature.