FT-IR spectroscopic and calorimetric characterization of the adsorbed forms of water on α-Fe2O3 obtained by thermal decomposition of α-FeOOH

Adsorption of water on α-Fe₂O₃ surfaces has been studied by FT-IR spectroscopy and heat flow microcalorimetry. Several different adsorbed forms have been observed. Their identification has been attempted on the basis of their chemical behaviour and of a discussion of the structures of the exposed crystal faces.     

Reversible Control of Physical Properties via an Oxygen‐Vacancy‐Driven Topotactic Transition in Epitaxial La0.7Sr0.3MnO3−δ Thin Films

The vacancy distribution of oxygen and its dynamics directly affect the functional response of complex oxides and their potential applications. Dynamic control of the oxygen composition may provide the possibility to deterministically tune the physical properties and establish a comprehensive understanding of the structure–property relationship in such systems. Here, an oxygen‐vacancy‐induced topotactic transition from perovskite to brownmillerite and vice versa in epitaxial La_0.7Sr_0.3MnO_3?δ thin films is identified by real‐time X‐ray diffraction. A novel intermediate phase with a noncentered crystal structure is observed for the first time during the topotactic phase conversion which indicates a distinctive transition route. Polarized neutron reflectometry confirms an oxygen‐deficient interfacial layer with drastically reduced nuclear scattering length density, further enabling a quantitative determination of the oxygen stoichiometry (La_0.7Sr_0.3MnO_2.65) for the intermediate state. Associated physical properties of distinct topotactic phases (i.e., ferromagnetic metal and antiferromagnetic insulator) can be reversibly switched by an oxygen desorption/absorption cycling process. Importantly, a significant lowering of necessary conditions (temperatures below 100 °C and conversion time less than 30 min) for the oxygen reloading process is found. These results demonstrate the potential applications of defect engineering in the design of perovskite‐based functional materials.     

Synthesis and magnetic property of silica/iron oxides nanorods

To better understand the shape dependent property of binary nanostructure, magnetic silica/iron oxides (α-Fe₂O₃ and Fe₃O₄) nanocomposites in rodlike shape have been synthesized using β-FeOOH nanorods as the starting material. The silica layer was coated on the surface of β-FeOOH nanorods, which were prepared by hydrolyzing of FeCl₃ under hydrothermal conditions. Silica/α-Fe₂O₃ nanorods were prepared by calcining silica/β-FeOOH nanorods, and magnetic silica/Fe₃O₄ nanorods were obtained after the reduction of silica/α-Fe₂O₃ nanorods in an inert atmosphere. The role of the silica layer during the phase transformation process was discussed. The magnetic properties of silica/iron oxides (α-Fe₂O₃ and Fe₃O₄) nanorods were investigated and the results revealed that silica/iron oxides nanorods showed higher magnetic saturation value compared with the reported data.     

Study of autoabsorption for total α and β counting

The RaMsEs Group (Radioprotection et Mesures Environnementales) of the IPHC performs research and offers services mainly in the field of radioactivity measurements and sample analysis. This report will describe some of our recent experience using a semiautomatic evaporation system to prepare large area thin deposits for total α and β counting and gives experimental and simulated results for the autoabsorption coefficients.     

Calculation of efficiency functions in 4π β-γ counting

An attempt is made to calculate an efficiency function applicable to 4πβ-γ coincidence measurements as the first stage of evaluating the order of the polynomial of the fitting function. For this purpose, the β-ray energy spectra and self-absorptions of spherical particle sources are calculated by the Monte Carlo simulation under the continuous slowing down approximation. On the other hand, it is shown that three sets of absorption coefficients and partial intensity ratios corresponding to a β-ray group give analytically the self-absorption for the same particle sources. Finally, we show that the efficiency functions applicable to ⁵⁹Fe and ¹³⁴Cs are easily obtained by using the energy spectra or self-absorptions.     

Mechanosynthesis and magnetic properties of nanocrystalline LaFeO3 using different iron oxides

The synthesis of the orthoferrite LaFeO₃ using high-energy ball-milling of La₂O₃ and Fe₃O₄ or α-Fe₂O₃ oxides and subsequent thermal treatments of resulting powders was studied. The phase evolution during the mechanical treatment was analyzed by X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). Also, magnetic properties of the obtained materials were measured at room temperature by vibrating sample magnetometry (VSM). From 30 min of mechanochemical activation the gradual disappearance of reactants and the formation of LaFeO₃ were observed. For both reactive mixtures the reaction was completed after 3 h of milling. Magnetic hysteresis loops of these mechanoactivated samples showed a significant ferromagnetic component in LaFeO₃. This behavior was interpreted on the basis of a spin-canting effect induced by the mechanochemical treatment. Thermal treatments allowed the relaxation of the distorted structure, resulting in the formation of the conventional antiferromagnetic LaFeO₃ phase.     

Comparative determination of the α/β phase fraction in α+β-titanium alloys using X-ray diffraction and electron microscopy

A comparison is made between the measured α/β phase fractions in Ti-6246 using X-ray diffraction (XRD) and electron microscopy. Image analysis of SEM and TEM images was compared to the phase fraction estimate obtained using electron backscattered diffraction, lab and high-energy synchrotron XRD. There was a good agreement between the electron microscopic and diffraction techniques, provided that the microstructural parameters of grain size and texture are estimated correctly when using quantitative Rietveld refinement.     

Enhanced Grain Refinement Through Deformation Induced α Precipitation in Hot Working of α + β Titanium Alloy

This study reports a novel forging process to fabricate bulk fine‐grained (grain size ≈ 1 µm) Ti–6Al–4V alloy, in which temperatures near the β transus (T_β) and strain rates around 0.15 s^?1 are used for the deformation. The formation of fine‐grained microstructure is mainly result from the deformation‐induced precipitation of α grains from the β matrix.     

Structural and electrochemical characterization of LiMn2−δVδOy spinels

The spinel phase compounds with the composition of LiMn_2−δV_δO_y were prepared by solid reaction of the mixture of LiNO₃·H₂O, MnCO₃ and NH₄VO₃ powders. Evolution of the crystalline phases of the samples versus the vanadium content was analyzed using X-ray diffraction (XRD) technique, EPR and FT-IR spectroscopes. Cubic spinel is the predominant phase in the powders under heat treatment at 550 °C for 5 h. The valence state of manganese ion changed from +4 to +3 with vanadium substitution for charge compensation. The vanadium substitution of manganese leads the decline in capacity and cyclic behavior of the powders. The electrochemical behaviors relating to the variation of structure corresponding to the vanadium substitution were discussed.     

Retransformation (α′→γ) kinetics of strain induced martensite in 304 stainless steel

Coupons of austenitic 304 stainless steel (γ) were transformed to approximately 90% martensite (α′) and 10% austenite by rolling at 77 K. Subsequently the reverse α′→γ transformation was instigated by heating the coupons to 680°C. The retransformation was monitored, in situ, by dilatometry and neutron Bragg edge diffraction (BED). Results from the two techniques show good agreement and suggest that the transformation kinetics are best described by two Avrami exponents, n=2.5 and n=0.2 respectively. A limited discussion of the lattice parameter evolution during the transformation is included. Possible mechanisms for growth dynamics and stress relaxation are discussed.     

In Situ Study of γ‐TiAl Lamellae Formation in Supersaturated α2‐Ti3Al Grains

In situ heating transmission electron microscopy (TEM) was used to investigate the initial stage of γ‐TiAl lamellae formation in an intermetallic Ti–45Al–7.5Nb alloy (in at.%). The material was heat treated and quenched in a non‐equilibrium state to consist mainly of supersaturated, ordered α₂‐Ti₃Al grains. Subsequently, specimens were annealed inside a TEM up to 750 °C. The in situ TEM study revealed that ultra‐fine γ‐TiAl laths precipitate in the α₂‐matrix at ≈730 °C which exhibit the classical Blackburn orientation relationship, i.e. (0001)α₂//(111)γ and [$11{\bar {2}}0$ ]α₂//<110]γ. The microstructural development observed in the in situ TEM experiment is compared to results from conventional ex situ TEM studies. In order to investigate the precipitation behavior of the γ‐phase with a complementary method, in situ high energy X‐ray diffraction experiments were performed which confirmed the finding that γ‐laths start to precipitate at ≈730 °C from the supersaturated α₂‐matrix.     

Investigations of MX and γ′/γ″ precipitates in the nickel-based superalloy 718 produced by electron beam melting

Samples with a composition similar to the nickel-based superalloy Inconel alloy 718 were produced by electron beam melting of prealloyed powder and investigated with respect to type and composition of the strengthening precipitates. The matrix consists of γ grains orientated in nearly the same direction, almost like a single crystal. Coarse precipitates (<2 μm), mostly of the (Ti,Nb)(C,N,B) type with B1 structure, are aligned along the growth direction. TEM and APFIM investigations of the γ matrix revealed very fine γ″ precipitates of around 5–10 nm in size. Additionally, at small angle grain boundaries, coarser γ″ precipitates of 50–100 nm in size have been observed. The 0 01 γ//0 0 1 γ″ and {1 0 0} γ//{1 0 0} γ″ orientation relationship between γ and γ″, known from literature [M. Sundararaman, P. Mukhopadhyay, Mater. Charact. 31 (1993) 191–196], was confirmed. Some γ′ precipitates of 2–5 nm in size were observed by means of FIM.     

Machining of γ-TiAl

Knowledge of the machining parameters for titanium aluminides of the type γ-TiAl is essential for the acceptance and application of this new heat-resistant light-weight material for high performance components in automobile and aircraft engines. This work evaluates drilling, turning, sawing, milling, electroerosion, grinding, and high-pressure water-jetting of primary castings. The results indicate that there is a potential for each machining process, but a high quality of surface finish can only be achieved by some of the processes.     

Gamma (γ) phase transformation in pulsed GTAW weld metal of duplex stainless steel

The cooling rate and large undercooling significantly affect the fusion zone microstructure in pulsed GTAW weldment under the same heat input condition. The weld pool solidified at fast cooling rate about 139 °C/s superimposed a relative amount of undercooling has a desired higher γ content of about 37 vol.% without tradition nitrogen addition or post-weld heat treatment. The final structure of the pulsed weld metal at 7 °C plate consists of a great amount of desirable intra-granular austenite γ^′₂ (IGA) inside the grain matrix, besides Widmannstätten austenite γ^′₂ (W) and grain boundary austenite γ₂ (GBA). It results in the weldment with an uniform microhardness distribution and a homogeneous mechanical property.     

The Dislocation Structure of a Single-Crystal γ + γ′ Two-Phase Alloy After Tensile Deformation

The dislocation structures of an industrial single-crystal γ + γ′ two-phase alloy DD3 after tensile deformation from room temperature to 1273K were studied by transmission electron microscopy. The strength of this alloy decreased with an increase in the temperature, and showed a strength peak at 1033K. At room temperature, the dislocations shearing the γ′ particles were found to be 1/3<112> partial dislocations on the dodecahedral slip system <112>{111}. Some dislocation pairs on the cubic <110>{100} system that blocked the glide of dislocations were found at a medium temperature of 873K. As a result, dislocation bands were formed. Shearing of γ′ particles by 1/3<112> partial dislocations on the dodecahedral slip system <112>{111} was also found at this temperature. At the peak temperature of 1033K, because of the strong interaction between dislocations on the {111} and {100} planes, the extent of dislocation bands with high dislocation densities was extensive. The 1/3<112> partial dislocations on the dodecahedral slip system <112>{111} also existed. When the temperature reached the high temperature of 1133K, the range of dislocation bands was limited. The γ′ particles were sheared by <110> dislocation pairs on the octagonal <110>{111} system and the cubic <110>{100} system. At 1273K, the regular hexagonal dislocation networks were formed in the γ matrix and at the γ/γ′ interface. The Burgers vectors of the network were found to be b₁ = 1/2[110], b₂ = 1/2[1–10], b₃ = [100], and the last one was formed by the reaction of b₁ + b₂ → b₃. Dislocations shearing the γ′ particles were found to be <110> dislocation pairs on the octagonal system <110>{111} and cubic slip system <110>{100} at 1273K.     

β to ω phase transformation due to aging in a Ti–Mo alloy deformed in impact compression

We investigated the roles of vacancies and their clusters introduced in a Ti–20mass% Mo alloy by high-speed compression in the formation of aged ω-phase crystals. Specimens were deformed by a static compression mode and a high-speed compression mode, and were then aged. The relationships between morphology of aged ω-phase crystals and deformation modes are discussed along with the roles of vacancies and their clusters in the nucleation and growth of aged ω-phase crystals. Aged ω-phase crystals were found to be smaller but of higher density in a high-speed deformation specimen. These results suggest that vacancies and their clusters easily become nucleation sites of aged ω-phase crystals. Several aged ω-phase crystals in a high-speed deformation specimen were of string-like shape. High-resolution electron microscopy confirmed that the string-like crystals have the ω-phase crystal structure. One of the roles of vacancies of and their clusters introduced by high-speed deformation is considered to be relief of compressive stress, which is predicted to arise in the course of transformation.