63Cu NMR investigation of effect of small additions of Sn to Al-1.7 at.%Cu in promoting accelerated phase transformations on aging

Very recently 63Cu NMR has been shown to be extremely sensitive in detecting and differentiating between the precipitate phases that form in Al-Cu alloys during heat treatment. This technique is now used to quantify the effectiveness of small additions of Sn to the alloy Al-1.7 at.% Cu in promoting the rapid nucleation and growth of the θ'-phase precipitate. Two parallel series of 63Cu NMR spectra were recorded for Al-1.7 at.% Cu and Al-1.7 at.% Cu-0.01 at.% Sn: (i) aged at 130° C to observe the comparative rate of phase evolution and (ii) aged at 200° C to observe the rate of growth of θ'-phase and to compare with the Vickers hardness of the alloys aged at 200° C for similar periods. Evidence is presented that a metastable precursor phase to θ' (labelled TPHM2757math001) is formed in Al-Cu-Sn which transforms to θ' on further aging.

Structural phase transformations of Mg3N2 at high pressure : experimental and theoretical studies

The structural behavior of Mg₃N₂ has been investigated up to 40.7 GPa at room temperature by means of angle-dispersive X-ray diffraction. A reversible, first-order structural phase transition from the ambient cubic phase (Ia3̅) to a high-pressure monoclinic phase (C2/m) is found to start at ~ 20.6 GPa and complete at ~ 32.5 GPa for the first time. The equation of state determined from our experiments yields bulk moduli of 110.7(2) and 171.5(1) GPa for the cubic and monoclinic phases, respectively, indicating higher incompressibility of the high-pressure phase of Mg₃N₂. First-principles calculations reproduced the phase stability and transition pressure determined in our experiment. In addition, a second phase transition from the monoclinic phase to a hexagonal phase (P3̅m₁) was predicted around 67 GPa for Mg₃N₂. The electronic band structures of three phases of Mg₃N₂ are also calculated and discussed.

Effect of cooling rate on phase transformations in a high-strength low-alloy steel studied from the liquid phase

The phase transformation and precipitation in a high-strength low-alloy steel have been studied over a large range of cooling rates, and a continuous cooling transformation (CCT) diagram has been produced. These experiments are unique because the measurements were made from samples cooled directly from the melt, rather than in homogenized and re-heated billets. The purpose of this experimental design was to examine conditions pertinent to direct strip casting. At the highest cooling rates which simulate strip casting, the microstructure was fully bainitic with small regions of pearlite. At lower cooling rates, the fraction of polygonal ferrite increased and the pearlite regions became larger. The CCT diagram and the microstructural analysis showed that the precipitation of NbC is suppressed at high cooling rates, and is likely to be incomplete at intermediate cooling rates.

Multi-phase microstructure design of a novel high strength TRIP steel through experimental methodology

The multi-phase structure of a novel low-alloy transformation induced plasticity (TRIP) steel was designed through experimental analysis. The evolutions of both microstructure and mechanical properties during the two-stage heat treatment were analyzed. The phase transformations during the intercritical annealing and the isothermal bainitic transformation were investigated by means of dilatometry. It was shown that two types of C diffusion were detected during intercritical annealing and a complex microstructure was formed after heat treatment. The processing parameters were selected in such a way to obtain microstructures with systematically different volume fractions of ferrite, bainite and retained austenite. The volume fractions of ferrite and retained austenite were found to be two main factors controlling the ductility. Furthermore, a high volume fraction of C-rich retained austenite, which was stabilized at room temperature, was the origin of a TRIP effect. The resulting material demonstrates a significant improvement in the ultimate tensile strength (1077. MPa) with good uniform elongation (22.5%), as compared to conventional TRIP steels. © 2014 Elsevier B.V.

Recent advances in machining of Austempered Ductile Iron to avoid machining induced microstructural phase transformation reaction

Austempered Ductile Iron (ADI) is a type of nodular, ductile cast iron subjected to heat treatments-austenitising and austempering. Whilst machining is conducted prior to heat treatment and offers no significant difficulty, machining post heat treatment is demanding and often avoided. Phase transformation of retained austenite to martensite leading to poor machinability characteristics is a common problem experienced during machining. Study of phase transformations is an investigative study on the factors-plastic strain (εp) and thermal energy (Q) which effect phase transformations during machining. The experimental design consists of face milling grade 1200 at variable Depth of Cut (DoC) range from 1 to 4 mm, coolant on/off, at constant speed, 1992 rpm and feed rate, 0.1 mm/tooth. Plastic strain (εp) and martensite content (M) at fracture point for each grade was evaluated by tensile testing. The effect of thermal energy (Q) on phase transformations was also verified through temperature measurements at DoC 3 and 1 mm using thermocouples embedded into the workpiece. Finally, the amount of plastic strain (εp) and thermal energy (Q) responsible for a given martensite increase (M) during milling was related and calculated using a mathematical function, M=f (εp, Q). The future work of the thesis involves an in-depth study on the new link discovered through this research: mathematical model relating the role of plastic strain and thermal energy in martensite formation.

Hardenability reduction in VN microalloyed eutectoid steels

By dilatometry, it is shown that vanadium microalloying additions to eutectoid carbon steels, which also contain an increased level of nitrogen, cause a marked decrease in hardenability when transforming from fine grained austenite.

Hydroxyapatite/titania sol-gel coatings on titanium-zirconium alloy for biomedical applications

A simple sol–gel method was developed for hydroxyapatite/titania (HA/TiO2) coatings on non-toxic titanium–zirconium (TiZr) alloy for biomedical applications. The HA/TiO2-coated TiZr alloy displayed excellent bioactivity when soaked in a simulated body fluid (SBF) for an appropriate period. Differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction and scanning electron microscopy-energy dispersive spectrometry were used to characterize the phase transformations and the surface structures and to assess the in vitro tests. The HA/TiO2 layers were spin-coated on the surface of TiZr alloy at a speed of 3000 rpm for 15 s, followed by a heat treatment at 600 °C for 20 min in an argon atmosphere sequentially. The TiO2 layer exhibited a cracked surface and an anatase structure and the HA layer displayed a uniform dense structure. Both the TiO2 and HA layers were 25 μm thick, and the total thickness of the HA/TiO2 coatings was 50 μm. The TiZr alloy after the above HA/TiO2 coatings displayed excellent bone-like apatite-forming ability when soaked in SBF and can be anticipated to be a promising load-bearing implant material.

Three-dimensional atom probe analysis of solute distribution in thermomechanically processed TRIP steels

Complex multiphase microstructures were obtained in transformation induced plasticity C–Mn–Si–(Nb–Al–Mo) steels by simulated controlled thermomechanical processing. These microstructures were characterized using transmission electron microscopy, X-ray diffraction and three-dimensional atom probe tomography (APT), which was used to determine the partitioning of elements between different phases and microconstituents. The measured carbon concentration (not, vert, similar0.25 at%) in the ferrite of carbide-free bainite was higher than expected from para-equilibrium between the austenite and ferrite, while the concentrations of substitutional elements were the same as in the parent austenite suggesting that incomplete bainite transformation occurred. In contrast, the distribution of substitutional elements between the ferrite lath and austenite in carbide-containing bainite indicated a complete bainite reaction. The average carbon content in the retained austenite (3.2 ± 1.6 at%) was somewhat higher than the T0 limit. On the basis of the APT measured composition, the calculated Ms temperatures for retained austenite were above room temperature, indicating its low chemical stability.

Sol-gel derived HA/TiO2 double coatings on Ti scaffolds for orthopaedic applications

Hydroxyapatite/titania (HA/TiO₂) double layers were coated onto Ti scaffolds throughout for orthopaedic applications by sol-gel method. Differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and X-ray diffractometry (XRD) were used for the characterisation of the phase transformations of the dried gels and coated surface structures. Scanning electron microscope (SEM) equipped with energy dispersive spectrometry (EDS) was used for the observation and evaluation of the morphology and phases of the surface layers and for the assessment of the in vitro tests. The in vitro assessments were performed by soaking the HA/TiO₂ double coated samples into the simulated body fluid (SBF) for various periods. The TiO₂ layer was coated by a dipping-coating method at a speed of 12 cm/min, followed by a heat treatment at 600 °C for 20 min. The HA layer was subsequently dipping-coated on the outer surface at the same speed and then heat-treated at difference temperatures. The results indicat that the HA phase begins to crystallize after a heat treatment at 560 °C. The crystallinity increases obviously at 760 °C. SEM observations find no delamination or crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA/TiO₂ coated Ti scaffolds displays excellent bone-like apatite forming ability when it is soaked into SBF. Ti scaffolds after HA/TiO₂ double coatings can be anticipated as promising implant materials for orthopaedic applications

Effect of isothermal dissolution and re-precipitation of austenite on the mechanical properties of duplex structures

The hot deformation behaviour of a duplex ferritic/austenitic stainless steel was studied after different deformation conditions. The results showed a strange and interesting behaviour in the strength of the material during post-deformation studies. For most deformation conditions, the flow stress of the material was un-expectedly increased after annealing of deformed structures. This phenomenon implied that microstructural hardening occurred in the material during the interpass annealing rather than the expected softening. Also, an interesting change was observed where the morphology of the austenite phase changed from stringers or layers of austenite to a widmanstätten structure. The microstructural studies suggest that the austenite was dissolved and re-precipitated during the annealing process and the hardening was mostly associated with the change in the morphology of austenite.

Atom probe tomography as a tool to advance steels design and performance

Development of modern steels consisting of complex or nano-scale microstructures with advanced properties requires in-depth understanding of the mechanisms responsible for their microstructure/property relationships. The evolution of microstructure during processing is often associated with various changes taking place at atomic level. These include solute distribution between phases as a result of phase transformations, formation of atmospheres at dislocations, clustering and precipitation phenomena due to various thermo-mechanical processing schedules and/or heat treatments. Atom probe tomography (APT) is invaluable tool for gaining insight into events at atomic scale determining the steel properties. This technique also contributes to the fundamental understanding of phase transformations, which is essential for nano-scale engineering of modern steels and optimization of their performance. In this work application of APT to study solute segregation, clustering and precipitation in TRIP steels and nanostructured bainitic steels after isothermal heat-treatment and after thermomechanical processing will be discussed.

Deactivation and regeneration of oxygen reduction reactivity on double perovskite Ba2Bi0.1Sc0.2Co1.7O6−x cathode for intermediate-temperature solid oxide fuel cells

in situ high-temperature X-ray diffraction and thermal gravimetric- differential thermal analysis on room-temperature powder, as well as X-ray diffraction, Raman spectroscopy, and transmission electron microscopy on quenched powder, were applied to study crystal structure and phase transformations in Ba₂Bi_0.1Sc_0.2Co _1.7O_6-x (BBSC). Heating BBSC in air to over 800 °C produces a pure cubic phase with space group Fm3m (no. 225), and cooling down below 800 °C leads to a mixture of three noncubic phases including an unknown phase between 200 and 650 °C, a 2H hexagonal BaCoO3 with space group P63/mmc (no. 194) between 600 and 800 °C, and an intermediate phase at 800 °C. These three phases exist concurrently with the major cubic phase. The weight gain and loss between 300 and 900 °C suggest the occurrence of cobalt reduction, oxidation, and disproportion reactions with dominant reduction reaction at above 600 °C. The thermal expansion of BBSC was also examined by dilatometry. BBSC has a highly temperature-dependent thermal expansion coefficient which relates well with its structure evolution. Furthermore, the oxygen reduction reaction (ORR) of BBSC was probed by symmetrical cell and three-electrode configurations. The presence of hexagonal phase at 700 °C rarely affects the ORR performance of BBSC as evidenced by a slight increase of its area-specific resistance (ASR) value following 48 h of testing in this three-electrode configuration. This observation is in contrast to the commonly held point of view that noncubic phase deteriorates performance of perovskite compounds (especially in oxygen transport applications). Moreover, cathodic polarization treatment, for example, current discharge from BBSC (tested in three-electrode configuration), can be utilized to recover the original ORR performance. The cubic structure seems to be retained on the cathodic polarization - the normal cathode operating mode in fuel cells. Stable 72-h performance of BBSC in cathodic polarization mode further confirms that despite the presence of phase impurities, BBSC still demonstrates good performance between 500 and 700 °C, the desired intermediate operating temperature in solid oxide fuel cells.

Microstructure evolution and softening processes in hot deformed austenitic and duplex stainless steels

The microstructure evolution and softening processes occurring in 22Cr-19Ni-3Mo austenitic and 21Cr-10Ni-3Mo duplex stainless steels deformed in torsion at 900 and 1200 °C were studied in the present work. Austenite was observed to soften in both steels via dynamic recovery (DRV) and dynamic recrystallisation (DRX) for the low and high deformation temperatures, respectively. At 900 °C, an "organised", self-screening austenite deformation substructure largely comprising microbands, locally accompanied by micro-shear bands, was formed. By contrast, a "random", accommodating austenite deformation substructure composed of equiaxed subgrains formed at 1200 °C. In the single-phase steel, DRX of austenite largely occurred through straininduced grain boundary migration accompanied by (multiple) twinning. In the duplex steel, this softening mechanism was complemented by the formation of DRX grains through subgrain growth in the austenite/ferrite interface regions and by large-scale subgrain coalescence. At 900 °C, the duplex steel displayed limited stress-assisted phase transformations between austenite and ferrite, characterised by the dissolution of the primary austenite, formation of Widmanstätten secondary austenite and gradual globularisation of the transformed regions with strain. The softening process within ferrite was classified as "extended DRV", characterised by a continuous increase in misorientations across the sub-boundaries with strain, for both deformation temperatures.

The development of ultrafine-grained hot rolling products using advanced thermomechanical processing

The aim of the work is development of industry guidance concerning production of ultrafine-grained (UFG) High Strength Low Alloy (HSLA) steels using strain-induced dynamic phase transformations during advanced thermomechanical processing. In the first part of the work, the effect of processing parameters on the grain refinement was studied. Based on the obtained results, a multiscale computer model was developed in the second part of the work that was subsequently used to predict the mechanical response of studied structures. As an overall outcome, a process window was established for the production of UFG steels that can be adopted in existing hot rolling mills. © 2014 Elsevier B.V.