Solid Transformation Research Articles

A novel experimental method to assess the fatigue behavior of pseudoelastic NiTi wires

A new experimental method for characterizing intrinsic uniaxial pull-pull pseudoelastic fatigue life of commercial NiTi wires is proposed. It consists in the generation of a virtual dog-boned shaped specimen combined with the use of snubbing type of gripping action in order to completely eliminate earlier failures induced by grip-sample interactions. The generation of a virtual dog-boned specimen is based on the localized character of the stress induced martensitic transformation and the evolution of the transformation stresses with further cycling. Reduced pseudoelastic cycles are performed to evaluate functional and structural fatigue with this method. Consistent longer fatigue lives have been obtained compared to traditional gripping methods with fractures occurring inside the region of interest. The present study clearly points to the role of the stress induced transformation in determining the fatigue life. This treatment of the structural fatigue considerable departs from classical approaches but takes into account essential facts like the localized character of the stress induced transformation, the heat effects associated with the first order solid to solid martensitic transformation and its impact on the critical transformation stresses.

The green biorefinery concept for the valorisation of pistachio shell by high-pressure CO2/H2O system

Abstract The use of high-pressure CO2/H2O in valorisation of pistachio shell to produce hemicellulose-derived, oligomeric and monomeric sugars and their further transformation to furfural as well as enzymatic transformation of cellulose-rich solids is presented in this work. Different pre-treatment conditions i.e. temperature ranged from 160 to 200 °C; reaction time varied between 0 and 30 min and liquid to solid mass ratio between 4 and 8 with constant initial pressure of CO2 of 50 bars were examined. At the optimal pre-treatment conditions, the concentrations of xylose and xylo-oligosaccharide were of 1.7 and 35.5 g/L. Furthermore, this work demonstrates the high-pressure CO2 catalysed production of furfural in an aqueous/tetrahydrofuran system. For model solution containing a mixture of xylose and acetic acid, the optimised furfural yield was as high as 53.3 mol%, while for real sample of hemicellulose hydrolysate, the furfural yield of 39.6 mol% and the selectivity of 40.0 mol% were obtained. Additionally, quantitative glucan to glucose conversion by enzymatic hydrolysis of pre-treated cellulose-rich biomasses was achieved. The promising results achieved confirm that the valorisation of food residues such as pistachio shell using greener alternative methods involving high-pressure CO2 is an efficient technology, which can be integrated into the biorefinery concept.

Self-Assembled Pd(II) Barrels as Containers for Transient Merocyanine Form and Reverse Thermochromism of Spiropyran.

Self-assembly of a cis-blocked Pd(II) 90° ditopic acceptor [ cis-(tmeda)Pd(NO3)2] (M) with a tetradentate donor L1 [benzene-1,4-di(4-terpyridine)] in 2:1 molar ratio yielded two isometric molecular barrels MB1 and MB3 in DMSO [tmeda = N, N, N' N'-tetramethylethane-1,2-diamine]. Exclusive formation of the symmetrical tetrafacial barrel (MB1) was achieved when the self-assembly was performed in aqueous medium. The presence of a large confined cavity makes MB1 a potential molecular container. Spiropyran (SP) compounds exist in stable closed spiro form in visible light and convert to transient open merocyanine (MC) form upon irradiation with UV-light or upon strong heating. The transient MC form readily converts to the stable closed SP form in visible light. MB1 has been employed as a safe container to store the planar and unstable merocyanine isomers (MC1/2) of different spiropyran molecules (SP1/2) [SP1/2 = 6-bromo-spiropyran and 6-nitrospiropyran] for several days. The transient MC forms (MC1 and MC2) were found to be stable inside the molecular container MB1 under visible light and even in the presence of different stimuli such as heat and UV light for a long time. Such stabilization of MC forms inside the confined cavity of MB1 is noteworthy. This phenomenon was generalized by utilizing a carbazole-based molecular barrel (MB2) as a host, which also showed a similar stabilization of transient MC form in visible light at room temperature. Moreover, reverse thermochromism was observed as a result of heating of the MC1 ⊂ MB2 complex, which de-encapsulates the guest in the form of SP1 to give a colorless solution. Moreover, both the host molecules (MB1, MB2) were capable of stabilizing transient MC2 even in the solid state. Such stabilization of transient MC forms in the solid state and transformation of SP forms to MC forms in the solid state in the presence of molecular barrel are remarkable, and these properties have been employed in developing a magic ink.

Monotropic polymorphism in a glass-forming metallic alloy

This study investigates the crystallization and phase transition behavior of the amorphous metallic alloy Au70Cu5.5Ag7.5Si17. This alloy has been recently shown to exhibit a transition of a metastable to a more stable crystalline state, occurring via metastable melting under strong non-equilibrium conditions. Such behavior had so far not been observed in other metallic alloys. In this investigation fast differential scanning calorimetry (FDSC) is used to explore crystallization and the solid–liquid–solid transition upon linear heating and during isothermal annealing, as a function of the conditions under which the metastable phase is formed. It is shown that the occurrence of the solid–liquid–solid transformation in FDSC depends on the initial conditions; this is explained by a history-dependent nucleation of the stable crystalline phase. The microstructure was investigated by scanning and transmission electron microscopy and x-ray diffraction. Chemical mapping was performed by energy dispersive x-ray spectrometry. The relationship between the microstructure and the phase transitions observed in FSDC is discussed with respect to the possible kinetic paths of the solid–liquid–solid transition, which is a typical phenomenon in monotropic polymorphism.

Crystalline modification of a rare earth nucleating agent for isotactic polypropylene based on its self-assembly.

In this paper, the crystalline modification of a rare earth nucleating agent (WBG) for isotactic polypropylene (PP) based on its supramolecular self-assembly was investigated by differential scanning calorimetry, wide-angle X-ray diffraction and polarized optical microscopy. In addition, the relationship between the self-assembly structure of the nucleating agent and the crystalline structure, as well as the possible reason for the self-assembly behaviour, was further studied. The structure evolution of WBG showed that the self-assembly structure changed from a needle-like structure to a dendritic structure with increase in the content of WBG. When the content of WBG exceeded a critical value (0.4 wt%), it self-assembled into a strip structure. This revealed that the structure evolution of WBG contributed to the Kβ and the crystallization morphology of PP with different content of WBG. In addition, further studies implied that the behaviour of self-assembly was a liquid–solid transformation of WBG, followed by a liquid–liquid phase separation of molten isotactic PP and WBG. The formation of the self-assembly structure was based on the free molecules by hydrogen bond dissociation while being heated, followed by aggregation into another structure by hydrogen bond association while being cooled. Furthermore, self-assembly behaviour depends largely on the interaction between WBG themselves.

Crystal defect associated selection of phase transformation orientation relationships (ORs)

Phase transformation in solids always follows specific orientation relationships (ORs). The OR usually ensures a minimum lattice deformation for the structure change. However, in many cases different ORs are respected by the same transformation. The selection role and the link between the OR and the existing crystal defects needs further investigation. Thus, in this work, the α to β heating phase transformation induced by high density Electric Current Pulse (ECP) treatments in an annealed Cu–40%Zn alloy was investigated. Results show that the β phase obeys the K-S OR when formed along the α grain boundaries or in their vicinities, or the N-W OR when formed in the α grain interiors. In the former sites, the {111}α/<11¯0>α dislocation arrays were frequently observed, whereas in the latter, the {111}α/<112¯>α stacking faults were often found. Transformation strain analyses revealed that under the K-S OR the maximum lattice deformation required is a shear on the {111}α plane in the <11¯0>α direction, whereas under the N-W OR the maximum deformation is a shear on the {111}α plane in the <112¯>α direction. Thus the existing {111}α/<11¯0>α dislocation arrays along the α grain boundaries and in their vicinities provide pre-strain required by the transformation via the K-S path, whereas the {111}α/<112¯>α stacking faults boarded by {111}α/<112¯>α partial dislocations offer pre-strain facilitating the transformation via the N-W path. The present results provide new information on the role of crystal defects on phase transformation strain path and the selection of transformation ORs.

Effect of Cooling Rates on γ → α Transformation and Metastable States in Fe–Cu Alloys with Addition of Ni

α/γ phase transformations occurring in Fe–10Cu–xNi alloys (0 ≤ x ≤ 15 in mass%) were studied using X-ray diffraction, scanning electron microscopy, electron back scattered diffraction, transmission electron microscopy and chemical analysis, combining X-ray microanalysis with energy dispersive spectrometry in the scanning electron microscope and electron microprobe analysis with wavelength dispersive spectrometry. The influence of cooling rate on the microstructure was investigated using ice-brine quenching and 2 °C/min slow cooling rate performed with dilatometry. Ni addition induces metastable transformations on cooling: massive and bainitic ferrite are formed depending on the alloy composition and cooling rate. Moreover, most of the Cu phase precipitates on cooling giving rise to a fine distribution of Cu particles in the ferrite grains. For both cooling conditions, the hardness increases with increasing Ni content and a higher hardness is obtained in the quenched alloy for each composition. The change in hardness is correlated to the effect of Ni solid solution, transformation structure and size of Cu particles.

Deformation and pattern transformation of porous soft solids under biaxial loading: Experiments and simulations

In this work, we combine both experiments and numerical simulations to study the large deformation mechanics of two-dimensional patterned porous silicone rubber under biaxial loading, by focusing on the combined compressive and tensile loading. Particularly, we design a loading apparatus to impose the biaxial loading and fabricate patterned porous silicone rubbers through 3D printing. Although the pattern transformation with alternating elliptic voids has been observed under uniaxial compression before, our results show that the pattern transformation can be promoted by biaxial compression, while biaxial compression/tension can delay it. When the ratio between tension and compression is larger than a critical value, a new pattern transformation has been observed. In addition, if the imposed tension in one direction is larger than the compression in the other direction, the pattern transformation with alternating elliptic voids cannot occur. Biaxial loading provides new opportunities to fabricate the tunable devices and imprint complex patterns with soft solids.

Phase Transformation Mechanism of Li-Ion Storage in Iron(III) Hydroxide Phosphates

Many ion storage compounds used for electrodes in Li-ion batteries undergo a first order phase transformation between the Li-rich and Li-poor end-members during battery charge and discharge. This often entails large transformation strains due to lattice misfits, which may hamper charge and discharge kinetics. Iron(III) hydroxide phosphate, Fe2–y(PO4)(OH)3–3y(H2O)3y−2 is a promising new cathode material with high Li-ion storage capacity, low production costs and low toxicity. Previous reports on this material indicate that the Li-ion intercalation and extraction in this material is accompanied by a second-order solid solution transformation. However, direct information about the transformation mechanism in Fe2–y(PO4)(OH)3–3y(H2O)3y−2 is lacking, and several details remain unclear. In this work, Fe2–y(PO4)(OH)3–3y(H2O)3y−2 is prepared by hydrothermal synthesis and characterized structurally, morphologically and by electrochemical analysis (galvostatic cycling and cyclic voltammetry). A wide range of synthes...

Structure analysis and conditions of formation of akimotoite in the Tenham chondrite

AbstractAkimotoite (Mg,Fe)SiO3 is one of the most common mineralogical indicators for high‐level shock metamorphism in meteorites. First described 1997, its occurrence has been amply confirmed in a number of highly shocked chondrites. Yet, a thorough structure analysis of natural akimotoite has remained extant. Here we report accurate cell parameters, fractional atomic coordinates, and site occupancies for natural akimotoite from the holotype specimen based on synchrotron microdiffraction. The variation of unit cell shape and volume with Fe content define mixing volumes. Based on the mixing volume relation for akimotoite and hemleyite, we constrain the unit cell volume of endmember hemleyite to 273.8 ± 1.0 Å3. We show that mixing is nearly ideal for low Fe content but evolves to positive excess volume toward the Fe endmember. Based on this finding and the actual composition of akimotoite in Tenham, we show that this mineral has formed by solid–solid transformation prograde from enstatite, not by crystallization from melt.

Nanoscale Detection of Intermediate Solid Solutions in Equilibrated LixFePO4 Microcrystals

Redox-driven phase transformations in solids determine the performance of lithium-ion batteries, crucial in the technological transition from fossil fuels. Couplings between chemistry and strain define reversibility and fatigue of an electrode. The accurate definition of all phases in the transformation, their energetics, and nanoscale location within a particle produces fundamental understanding of these couplings needed to design materials with ultimate performance. Here we demonstrate that scanning X-ray diffraction microscopy (SXDM) extends our ability to image battery processes in single particles. In LiFePO4 crystals equilibrated after delithiation, SXDM revealed the existence of domains of miscibility between LiFePO4 and Li0.6FePO4. These solid solutions are conventionally thought to be metastable, and were previously undetected by spectromicroscopy. The observation provides experimental verification of predictions that the LiFePO4-FePO4 phase diagram can be altered by coherency strain under certain interfacial orientations. It enriches our understanding of the interaction between diffusion, chemistry, and mechanics in solid state transformations.

Thermodynamic simulation of hydrogen based solid sorption heat transformer

The hydrogen absorption and desorption pressure-concentration isotherms (PCI) of La0.9Ce0.1Ni5 and LaNi4.6Al0.4 alloys are measured by static and dynamic method. The hydrogen absorption and desorption kinetics of the alloys also measured. The measured properties are used to study the performance of hydrogen based solid sorption heat transformer (MHHT). The thermodynamic simulation of MHHT is conducted using statically and dynamically measured PCI and thermodynamic properties. Due to variation in statically and dynamically measured metal hydride properties, significant variations in coefficient of performance (COP) and heat transformation capacity of MHHT are observed. In case of thermodynamic analysis using dynamically measured properties the heat transformation capacity and COP are decreased by 42.6% and 22.2% respectively, compared to statically measured data. This is due to the decrease in amount of hydrogen transmission and pressure differential between paired metal hydride reactors, and increase in reaction enthalpies. Later, the actual thermodynamic cycle for MHHT is constructed by considering the variation in pressure during hydrogen transfer processes between the metal hydride reactors.

Thermal conductivity changes across a structural phase transition: The case of high-pressure silica

By means of first-principles calculations, we investigate the thermal properties of silica as it evolves, under hydrostatic compression, from a stishovite phase into a CaCl$_2$-type structure. We compute the thermal conductivity tensor by solving the linearized Boltzmann transport equation iteratively in a wide temperature range, using for this the pressure-dependent harmonic and anharmonic interatomic couplings obtained from first principles. Most remarkably, we find that, at low temperatures, SiO$_2$ displays a large peak in the in-plane thermal conductivity and a highly anisotropic behavior close to the structural transformation. We trace back the origin of these features by analyzing the phonon contributions to the conductivity. We discuss the implications of our results in the general context of continuous structural transformations in solids, as well as the potential geological interest of our results for silica.

Metallurgists’ Insights on Diffusion-Assisted Dissimilar-Joints of Light- and Heavy-Alloys

In metallurgy and materials engineering, a number of phase transformation in solids like precipitation, oxidation, creep, annealing, homogenization, etc. are brought about by the process of diffusion. Many industrial manufacturing processes utilize solid-state diffusion principle, to name a few: 1. Rotating or sliding parts of steel have a hard outside case for wear resistance and a tough inner core for fracture resistance by gas carburizing procedure; 2. Integrated circuits were produced by diffusing impurity into silicon wafers; and 3. Joints between similar and dissimilar metals, alloys, and non-metals, were made using diffusion bonding (DB) technique. Day by day, the science of solid-state diffusion phenomenon is spreading inevitably into new areas of engineering and technology. Diffusion-Assisted-Joints (DAJs) meet the requirements for most critical structures in terms of strength, toughness, tightness, and resistance to heat and corrosion. DAJs can be made out of 730 pairs of dissimilar metals. Hence, DB is considered as an engineering marvel among all the physical welding metallurgists. Herein, experiments were performed to exactly map the quantum influence of the bonding temperature variation on the dissimilar joints of a popular light alloy, Ti-6Al-4V (TiA), and a heavily used heavy alloy, stainless steel (SS), using diffusion mechanism in high-vacuum environment. Cu foil (~200μm) was used as an interlayer. Necessary characterization tools for metallurgical investigations were used to understand the extent of diffusion along the TiA/Cu and Cu/SS interfaces, room-temperature mechanical properties, fracture morphologies, and fracture path of the TiA/Cu/SS DAJs. This paper discussed rational reasons backing the results of the characterizations.

A mathematical model to measure instantaneous moisture content in transformer insulation cellulose

Solid transformer insulation is mainly composed of cellulosic materials, in the form of pressboard, Kraft paper and wood. Oil is used to impregnate voids in the cellulose. The water content of cellulose usually increases over the life of the transformer, caused by both moisture ingress and the gradual degradation of cellulose, which produces moisture as an aging by-product. Equilibrium curves are used to estimate the moisture content of cellulosic insulation using the vapor pressure of water dissolved in the oil. However, a very long duration is required for water to attain this equilibrium partition, much longer than the usual daily cyclic temperature profile of a transformer, and thus it is very unlikely for the insulation to reach this state. In this paper a novel method to estimate the moisture in cellulose during non-equilibrium conditions is presented. The water adsorbed by the cellulose migrates in and out the oil, and the diffusivity depends on the temperature and the concentration of moisture in the cellulosic insulation. This diffusion is mainly governed by Fick's law. For a transformer, the change in moisture content of oil in a small duration is mainly due to the moisture content in the cellulosic insulation. This paper presents a method to estimate the moisture content of cellulosic insulation of the transformer at that instant from the change in the moisture content of the oil.

From the Atomistic to the Mesoscopic Scale Modeling of Phase Transition in Solids

The phase-field method is a very powerful tool to model the phase transformation and microstructural evolution of solids at mesoscopic scale. However, several important phenomena, like defect formation, grain boundary motion, or reconstructive phase transitions require an atomic scale study. Recently an approach called the quasi-particle approach, based on the Atomic Density Function theory was developed to incorporate the atomic-level crystalline structures into standard continuum theory for pure and multicomponent systems. This review focuses on the description of different computational methods used to model microstructural evolution and self-assembly phenomena at mesoscopic and atomistic scales. Various application examples of these methods are also presented.

Solid surface-mediated photochemical transformation of decabromodiphenyl ether (BDE-209) in aqueous solution

Polybrominated diphenyl ethers (PBDEs) are brominated flame retardants which have received considerable attention due to their global distribution, bioaccumulation potential, environmental persistence, and possible toxic effects. In this work, the photodegradation of decabromodiphenyl ether (BDE-209) in aqueous system was investigated by preloading it on the surface of various solid matrices. After 6 h of Xe lamp irradiation, almost complete degradation of BDE-209 was observed on silica gel (SG), with much slower degradation occurring in other adsorbents. The degradation of BDE-209 on SG sample followed pseudo-first-order kinetics, and the observed reaction rate constant was decreased by lowering pH, adding humic acid and increasing the initial BDE-209 concentration. In addition to direct photolysis, BDE-209 could be oxidized by hydroxyl radicals generated from SG, as confirmed by the electron paramagnetic resonance (EPR) technology. Product analysis showed that BDE-209 was mainly decomposed into lower brominated PBDEs, polybrominated dibenzofurans (PBDFs), hydroxylated PBDEs (OH-PBDEs), hydroxylated PBDFs (OH-PBDFs), bromophenols and bromide ions. Thus, consecutive debromination, intramolecular elimination of HBr, hydroxyl addition and the cleavage of ether bond were proposed as the degradation pathways. This study may help understanding the photochemical transformation of solid surface adsorbed BDE-209 in natural surface waters, which is important to evaluate the environmental fate of PBDEs.

Crack-tip process zone as a bifurcation problem.

Stress concentration at a crack tip generates a solid structural transformation in its vicinity, the process zone. We argue that its formation represents a local phase transition described by a multicomponent order parameter. We derive a system of equations describing the dynamics of the order parameter driven by an inhomogeneous, time-dependent stress field in the solid and show that it exhibits a bifurcation. The latter corresponds to the emergence of a process zone characterized by the distribution of the order parameter localized in the vicinity of the crack tip. The emergence temperature T_{*} considerably differs from the temperature of the bulk phase transformation T_{c}. We demonstrate that T_{*} exhibits a universal behavior T_{*}-T_{c}∼K_{I}^{4/3}, in terms of the stress intensity factor K_{I}, and that the zone universally vanishes upon achieving a critical velocity. These facts together give rise to a universal dynamic phase diagram.

Multi-phase field simulation of grain growth in multiple phase transformations of a binary alloy**Project supported by the National Natural Science Foundation of China (Grant Nos. 51661020, 11504149, and 11364024).

This work establishes a temperature-controlled sequence function, and a new multi-phase-field model, for liquid–solid–solid multi-phase transformation by coupling the liquid–solid phase transformation model with the solid–solid phase transformation model. Taking an Fe–C alloy as an example, the continuous evolution of a multi-phase transformation is simulated by using this new model. In addition, the growth of grains affected by the grain orientation of the parent phase (generated in liquid–solid phase transformation) in the solid–solid phase transformation is studied. The results show that the morphology of ferrite grains which nucleate at the boundaries of the austenite grains is influenced by the orientation of the parent austenite grains. The growth rate of ferrite grains which nucleate at small-angle austenite grain boundaries is faster than those that nucleate at large-angle austenite grain boundaries. The difference of the growth rate of ferrites grains in different parent phase that nucleate at large-angle austenite grain boundaries, on both sides of the boundaries, is greater than that of ferrites nucleating at small-angle austenite grain boundaries.

Phase Selection during Solidification of Ni-10.95 at. % and B-3.23 at. % Si Alloy

To gain insight into the solidification of the Ni-10.95 at. % and B-3.23 at. % Si alloy, 29 cast samples extracted from a casting of this alloy were remelted under an Ar atmosphere, using either DSC or an in-house thermal analysis apparatus. Ni(fcc) and Ni3B phases were identified by X-ray diffraction of both the remelted and original cast samples; however, microstructural differences were observed between the two. These microstructural differences are associated with the high undercooling observed during the eutectic reaction in the remelted samples. This high undercooling results from the difficulty of Ni3B nucleation, which allows the formation of a NixBy metastable phase. Metallographic inspection shows that the metastable phase solidifies at least partially through a non-cooperative growth mechanism. This metastable phase may be the elusive Ni23B6 phase. The melting temperature of the metastable phase is 985 °C, and it solidifies below 943 °C under the experimental conditions used in this study. The temperature of solid transformation of the metastable constituent to Ni3B and Ni is strongly dependent on the amount of Ni3B formed during solidification. The minimal temperature of such transformation, 834 °C, corresponds to samples where Ni3B solidification was not detected in the thermal curves.