Reverse Transformation Research Articles

Effects of Tryptophan and Tyrosine on the Transformation of Monophenols in Chromophoric Dissolved Organic Matter Solutions: Enhance the Forward Transformation and Reduce the Reverse Transformation.

Tryptophan (Trp) and tyrosine (Tyr) are the primary precursors of protein-like components in dissolved organic matter. Phenolic compounds are ubiquitous in aquatic environments and are considered the main electron donor in chromophoric dissolved organic matter (CDOM). Our results showed that Trp and Tyr (50 μM) enhanced the transformation of six monophenols (20 μM) with varying numbers of -CH3 and -OCH3 substituent groups by a factor of 1.0-1.8. The enhancement factor increased with the ratio of Trp (Tyr) to monophenols. In four different CDOM solutions (5 mg C/L, pH 8.0), a maximum enhancement factor of 3.2-6.7 was observed at a Trp/monophenol concentration ratio of 50. Conversely, monophenols greatly inhibited the transformation of Trp or Tyr. The enhancement factor decreased as the initial pH increased from 3.0 to 10.0. Additionally, the enhancement factor was not directly proportional to the oxidation potential of monophenol. We propose that the promotion effects are generated through the direct oxidation of monophenols by Trp (Tyr) radicals as well as through the reaction between Trp (Tyr) radicals and the one-electron reductant of CDOM.

Effect of heat treatment on phase transformation behavior and properties of Ni-Co-Mn-Al-Y shape memory alloy by laser direct energy deposition

Laser direct energy deposition (LDED) of Ni-Co-Mn-Al-Y magnetic shape memory alloys (MSMAs) with high elastocaloric properties has important application prospects in solid-state refrigeration. However, because the microstructure of laser non-equilibrium metallurgy does not have reversible martensitic transformation, further regulating the microstructure of deposited samples through scientific post-heat treatment to obtain better properties is still a top priority. In this work, Ni-Co-Mn-Al-Y alloy samples were prepared by an optimized LDED process, and then the deposited samples were heat-treated with different temperatures. The results showed that the sample subjected to heat treatment with 550 °C × 3.5 h + 1100 °C × 20 h had maximum entropy change of the phase transformation, compressive properties, and elastocaloric effect. The compressive fracture strength was up to 1327 MPa, the maximum compressive strain was up to 26.2%, and an adiabatic temperature change was up to −4.3 K under the condition of rapid unloading. Characterization of the microstructure changes of the alloy under 11 cycles of compression revealed that the deformation mechanism was mainly planar sliding of dislocations in the martensite and dislocation cutting the γ(Y-rich) phase. The alloy prepared by the optimizing LDED and heat treatment process had better cycle stability and preliminary refrigeration capacity.

Dehydration-Induced Cluster Consolidation in a Metal-Organic Framework for Sieving Hexane Isomers.

Metal-organic frameworks (MOFs) that exhibit dynamic phase-transition behavior under external stimuli could have great potential in adsorptive separations. Here we report on a zinc-based microporous MOF (JNU-80) and its reversible transformation between two crystalline phases: large pore (JNU-80-LP) and narrow pore (JNU-80-NP). Specifically, JNU-80-LP can undergo a dehydration-induced cluster consolidation under heat treatment, resulting in JNU-80-NP with a reduced channel that allows exclusion of di-branched hexane isomers while high adsorption of linear and mono-branched hexane isomers. We further demonstrate the fabrication of MOF-polymer composite (JNU-80-NP-block) and its application in the purification of di-branched isomers from liquid-phase hexane mixtures (98 % di-branched) at room temperature, affording the di-branched hexane isomers with 99.5 % purity and close to 90 % recovery rate over ten cycles. This work illustrates an interesting dehydration-induced cluster consolidation in MOF structure and the ensuing channel shrinkage for sieving di-branched hexane isomers, which may have important implications for the development of MOFs with dynamic behavior and their potential applications in non-thermal driven separation technologies.

Dehydration‐Induced Cluster Consolidation in a Metal‐Organic Framework for Sieving Hexane Isomers

AbstractMetal‐organic frameworks (MOFs) that exhibit dynamic phase‐transition behavior under external stimuli could have great potential in adsorptive separations. Here we report on a zinc‐based microporous MOF (JNU‐80) and its reversible transformation between two crystalline phases: large pore (JNU‐80‐LP) and narrow pore (JNU‐80‐NP). Specifically, JNU‐80‐LP can undergo a dehydration‐induced cluster consolidation under heat treatment, resulting in JNU‐80‐NP with a reduced channel that allows exclusion of di‐branched hexane isomers while high adsorption of linear and mono‐branched hexane isomers. We further demonstrate the fabrication of MOF‐polymer composite (JNU‐80‐NP‐block) and its application in the purification of di‐branched isomers from liquid‐phase hexane mixtures (98 % di‐branched) at room temperature, affording the di‐branched hexane isomers with 99.5 % purity and close to 90 % recovery rate over ten cycles. This work illustrates an interesting dehydration‐induced cluster consolidation in MOF structure and the ensuing channel shrinkage for sieving di‐branched hexane isomers, which may have important implications for the development of MOFs with dynamic behavior and their potential applications in non‐thermal driven separation technologies.

Thermomechanics of phase transformation induced localization in NiTi tubes. Part II constitutive modeling and simulations

In an isobaric test, typically used for establishing the transformation temperatures of SMAs, a specimen is taken through a cool/heat cycle at a prescribed stress level. The companion paper, Part I, demonstrated that such tests on NiTi tubes result in rather complex interactions between the helical bands of localized deformation induced by phase transformations, the associated latent heat, and the thermal exchange with the environment. These interactions were quantified using accurately controlled testing conditions and full-field diagnostics, and provide a challenging platform for evaluating analyses. In Part II this challenge is met by first extending the thermomechanical constitutive framework developed by our group to include variations of transformation stress, strain, and latent heat with temperature. Unique features of the model include: modeling the reversible phase transformations of NiTi through a single surface in the deviatoric stress–temperature space with the transformation strain and entropy as the internal variables; and use of softening to model the inhomogeneous deformation exhibited in tension. The model is calibrated to the isothermal results of Part I. The constitutive model is then incorporated into a fully coupled static displacement-thermally transient finite element analysis that is used to simulate the isobaric experiments on NiTi tubes of Part I over a range of stresses. The clamped ends of the experiment are idealized as radial constraints. Heat exchange between the structure and the environment is strictly by convection. Isobaric testing is simulated by taking the model tube through the cool/heat cycle of the experiment at the prescribed stress level. A small thickness depression at one of the ends is used to initiate localized transformation. The temperature-strain response is reproduced with the two transformations initiating at essentially the same temperatures as in the experiments, producing the correct transformation strains for all stress levels. Transformation of M propagates via a helical band at similar speeds as in the experiments, while transformation of A is via multipronged fronts for all cases. Successful reproduction of the velocities of the banded transformations is governed by the value of the convection coefficient. Overall, the reproduction of the isobaric experiments over a range of stress levels, validates the constitutive and structural models. It also points to the limitations of modeling the heat exchange between the specimen and the environment only by convection.

Thermomechanics of phase transformation induced localization in NiTi tubes. Part I experiments

This two-Part study aims to illustrate and elucidate the effects of thermomechanical interactions in pseudoelastic NiTi structures that arise in the course of the reversible transformations between the austenitic and martensitic phases. Transformation leads to inhomogeneous deformation with the two phases coexisting and to latent heat-induced local heating/cooling. Part I first presents the results of displacement-controlled isothermal tension and compression experiments on NiTi tubes covering the pseudoelastic temperature regime. The experiments are conducted in a constant temperature circulating bath which suppresses thermomechanical interactions so the transformation front velocity is governed strictly by the applied displacement rate. The load/unload hystereses traced, quantify the transformation stresses and strains and will be used to calibrate the constitutive model of Part II. A set of isobaric experiments in which NiTi tubes are taken through a cool/heat cycle under constant stresses of different levels follow. The experiments are conducted in a custom small-scale environmental chamber with a circulating air stream run by a feedback temperature controller, coupled to load-controlled mechanical loading. The evolution of helical bands of the alternate phase is captured using digital image correlation. The results demonstrate that under such loading histories a strong interaction develops between the evolving inhomogeneous deformation, the latent heat and the surrounding environment. The speed of propagation of the helical fronts slows down or accelerates so as to match the rate at which heat is removed/added to the specimen by the airflow. Thus, here the evolution of localized deformation is strongly coupled to the interaction between the latent heats and heat transfer from the environment. The effect of the stress level on these events is examined through eight isobaric experiments, which provide a rich data set for evaluating constitutive models and structural analyses of these experiments such as those in Part II.

Heterostructure catalyst coupled wood-derived carbon and cobalt-iron alloy/oxide for reversible oxygen conversion

As promising energy-storage devices, zinc–air batteries (ZABs) exhibit slow reaction kinetics for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurring at their electrodes. High-performance bifunctional catalysts must thus be synthesized to accelerate the reversible conversion of oxygen and improve the rate and overall performance of ZABs. Herein, we reported the promising prospects of self-supported composite electrodes composed of wood-derived carbon (WDC) and bimetallic cobalt-iron alloys/oxides (CoFe-CoFe2O4@WDC) as efficient electrocatalysts for alkaline ORR/OER. WDC provided a favorable three-phase interface for heterogeneous reactions owing to its layered porous structure and genetic stability, thereby enabling mass diffusion and improving reaction kinetics. The CoFe2O4 spinel surface was reduced to bimetallic CoFe alloy to form abundant heterostructure interfaces that promote electron transfer. Under alkaline conditions, the optimized composite electrode exhibited a remarkable high half-wave potential of 0.85 V and an exceptionally low overpotential of 1.49 V. It also exhibited stable performance over an impressive 2340 cycles in a ZAB. Theoretical calculations also confirmed that the heterointerface addresses the issue of proton scarcity throughout the reaction and actively facilitates the creation of O–O bonds during the reversible transformation of oxygen. This study introduces a new concept for developing bifunctional and efficient electrocatalysts based on charcoal and encourages the sustainable and high-value use of forest biomass resources.Graphical

Metastable microporous lanthanide silicates – Light emitters capable of 3D-2D-3D transformations

The synthesis of zeolites and porous heteropolyhedral silicates is usually accompanied by crystal phase transformations. Typically, this process is irreversible and characterized by a conversion from a metastable phase to a stable one. Here we demonstrate a reversible transformation between porous (K3LnSi3O9·nH2O) and layered (K3LnSi3O8(OH)2) structures exemplified by a dual synthesis (hydrothermal and solid-state transformation). We discuss structural and photoluminescent properties of the obtained microporous lanthanide silicates MS-4 (Minho-Sofia, solid number 4; K3LnSi3O9·nH2O, Ln = Y, Dy; orthorhombic, Pmc21). These materials are metastable, transforming from 3D porous to a 2D layered structure after prolonged crystallization time at hydrothermal conditions and returning to the same but distorted (≈ 2 % smaller lattice volume) porous 3D framework by calcination of 2D structure. The mechanism of 3D-2D structure transformation is driven by interzeolite-like transformation, while the rearrangement of common structural fragments controls 2D-to-3D conversion. We also show how the avoidance of Dy and preference for Y ions during MS-4 hydrothermal synthesis may be overcome by a 2D-3D conversion, allowing the production of white light emitters with controllable photoluminescence.

Breathing Behavior and Superprotonic Conductivity of Two-Dimensional Flexible Metal-Organic Frameworks Tuned with Alkoxy Groups.

Flexible metal-organic frameworks (FMOFs) exhibit reversible structural transitions ("breathing" behaviors), which can regulate the proton transport passageway effectively. This property offers remarkable advantages for improving the proton conductivity. Our objective of this work is to design a single-variable flexibility synergistic strategy for the fabrication of FMOFs with high conductivity. Herein, four two-dimensional FMOFs, {[Co(4-bpdb)(R-ip)]·xsolvents}n (x = rich, 1-4), have been successfully designed and assembled (4-bpdb = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene and R-ip = MeO/EtO/n-PrO/n-BuO-isophthalate). Upon the release and/or absorption of different solvent molecules, they display reversible breathing behaviors, thereby resulting in the formation of the partial and complete solvent-free compounds {[Co(4-bpdb)(R-ip)]·ysolvents}n (y = free or poor, 1A-4A). This breathing behavior involves the synergistic self-adaption of the dynamic torsion of alkoxy groups and reversible structural transformation, leading to remarkable changes in cell parameters and void space, as evidenced by single-crystal X-ray diffraction, powder X-ray diffraction, and N2 and CO2 adsorption analyses. At 363 K and 98% relative humidity, 2A exhibits the best proton conductivity among the FMOFs. Its conductivity reaches 4.08 × 10-2 S cm-1 and is one of the highest conductivities shown by reported unmodified MOF-based proton conductors.

Ultraslow calorimetric studies of the martensitic transformation of NiFeGa alloys: detection and analysis of avalanche phenomena

We study the thermal properties of a bulk Ni55Fe19Ga26\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\hbox {Ni}_{55}\\hbox {Fe}_{19}\\hbox {Ga}_{26}$$\\end{document} Heusler alloy in a conduction calorimeter. At slow heating and cooling rates (∼1Kh-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\sim {1}\\,\\hbox {K h}^{-1}$$\\end{document}), we compare as-cast and annealed samples. We report a smaller thermal hysteresis after the thermal treatment due to the stabilization of the 14 M modulated structure in the martensite phase. In ultraslow experiments (40mKh-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${40}\\,\\hbox {mK h}^{-1}$$\\end{document}), we detect and analyze the calorimetric avalanches associated with the direct and reverse martensitic transformation from cubic to 14 M phase. This reveals a distribution of events characterized by a power law with exponential cutoff p(u)∝u-εexp(-u/ξ)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$p(u)\\propto u^{-\\varepsilon }\\exp (-u/\\xi )$$\\end{document} where ε∼2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\varepsilon \\sim 2$$\\end{document} and damping energies ξ=370μJ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\xi ={370}{\\upmu {\\rm J}}$$\\end{document} (direct) and ξ=27μJ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\xi ={27}{\\upmu {\\rm J}}$$\\end{document} (reverse) that characterize the asymmetry of the transformation.

Post-dynamic transformation from α to β phase and reverse transformation in Ti-10V-2Fe-3Al alloy during interrupted hot deformation

Interrupted hot deformation tests were carried out to study the phase transformation behavior of Ti-10V-2Fe-3Al alloy during isothermal holding after deformation. The results show that post-dynamic transformation (post-DT) from α to β phase occurred first during isothermal holding and the meta-β phase retransformed to α phase after a long holding time. This phenomenon is quite different from α+β titanium alloys in which only reverse transformation (RT, βα) took place during isothermal holding. Microstructure evolution of β-matrix was also investigated and it was found that static recovery was the main softening mechanism. Furthermore, phase transformation has a great influence on the static softening and mechanical response of interrupted hot deformation. Due to the occurrence of post-DT, the yield strength of reloading pass reduced and became lower than the initial pass when the holding time exceeds 900 s. And significant static softening was achieved. The driving and opposing force for post-DT and RT were derived and compared based on thermodynamic analysis. Since the deformation and holding temperature is close to β-transus temperature, post-DT has a lower energy barrier which can be easily overcome by stored energy. This may explain why the phase transformation direction in Ti-10 V-2Fe-3Al alloy is opposite to that in α+β titanium alloys during isothermal holding.

Dynamic Electrostatic Interfacial Engineering for Block Copolymer Microparticles with Reversible Structures.

Responsive nanoparticle surfactants (NPSs) can dynamically and reversibly modulate the interfacial interactions between incompatible components, which are essential in the interfacial catalysis, corrosion, and self-assembly of block copolymers (BCPs). However, NPSs with stimuli-responsive behavior often involve tedious chemical synthesis and surface modifications. Herein, we propose a strategy to in situ construct a kind of dynamic and reversible NPSs by the interfacial electrostatic interaction between the negatively charged nanoparticles (NPs) and the positively charged homopolymers. The NPSs assembled at the oil/water interface reduce the interfacial tension and direct the confined assembly of BCP. Meanwhile, the dynamic NPSs can be disassembled by increasing the pH value or introducing competitive electrostatic attractions, which can dynamically and reversibly change the interfacial properties as well as the alignment of polymer chains, enabling BCP microparticles with reversibly switchable lamellar and cylindrical structures. Furthermore, by the introduction of aggregation-induced emission luminogens as tails to the NPSs, the reversible transformation of BCP microparticles can be visualized by fluorescence emission, which is dependent on the nanostructures of microparticles. This work establishes a concept for dynamically manipulating interfacial interactions and reversibly switching BCP microparticles without time-consuming NPS synthesis, showing promising applications in the fabrication of smart materials with switchable structures and properties.

Predominant P3-Type Solid-Solution Phase Transition Enables High-Stability O3-Type Na-Ion Cathodes.

Layered O3-type oxides are one of the most promising cathode materials for Na-ion batteries owing to their high capacity and straightforward synthesis. However, these materials often experience irreversible structure transitions at elevated cutoff voltages, resulting in compromised cycling stability and rate performance. To address such issues, understanding the interplay of the composition, structure, and properties is crucial. Here, we successfully introduced a P-type characteristic into the O3-type layered structure, achieving a P3-dominated solid-solution phase transition upon cycling. This modification facilitated a reversible transformation of the O3-P3-P3' structure with minimal and gradual volume changes. Consequently, the Na0.75Ni0.25Cu0.10Fe0.05Mn0.15Ti0.45O2 cathode exhibited a specific capacity of approximately 113 mAh/g, coupled with exceptional cycling performance (maintaining over 70% capacity retention after 900 cycles). These findings shed light on the composition-structure-property relationships of Na-ion layered oxides, offering valuable insights for the advancement of Na-ion batteries.

Frequency effect on low‐cycle fatigue behavior of pseudoelastic NiTi alloy

AbstractThis study presents experimental results on the effect of loading frequency during low‐cycle fatigue on the fracture mechanism and properties of pseudoelastic NiTi wire. The uniaxial tensile tests were performed in stress‐controlled mode over the 0.1–10 Hz frequency range. It was shown that the number of cycles before specimen failure decreased with increasing frequency from 0.1 Hz to 1 Hz but increased at frequencies above 1 Hz. It was fractographically shown that fatigue striations were observed on the fracture surfaces of specimens tested at all loading frequencies. A new type of fatigue striations was described on fracture specimens tested at frequencies up to 1 Hz. They are characterized by different spacing between successive striations with a change in the slope of the fracture at the transitions between them. This feature may be associated with forward and reverse phase transformations during half‐periods of loading and unloading of nitinol.

Intramolecular Charge Transfer and Stimuli-Responsive Emission in Cholesterol-Appended Phenothiazine-Cyanostyryl-Based Donor-Acceptor Systems.

Organic fluorescent molecules have received considerable attention owing to their various optoelectronic applications. Herein, we report the design and synthesis of two cholesterol-functionalized cyanostyrene-phenothiazine-based D-π-A systems that are emissive in both the solution and solid states. The newly synthesized cholesterol-appended phenothiazine-cyanostyrene diads PTCS-1 and PTCS-2 vary in the N-alkylation of phenothiazine, respectively, with─octyl and─hexyl chains. Both molecules are highly fluorescent and show reasonably good quantum yields in nonpolar solvents because of twisted intramolecular charge transfer (TICT). The molecules exhibit aggregation-induced emission in the solid state. Due to the presence of flexible alkyl chains in the phenothiazine and cholesterol moieties, PTCS-1 and PTCS-2 show mechanochromic luminescence switching in response to external shear stress and emission recovery under methanol vapor. Powder X-ray diffraction studies prove that the emission switching on the applied stimuli in both PTCS-1 and PTCS-2 is attributed to the reversible transformation between the crystalline and amorphous states. Time-dependent density functional theory (TD-DFT) studies are carried out to gain insight into the ICT interactions. TD-DFT analysis at the TD-M06-2X/def2-TZVP level further revealed that in both molecules, the lowest unoccupied molecular orbital (LUMO) + 2, LUMO, highest occupied molecular orbital (HOMO), and HOMO - 1 orbitals are responsible for the charge transfer interactions. These ICT interactions are identified as π-π* type interactions.

Temperature effects on the structure of lead metasilicate glass, supercooled liquid, crystal, and liquid: Vibrational anharmonicity and configurational transformations analyzed by molecular dynamics and Raman scattering

Raman spectroscopy and Molecular Dynamics (MD) simulations were employed to explore in detail the effects of temperature on the four stages of the PbO∙SiO2 system: glass, supercooled liquid, crystalline phases, and liquid. The Qn distribution up to 1153 K and the wavenumber temperature coefficients derived from vibrational anharmonicity were determined from the Raman data, whereas the structural transformation reflected in changes in the Qn population distribution up to 2400 K was inferred from MD simulations. The results indicate that reversible configurational transformations occur only in the higher temperature ranges of the supercooled liquid and more notably in the liquid state. During these transformations, the increase in the Q0 and Q1 populations occurs at the expense of the Q3 and Q4 populations. On the other hand, only vibrational anharmonicity was observed in the glass and crystalline states.

Tuning the Thermochemistry and Reactivity of a Series of Cu-Based 4H+/4e- Electron-Coupled-Proton Buffers.

Electron-coupled-proton buffers (ECPBs) store and deliver protons and electrons in a reversible fashion. We have recently reported an ECPB based on Cu and a redox-active ligand that promoted 4H+/4e- reversible transformations (J. Am. Chem. Soc. 2022, 144, 16905). Herein, we report a series of Cu-based ECPBs in which the ability of these to accept and/or donate H• equivalents can be tuned via ligand modification. The thermochemistry of the 4H+/4e- ECPB equilibrium was determined using open-circuit potential measurements. The reactivity of the ECPBs against proton-coupled electron transfer (PCET) reagents was also analyzed, and the results obtained were rationalized based on the thermochemical parameters. Experimental and computational analysis of the thermochemistry of the H+/e- transfers involved in the 4H+/4e- ECPB transformations found substantial differences between the stepwise (namely, BDFE1, BDFE2, BDFE3, and BDFE4) and average bond dissociation free energy values (BDFEavg.). Our analysis suggests that this "redox unleveling" is critical to promoting the disproportionation and ligand-exchange reactions involved in the 4H+/4e- ECPB equilibria. The difference in BDFEavg. within the series of Cu-based ECPBs was found to arise from a substantial change in the redox potential (E1/2) upon modification of the ligand scaffold, which is not fully compensated for by a change in the acidity/basicity (pKa), suggesting "thermochemical decompensation".

Versatile morphology transition of nano-assemblies via ultrasonics/microwave assisted aqueous polymerization-induced self-assembly based on host–guest interaction

Nano-assemblies have wide applications in biomedicine, functional coatings, Pickering emulsifiers, hydrogels, and so forth. The preparation of assemblies mainly utilizes the polymerization-induced self-assembly (PISA) method, which can produce high-concentration nanoscale assemblies in one step. However, the initiation processes of most reported PISA are limited to thermal initiation. Here, we reported two green and efficient methods for synthesizing nano-assemblies with various morphologies using ultrasound (20 kHz)/ microwave (500 W) assisted aqueous-phase RAFT-PISA in 3 h and 1 h. Cyclodextrin (CD) and styrene (St) nucleating monomer were complexed in a 1:1 ratio. Then, using Poly (ethylene glycol) methyl ether as the macromolecular reversible addition-fragmentation chain transfer (RAFT) agent (PEG-CTA) to control the CD/St complexes, the conversion rate of St monomer was respectively 27 %–60 %, 20 %–30 % within 3 h and 1 h under ultrasonics/microwave assisted PISA. Results showed that the morphologies of the assemblies are not only related to the length of PS block, but also to the assistance types and the remaining monomer concentration. The results showed that only PEG45-b-PS90 and PEG45-b-PS241 assemblies prepared by ultrasonics assisted PISA form evolved lamellaes and vesicles (100 nm), which break through the limitation of kinetic freezing. But the ultrasonic reaction on morphology of assemblies is not all favourable. For one thing, it can promote the movement of particles; for another, it makes reverse morphology transformation and sphere is preferred morphology. Therefore, the main reason of morphology evolution is the remaining monomer concentration of PEG45-b-PS90 and PEG45-b-PS241 assemblies reaches to 55 %–65 %, which promoting the segment movement. The results showed that the morphology of the assemblies prepared by microwave assisted PISA changed from spherical micelles to short rods, and finally to vesicles (120–140 nm) as the length of hydrophobic PS block increases. The kinetic freezing problem was solved in microwave-assisted PISA due to the action of microwaves and more remaining monomer concentration. Both them can boost particles movement.

Origins of functional fatigue and reversible transformation of precipitates in NiTi shape memory alloy

The work clarifies several key questions in shape memory research that have eluded previous studies. The findings show that dislocation slip emanates at austenite-martensite interfaces during unloading and aligns with the internal twin boundary interface of martensite. It was observed that the type II internal twins of the martensite become parallel dislocations in the austenite. During reloading, these dislocations act as nucleation sites for the martensitic twins, reducing the nucleation barrier and the transformation stress. The precipitates facilitate martensite nucleation but also act as an obstacle to martensite front motion, restrict detwinning, and pin the interfacial dislocations during unloading, thereby contributing to residual strains and martensite stabilization. Martensite nucleation is not suppressed by the size of the thin film, which is of the order of 85 to 105 nanometers thick, and repeated transformation occurred cycle after cycle. Single crystals deformed in the <101>LD exhibited the best recoverability of up to 5.5 % and tensile stresses of up to 1.4 GPa. It was demonstrated for the first time that, when favorably oriented, Ni4Ti3 precipitates undergo a reversible phase transformation to R-phase and can accommodate up to 4 % reversible strains.

Enhanced deformation-induced FCC-HCP transformation of a metastable high-entropy alloy induced by a smaller grain size

This study reports the grain-size-dependent deformation-induced face-centered cubic (FCC)–hexagonal close-packed (HCP) transformation behavior of Fe49.5Mn30Co10Cr10C0.2Ti0.1V0.1Mo0.1 (at. %) high-entropy alloy in the medium grain size range (10–20 μm), their mechanical properties, and deformation mechanisms. The materials annealed at 900 °C for 1 h (A900-1) and 10 h (A900-10) showed a fully FCC, recrystallized microstructure with a larger grain size in the latter owing to grain growth during annealing. The A900-1 sample exhibited a larger strength–ductility balance and a higher strain hardening rate than the A900-10 sample. The A900-1 sample, with a larger number of grain boundary nucleation sites of the deformation-induced HCP phase, exhibited a higher HCP transformation rate than the A900-10 sample in the early stage of deformation below 10 % strain, whereas both materials showed similar HCP transformation rates at strain levels higher than 30 %. The emission of deformation-induced HCP plates in both neighboring grains from the same grain boundary (A900-1) and the activation of the deformation-induced HCP phase in a single grain and only dislocations in the neighboring grains (A900-10) suggest the importance of grain boundary stress in the observed phenomena. The observed additional mechanisms other than dislocation slip and deformation-induced HCP phase, that is, reverse FCC-HCP transformation, HCP {101‾2} twinning, and kink banding, could contribute to deformation accommodation and stress relaxation, thereby leading to the excellent ductility of the investigated materials.