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At least 1,297 records · Page 72

Use of friction stir processing to synthesize nanocrystalline, grain boundary segregating Fe-Ti alloys

Grain boundary segregating alloys, a class of alloys designed such that nanocrystalline grain sizes are thermodynamically stabilized by the presence of high segregation energy solutes at the grain boundaries, are typically produced through geometrically limited processing techniques such as equal channel angular extrusion or thin film sputtering. Here, this study explores the use of friction stir processing (FSP) as a novel means of studying and producing these alloys using a test system of Fe-6at%Ti. Spot FSPs with a range of processing parameter sets were produced on bulk, coarse grained bars of material and optimal parameters were identified. Microscopy identified a range of processed materials which achieved nanocrystalline grains on the order of 100 nm, delineating a critical window of processing parameters which limit heat input while inducing sufficient plastic deformation for grain refinement. The finest grained nanocrystalline Fe-Ti achieved a hardness of 7.68 GPa, a significant increase in hardness over pure Fe with a similar microstructure due to increased dislocation density from FSP as well as several strengthening mechanisms produced through the presence and segregation of Ti. These results demonstrated the feasibility of using FSP to produce nanocrystalline grain boundary segregating alloys.

Fe alloys↗

Tuning gas separation performance of polyimide membranes with macrocyclic crown ether units

Membrane-based gas separation is an energy-efficient alternative to conventional thermally-driven separation processes. However, polymer membranes face the permeability-selectivity trade-off challenge, which stems from the broad size distribution of free volume voids. Here, this study reports a molecular design strategy to address this challenge through incorporating macrocyclic crown ether (CE) moieties into the backbone of Matrimid® polyimide, a commercial gas separation membrane. A series of CE-containing Matrimid®-like copolyimides were synthesized with systematically varied CE molar contents ranging from 3 to 20%. These copolyimides formed ductile, defect-free thin films suitable for membrane fabrication. Gas permeation tests revealed a non-monotonic relationship between permeability/selectivity and CE content. Notably, the copolyimide with only 5% CE demonstrated a 61% increase in CO 2 /CH 4 selectivity and a 13% increase in CO 2 permeability relative to pristine Matrimid®. Higher CE contents did not yield further performance improvements, which is likely due to the competing effects of chain packing disruption and π–π interactions among CE moieties at high content. This hypothesis was supported by wide-angle X-ray scattering (WAXS) analysis, density measurements, and fractional free volume calculations. These findings highlight the potential of macrocyclic crown ether incorporation strategies in fine tuning the microstructure of commercial polyimide gas separation membranes to surpass the traditional permeability-selectivity trade-off.

CO2 separation↗

Electric-field control of the nucleation and motion of isolated three-fold polar vertices

Recently various topological polar structures have been discovered in oxide thin films. Despite the increasing evidence of their switchability under electrical and/or mechanical fields, the dynamic property of isolated ones, which is usually required for applications such as data storage, is still absent. Here, we show the controlled nucleation and motion of isolated three-fold vertices under an applied electric field. At the PbTiO 3 /SrRuO 3 interface, a two-unit-cell thick SrTiO 3 layer provides electrical boundary conditions for the formation of three-fold vertices. Utilizing the SrTiO 3 layer and in situ electrical testing system, we find that isolated three-fold vertices can move in a controllable and reversible manner with a velocity up to ~629 nm s -1 . Microstructural evolution of the nucleation and propagation of isolated three-fold vertices is further revealed by phase-field simulations. This work demonstrates the ability to electrically manipulate isolated three-fold vertices, shedding light on the dynamic property of isolated topological polar structures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optimizing thermal stability and mechanical behavior in segregation-engineered nanocrystalline Al–Ni–Ce alloys: A combinatorial study

The deliberate use of solute enrichment at grain boundaries, otherwise known as segregation engineering, is a promising approach to tailor the properties of interface-dominated materials such as nanocrystalline alloys. Here, the ensuing chemical and structural evolution at grain boundaries can give rise to thermal stability and excellent mechanical properties, but the interplay between enrichment, phase decomposition, grain growth, and mechanical behavior exists in a vast composition and processing space. In this study, a combinatorial synthesis and rapid characterization approach was applied to segregation-engineered nanocrystalline Al–Ni–Ce alloys to assess the evolution of microstructure and resulting mechanical behavior as functions of alloying content and annealing conditions. In addition to the identification of alloys and processing conditions that give rise to exceptional thermal stability, strength retention, and homogeneous plastic flow, we construct combined thermal stability and deformation mechanism maps that demarcate several important regimes of behavior.

36 MATERIALS SCIENCE↗

Elucidating Design Rules toward Enhanced Solid-State Charge Transport in Oligoether-Functionalized Dioxythiophene-Based Alternating Copolymers

This study investigates the solid-state charge transport properties of the oxidized forms of dioxythiophene-based alternating copolymers consisting of an oligoether-functionalized 3,4-propylenedioxythiophene (ProDOT) copolymerized with different aryl groups, dimethyl ProDOT (DMP), 3,4-ethylenedioxythiophene (EDOT), and 3,4-phenylenedioxythiophene (PheDOT), respectively, to yield copolymers P(OE3)-D, P(OE3)-E, and P(OE3)-Ph. At a dopant concentration of 5 mM FeTos 3 , the electrical conductivities of these copolymers vary significantly (ranging between 9 and 195 S cm –1 ) with the EDOT copolymer, P(OE3)-E, achieving the highest electrical conductivity. UV–vis–NIR and X-ray spectroscopies show differences in both susceptibility to oxidative doping and extent of oxidation for the P(OE3) series, with P(OE3)-E being the most doped. Wide-angle X-ray scattering measurements indicate that P(OE3)-E generally demonstrates the lowest paracrystallinity values in the series, as well as relatively small π–π stacking distances. The significant (i.e., order of magnitude) increase in electrical conductivity of doped P(OE3)-E films versus doped P(OE3)-D or P(OE3)-Ph films can therefore be attributed to P(OE3)-E exhibiting both the highest carrier ratios in the P(OE3) series, along with good π–π overlap and local ordering (low paracrystallinity values). Furthermore, these trends in the extent of doping and paracrystallinity are consistent with the reduced Fermi energy level and transport function prefactor parameters calculated using the semilocalized transport (SLoT) model. Observed differences in carrier ratios at the transport edge (c t ) and reduced Fermi energies [η(c)] suggest a broader electronic band (better overlap and more delocalization) for the EDOT-incorporating P(OE3)-E polymer relative to P(OE3)-D and P(OE3)-Ph. Ultimately, we rationalize improvements in electrical conductivity due to microstructural and doping enhancements caused by EDOT incorporation, a structure–property relationship worth considering in the future design of highly electrically conductive systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dictating Pt-Based Electrocatalyst Performance in Polymer Electrolyte Fuel Cells, from Formulation to Application

In this study, in situ electrochemical diagnostics designed to probe ionomer interactions with platinum and carbon were applied to relate ionomer coverage and conformation, gleaned from anion adsorption data, with O 2 transport resistance for low-loaded (0.05 mg Pt cm -2 ) platinum-supported Vulcan carbon (Pt/Vu)-based electrodes in a polymer electrolyte fuel cell. Coupling the in situ diagnostic data with ex situ characterization of catalyst inks and electrode structures, the effect of ink composition is explained by both ink-level interactions that dictate the electrode microstructure during fabrication and the resulting local ionomer distribution near catalyst sites. Electrochemical techniques (CO displacement and ac impedance) show that catalyst inks with higher water content increase ionomer (sulfonate) interactions with Pt sites without significantly affecting ionomer coverage on the carbon support. Surprisingly, the higher anion adsorption is shown to have a minor impact on specific activity, while exhibiting a complex relationship with oxygen transport. Ex situ characterization of ionomer suspensions and catalyst/ionomer inks indicates that the lower ionomer coverage can be correlated with the formation of large ionomer aggregates and weaker ionomer/catalyst interactions in low-water content inks. These larger ionomer aggregates resulted in increased local oxygen transport resistance, namely, through the ionomer film, and reduced performance at high current density. In the water-rich inks, the ionomer aggregate size decreases, while stronger ionomer/Pt interactions are observed. The reduced ionomer aggregation improves transport resistance through the ionomer film, while the increased adsorption leads to the emergence of resistance at the ionomer/Pt interface. Overall, the high current density performance is shown to be a nonmonotonic function of ink water content, scaling with the local gas (H 2 , O 2 ) transport resistance resulting from pore, thin film, and interfacial phenomena.

30 DIRECT ENERGY CONVERSION↗

Corrosion Behavior of 316L Stainless Steel Fabricated by Selective Laser Melting Under Different Scanning Speeds

This work discussed the effects of different scanning speeds (800, 1083, 1200 and 1400 mm/s) on the microstructure of 316L stainless steel manufactured by selective laser melting (SLM) and the related corrosion behavior. Results showed that there were more voids with faster scanning speeds, and there were oxide powder and non-melt silicon inside the defects. The SLM 316L exhibited a full gamma austenite phase filled with sub-grains, and the average grain size of SLM-1083 mm/s 316L was approximately 42 μm, three times larger than that of the quenched 316L. The pitting potentials for the SLM 316L were all approximately 300 mV higher than that of the quenched due to the modification of inclusions in SLM, but the corrosion rate for the SLM 316L was faster, which was attributed to the voids and unstable passive film. The number of pitting sites increased with the scanning speed, and the pits occurred preferentially at the voids in SLM 316L.

36 MATERIALS SCIENCE↗

Development of a new generation of quench and partitioning steels: Influence of processing parameters on texture, nanoindentation, and mechanical properties

A novel quenching and partitioning process (Q&P) including the hot stamping (HS) process was studied, using two stamping temperatures (750 °C and 800 °C) and two quenching temperatures (318 °C and 328 °C). This combination is here called Hot Stamping and Quenching and Partitioning process (HSQ&P). The partitioning step was performed at 400 °C for 100 s in all cycles. Microstructural features were comprehensively studied using electron backscattered diffraction and nanoindentation techniques. HSQ&P samples showed a good combination of ductility and high-strength due to the presence of: retained austenite, inter-critical ferrite with low stored internal strain energy, grain refinement via DIFT-effect (deformation induced ferrite transformation), martensite, and bainite. Significant internal stress relief was caused by carbon partitioning, which was induced by the DIFT-effect and the partitioning stage. This also led to a considerable stored energy, which was characterized by the Kernel average dislocation and geometrically necessary dislocation analysis. In addition, predominant {110}//strain direction crystallographic texture was identified, which promotes slip deformation and enhances the mechanical properties. Moreover, remarkable amounts of fine film-like retained austenite oriented along compact crystallographic directions (i.e., $\langle$111$\rangle$ and $\langle$112$\rangle$) were observed. Finally, subsize tensile test verified the optimum mechanical behavior of HSQ&P specimens.

36 MATERIALS SCIENCE↗

Pore-scale water dynamics during drying and the impacts of structure and surface wettability

Plants and microbes secrete mucilage into soil during dry conditions, which can alter soil structure and increase contact angle. Structured soils exhibit a broad pore size distribution with many small and many large pores, and strong capillary forces in narrow pores can retain moisture in soil aggregates. Meanwhile, contact angle determines the water repellency of soils, which can result in suppressed evaporation rates. Although they are often studied independently, both structure and contact angle influence water movement, distribution, and retention in soils. Here drying experiments were conducted using soil micromodels patterned to emulate different aggregation states of a sandy loam soil. Micromodels were treated to exhibit contact angles representative of those in bulk soil (8.4° ± 1.9°) and the rhizosphere (65° ± 9.2°). Drying was simulated using a lattice Boltzmann single-component, multiphase model. In our experiments, micromodels with higher contact angle surfaces took 4 times longer to completely dry versus micromodels with lower contact angle surfaces. Microstructure influenced drying rate as a function of saturation and controlled the spatial distribution of moisture within micromodels. In conclusion, lattice Boltzmann simulations accurately predicted pore-scale moisture retention patterns within micromodels with different structures and contact angles.

Variation in Morphology and Kinetics of Granular Bainite with Welding Thermal Cycles in High-Nb Fire-Resistant Steel: Experiments and Theoretical Calculations

The microstructure and kinetics of granular bainite (GB) were investigated in novel fire-resistant steel containing high niobium and subjected to simulated welding thermal cycles. The dilatometric data were analyzed to determine the activation energy and Avrami exponents. It was observed that austenite transformed to GB over a wide range cooling rates of 0.5-100 K/s. Theoretical calculations indicated that Avrami exponent (n) decreased with increased transformed volume fraction (f{sub b}) and cooling rate. At a moderate cooling rate of 20-6 K/s, bainitic ferrite as sheaves formed from austenite and the corresponding Avrami exponent was 2 < n < 3. Martensite in martensite/austenite constituent formed with Avrami exponent n ~ 1. At the fastest cooling rate of 50 K/s, lath bainitic ferrite and film-like retained austenite (RA) were obtained with the corresponding Avrami exponent n ~ 1. At lower cooling of 1 and 0.5 K/s, plate-like bainitic ferrite and block-like microphase composed of lamellar RA and ferrite were obtained with Avrami exponent n > 3. The local activation energy for austenite transformation to bainitic ferrite decreased from ~ 198 to ~ 182 kJ/mol with increasing f{sub b} from 0.05 to 0.95, while the local activation energy for austenite transformation to martensite decreased from ~ 80 to ~ 71 kJ/mol with increasing f{sub b} from 0.05 to 0.95.

36 MATERIALS SCIENCE↗

Microstructural, chemical and textural characterization of ZnO nanorods synthesized by aerosol assisted chemical vapor deposition

ZnO nanorods were synthesized by aerosol assisted chemical vapor deposition onto TiO{sub 2} covered borosilicate glass substrates. Deposition parameters were optimized and kept constant. Solely the effect of different nozzle velocities on the growth of ZnO nanorods was evaluated in order to develop a dense and uniform structure. The crystalline structure was characterized by conventional X-ray diffraction in grazing incidence and Bragg–Brentano configurations. In addition, two-dimensional grazing incidence synchrotron radiation diffraction was employed to determine the preferred growth direction of the nanorods. Morphology and growth characteristics analyzed by electron microscopy were correlated with diffraction outcomes. Chemical composition was established by X-ray photoelectron spectroscopy. X-ray diffraction results and X-ray photoelectron spectroscopy showed the presence of wurtzite ZnO and anatase TiO{sub 2} phases. Morphological changes noticed when the deposition velocity was lowered to the minimum, indicated the formation of relatively vertically oriented nanorods evenly distributed onto the TiO{sub 2} buffer film. By coupling two-dimensional X-ray diffraction and computational modeling with ANAELU it was proved that a successful texture determination was achieved and confirmed by scanning electron microscopy analysis. Texture analysis led to the conclusion of a preferred growth direction in [001] having a distribution width Ω = 20° ± 2°. - Highlights: • Uniform and pure single-crystal ZnO nanorods were obtained by AACVD technique. • Longitudinal and transversal axis parallel to the [001] and [110] directions, respectively. • Texture was determined by 2D synchrotron diffraction and electron microscopy analysis. • Nanorods have its [001] direction distributed close to the normal of the substrate. • Angular spread about the preferred orientation is 20° ± 2°.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Photovoltaic Blend Microstructure for High Efficiency Post-Fullerene Solar Cells. To Tilt or Not To Tilt?

Achieving efficient polymer solar cells (PSCs) requires a structurally optimal donor-acceptor heterojunction morphology. In this paper, we report the combined experimental and theoretical characterization of a benzodithiophene benzothiadiazole donor polymer series (PBTZF4-R; R = alkyl substituent) blended with the non-fullerene acceptor ITIC-Th, and analyse the effects of substituent dimensions on blend morphology, charge transport, carrier dynamics, and PSC metrics. Varying substituent dimensions has a pronounced effect on the blend morphology with a direct link between domain purity, to some extent domain dimensions, and charge generation and collection. The polymer with the smallest alkyl substituent yields the highest PSC power conversion efficiency (PCE, 11%), reflecting relatively small, high-purity domains, and possibly benefiting from “matched” donor polymer - small molecule acceptor orientations. The distinctive morphologies arising from the substituents are investigated using molecular dynamics (MD) computation which reveals that substituent dimensions dictate a well-defined set of polymer conformations, in turn driving chain aggregation, and ultimately, the various film morphologies and mixing with acceptor small molecules. Finally, a straightforward energetic parameter explains the experimental polymer domain morphological trends, hence PCE, and suggests strategies for substituent selection to optimize PSC materials morphologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exceptional Alignment in a Donor–Acceptor Conjugated Polymer via a Previously Unobserved Liquid Crystal Mesophase

Abstract Orienting polymer semiconductors is desirable to optimize device characteristics, provide insight into microstructure, and magnify subtle phase behavior. Here, a combination of uniaxial strain and subsequent heating of the donor–acceptor (DA) polymer PBnDT‐FTAZ is discovered to lead to exceptional optical dichroic ratios of up to 38 (and close to 50 near the polymer's absorption edge). This alignment is achieved due to the existence of a previously undetected thermotropic liquid crystal (LC) mesophase. The LC transition, not discernable through calorimetry, is uncovered through a combination of in situ UV–vis spectroscopy, X‐ray scattering, and dynamic mechanical analysis (DMA). Comparing PBnDT‐FTAZ to the non‐fluorinated PBnDT‐HTAZ and the homo polymer PBnDT, all of which show similar thermal transitions, reveals that exceptional alignment is only found in PBnDT‐FTAZ. This is attributed to the PBnDT‐FTAZ film having two distinct liquid crystal populations, and the polymer templating to a highly aligned, high‐clearing temperature population when heated. The DMA thermal relaxation behavior observed here is also seen in other DA conjugated polymers suggesting that such thermotropic LC mesophases may be common in these materials. These findings demonstrate a polymer semiconductor with remarkable alignment and uncover phase behavior with broad implications for process‐structure‐property relationships in polymer semiconductors.

36 MATERIALS SCIENCE↗

Flash Formation of I-Rich Clusters during Multistage Halide Segregation Studied in MAPbI 1.5 Br 1.5

Wide band gap mixed halide perovskites such as MAPb(I 1–x Br x ) 3 sparked great research interest because of their outstanding optoelectronic properties, ease of fabrication, and band gap tunability. Their application thus far is however limited by light-induced halide segregation in which microscopic clusters with a high iodide content are formed and act as recombination centers. The key mechanism(s) underlying this halide segregation process are still debated. Here, we present a study on the photoluminescence evolution in MAPb(I 1.5 Br 1.5 ) perovskites with varying microstructures under constant illumination at room temperature and at elevated temperature. Our findings reveal a more complicated picture of the segregation mechanism occurring in three stages instead of two as commonly reported. The process starts with a flash formation of I-rich domains. Following is a rapid blue shift before the gradual and typically observed red shift occurs. The evolution of the three stages is fully reversible in the dark and is also present at elevated temperatures (50 °C). We explain the existence of multiple stages during light-induced halide segregation by natural compositional fluctuations of the halides and the formation of halide clusters with a dynamically changing distribution in I–Br content. The variation in the I–Br ratio depends on the grain size and film heterogeneity. Overall, these findings add further details in the quest of unraveling the underlying segregation mechanism(s), which need to be identified to stabilize halides in wide band gap perovskites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanoindentation of Micrograins in Polycrystals under Multiaxial Stress: Control of Abrupt & Stochastic Plastic Events

Deforming objects in the world of the small has proven a much more complex task than just bending a common-sized object like a spoon. Over the last decade, it has become clear that the application of stress on micron-sized objects, such as micropillars, leads to abrupt and stochastic plastic strain jumps that do not satisfy Weibull statistics (as expected for uncorrelated defect yielding) but instead seem to follow highly wide, power-law distributions, pointing towards cooperative dislocation plasticity. Are power-law distributed plastic events the rule or the exception in crystals? If the rule, can we design protocols to control and suppress them in order to achieve deterministic and smooth microforming processes? We propose to combine experiments and theory to unravel the mysteries of abrupt microplastic deformation in a natural dislocation environment: micron-sized grains (\micrograins") of polycrystals. We propose a novel experimental design that utilizes nanoindentation and 4-point bending techniques on the substrate of polycrystalline thin films of two typical FCC metals (Al and Cu), and make concrete theoretical conjectures, based on intuition built from previous theoretical and experimental efforts in micropillar compression and nanoindentation. Based on a wide set of observations over the last decade, we put forward two distinct hypotheses that we propose to investigate in both theory and experiments: Our first conjecture is that crystal plasticity in the central region of micron-sized grains has micropillar-like stochastic features: power-law plastic strain jumps at stresses above the macroscale yield strength, displaying strong size and rate effects. We will demonstrate this similarity in spherical nanoindentation experiments in the central-region of multi-orientation grains of Al and Cu thin films. Al and Cu are selected for their disparity in stacking fault energy and consequently, their different propensity for cross-slip relaxation; however, our protocol may be applied to any crystalline material of technological interest. We will test our hypothesis by performing two-dimensional extended discrete dislocation plasticity (2.5D-DDP) simulations, inspired by comparable successful studies of micropillar plasticity, and extended to model nanoindentation with two slip systems and on a surface of a bicrystal with microhard grain-boundaries (GB), ie. not allowing dislocation absorption (116). Our model will include effective three dimensional dislocation mechanisms such as dislocation multiplication and double-cross-slip assisted glide. Second, we hypothesize that the application of uniform in-plane stress on our thin films below the yield point can smoothen the micrograin plastic response during nanoindentation. On a technological level, we propose that indentation-induced localization (sink-in) may be diminished by the application of concurrent in-plane stress that activates slow, viscoplastic relaxations near GBs. We aim to demonstrate our hypothesis through a 4-point bending apparatus that introduces a homogeneous in-plane stress state before indentation. We will perform simulations of a coarse-grained mesoscale theory of plasticity in a system with microhard GBs, benchmarked through 2.5D-DDP simulations, which will capture the effects of slow viscoplastic relaxations. Our nanoindentation abrupt event statistics studies, either in the micrograin interior or near GBs, will be correlated to direct observations of induced surface dislocation microstructures. For we will use TEM-based methods (PACOM/TKD) in combination with EBSD. Indents placed in the center of grains will be analyzed based on the orientation of the grain, while those near to GBs will be analyzed based on the orientation of each grain, the distance from the GB and the 5 degrees of freedom of the GB.

36 MATERIALS SCIENCE↗

Asymmetric Wettability Directs Leidenfrost Droplets

Leidenfrost phenomena on nano- and microstructured surfaces are of great importance for increasing control over heat transfer in high power density systems utilizing boiling phenomena. They also provide an elegant means to direct droplet motion in a variety of recently emerging fluidic systems. Here, we report the fabrication and characterization of tilted nanopillar arrays (TNPAs) that exhibit directional Leidenfrost water droplets under dynamic conditions, namely on impact with Weber numbers 40 at T 325 C. The batch fabrication of the TNPAs was achieved by glancing-angle anisotropic reactive ion etching of a thermally dewet platinum mask, with mean pillar diameters of 100 nm and heights of 200-500 nm. In contrast to previously implemented macro- and microscopic Leidenfrost ratchets, our TNPAs induce no preferential directional movement of Leidenfrost droplets under conditions approaching steady-state film boiling, suggesting that the observed droplet directionality is not a result of asymmetric vapor flow. Using high-speed imaging, phase diagrams were constructed for the boiling behavior upon impact for droplets falling onto TNPAs, straight nanopillar arrays, and smooth silicon surfaces. The asymmetric impact and directional trajectory of droplets was exclusive to the TNPAs for impacts corresponding to the transition boiling regime, revealing that asymmetric wettability upon impact is the mechanism for the droplet directionality.

asymmetric rebound↗