Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “phase boundary”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Investigation of interfacial strength in nacre-mimicking tungsten heavy alloys for nuclear fusion applications

Abstract Tungsten heavy alloys have been proposed as plasma facing material components in nuclear fusion reactors and require experimental investigation in their confirmation. For this purpose, a 90W–7Ni–3Fe alloy has been selected and microstructurally manipulated to present a multiphase brick-and-mortar structure of W-phase ‘bricks’ surrounded by a ductile ‘mortar’. This work draws inspiration from nature to artificially imitate the extraordinary combination of strength and stiffness exhibited by mollusks and produce a nacre-mimicking metal matrix composite capable of withstanding the extremely hostile environment of the reactor interior and maintaining structural integrity. The underlying mechanisms behind this integrity have been probed through high-resolution structural and chemical characterization techniques and have revealed chemically diffuse phase boundaries exhibiting unexpected lattice coherency. These features have been attributed to an increase in the energy required for interfacial decohesion in these systems and the simultaneous expression of high strength and toughness in tungsten heavy alloys.

36 MATERIALS SCIENCE↗
DOE OSTI2018

High-rate electroreduction of carbon monoxide to multi-carbon products

Carbon monoxide electrolysis has previously been reported to yield enhanced multi-carbon (C 2+ ) Faradaic efficiencies of up to ~55%, but only at low reaction rates. This is due to the low solubility of CO in aqueous electrolytes and operation in batch-type reactors. Here, we present a high-performance CO flow electrolyser with a well controlled electrode–electrolyte interface that can reach total current densities of up to 1 A cm –2 , together with improved C 2+ selectivities. Computational transport modelling and isotopic C 18 O reduction experiments suggest that the enhanced activity is due to a higher surface pH under CO reduction conditions, which facilitates the production of acetate. Here, at optimal operating conditions, we achieve a C 2+ Faradaic efficiency of ~91% with a C 2+ partial current density over 630 mA cm –2 . Further investigations show that maintaining an efficient triple-phase boundary at the electrode–electrolyte interface is the most critical challenge in achieving a stable CO/CO 2 electrolysis process at high rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Large electromechanical strain and unconventional domain switching near phase convergence in a Pb-free ferroelectric

In many ferroelectrics, large electromechanical strains are observed near regions of composition- or temperature- driven phase coexistence. Phenomenologically, this is attributed to easy re-orientation of the polarization vector and/or phase transition, although their effects are highly convoluted and difficult to distinguish experimentally. Here, we used synchrotron X-ray scattering and digital image correlation to differentiate between the microscopic mechanisms leading to large electrostrains in an exemplary Pb-free piezoceramic Sn-doped barium calcium zirconate titanate. Large electrostrains of ~0.2% measured at room-temperature are attributed to an unconventional effect, wherein polarization switching is aided by a reversible phase transition near the tetragonal-orthorhombic phase boundary. Additionally, electrostrains of ~0.1% or more could be maintained from room temperature to 140°C due to a succession of different microscopic mechanisms. In situ X-ray diffraction elucidates that while 90° domain reorientation is pertinent below the Curie temperature ( T C ), isotropic distortion of polar clusters is the dominant mechanism above T C .

36 MATERIALS SCIENCE↗
DOE OSTI2017

Strain-induced alignment and phase behavior of blue phase liquid crystals confined to thin films

Here, we report on the influence of surface confinement on the phase behavior and strain-induced alignment of thin films of blue phase liquid crystals (BPs). Confining surfaces comprised of bare glass, dimethyloctadecyl [3-(trimethoxysilyl)propyl] ammonium chloride (DMOAP)-functionalized glass, or polyvinyl alcohol (PVA)-coated glass were used with or without mechanically rubbing to influence the azimuthal anchoring of the BPs. These experiments reveal that confinement can change the phase behavior of the BP films. For example, in experiments performed with rubbed-PVA surfaces, we measured the elastic strain of the BPs to change the isotropic–BPII phase boundary, suppressing formation of BPII for film thicknesses incommensurate with the BPII lattice. In addition, we observed strain-induced alignment of the BPs to exhibit a complex dependence on both the surface chemistry and azimuthal alignment of the BPs. For example, when using bare glass surfaces causing azimuthally degenerate and planar anchoring, BPI oriented with (110) planes of the unit cell parallel to the contacting surfaces for thicknesses below 3 μm but transitioned to an orientation with (200) planes aligned parallel to the contacting surfaces for thicknesses above 4 μm. In contrast, BPI aligned with (110) planes parallel to confining surfaces for all other thicknesses and surface treatments, including bare glass with uniform azimuthal alignment. Complementary simulations based on minimization of the total free energy (Landau–de Gennes formalism) confirmed a thickness-dependent reorientation due to strain of BPI unit cells within a window of surface anchoring energies and in the absence of uniform azimuthal alignment. In contrast to BPI, BPII did not exhibit thickness-dependent orientations but did exhibit orientations that were dependent on the surface chemistry, a result that was also captured in simulations by varying the anchoring energies. Overall, the results in this paper reveal that the orientations assumed by BPs in thin films reflect a complex interplay of surface interactions and elastic energies associated with strain of the BP lattice. The results also provide new principles and methods to control the structure and properties of BP thin films, which may find use in BP-templated material synthesis, and BP-based optical and electronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Enhanced magnetism in lightly doped manganite heterostructures: strain or stoichiometry?

Lattice mismatch induced epitaxial strain has been widely used to tune functional properties in complex oxide heterostructures. Apart from the epitaxial strain, a large lattice mismatch also produces other effects including modulations in microstructure and stoichiometry. However, it is challenging to distinguish the impact of these effects from the strain contribution to thin film properties. Here, we use La 0.9 Sr 0.1 MnO 3 (LSMO), a lightly doped manganite close to the vertical phase boundary, as a model system to demonstrate that both epitaxial strain and cation stoichiometry induced by strain relaxation contribute to functionality tuning. The thinner LSMO films are metallic with a greatly enhanced T C which is 97 K higher than the bulk value. Such anomalies in T C and transport cannot be fully explained by the epitaxial strain alone. Detailed microstructure analysis indicates La deficiency in thinner films and twin domains formation in thicker films. Our results have revealed that both epitaxial strain and strain relaxation induced stoichiometry/microstructure modulations contribute to the modified functional properties in lightly doped manganite perovskite thin films.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Investigation of n-type doping strategies for Mg 3 Sb 2

Recent, and somewhat surprising, successful n-type doping of Mg 3 Sb 2 was the key to realizing high thermoelectric performance in this material. Herein, we use first-principles defect calculations to investigate different extrinsic n-type doping strategies for Mg 3 Sb 2 and to reveal general chemical trends in terms of dopant solubilities and maximal achievable electron concentrations. In agreement with experiments, we find that Sb substitution is an effective doping strategy, with Se and Te doping predicted to yield up to ~8 × 10 19 cm –3 electrons. However, we also find that Mg substitution with trivalent (or higher) cations can be even more effective; in particular, the predicted highest achievable electron concentration (~5 × 10 20 cm –3 ) with La as an extrinsic dopant exceeds that of Se and Te doping. Interstitial doping (Li, Zn, Cu, Be) is found to be largely ineffective either due to self-compensation (Li) or high formation energy (Zn, Cu, Be). Lastly, our results offer La as an alternative dopant to Te and Se and reinforce the need for careful phase boundary mapping in achieving high electron concentrations in Mg 3 Sb 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2021

An octanol hinge opens the door to water transport

Despite their pharmacological relevance, the mechanism of transport across water/octanol phase boundaries has remained unexplored. Octanol molecular assemblies are demonstrated to reversibly bind water and swing like the hinge of a door.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Symmetry mismatch controlled ferroelastic domain ordering and the functional properties of manganite films on cubic miscut substrates

We have studied the magnetotransport properties and strain release mechanisms in ferroelastic La 0.9 Sr 0.1 MnO 3 (LSMO) epitaxial thin films on SrTiO 3 (STO)(001) substrates with different miscut angles. The substrate miscut angle plays a critical role in releasing shear strain and has a huge impact on the properties of the films. The strain relaxes by monoclinic distortion for films on low miscut substrates and for higher miscut substrates, the strain relaxation causes the formation of periodic twin domains with larger periodicities. Furthermore, we observe that the Curie temperature (T C ) decreases systematically, and magnetoresistance (MR) increases with increasing the miscut angle. Such changes in the magnetic and transport properties could be due to the increased density of phase boundaries (PBs) with the increase of miscut angle. This work provides a way to tailor film microstructures and subsequent functional properties of other complex oxide films on miscut substrates with symmetry mismatch.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Unexpected inverse correlations and cooperativity in ion-pair phase transfer

Liquid/liquid extraction is one of the most widely used separation and purification methods, where a forefront of research is the study of transport mechanisms for solute partitioning and the relationships that these have to solution structure at the phase boundary. To date, organized surface features that include protrusions, water-fingers, and molecular hinges have been reported. Many of these equilibrium studies have focused upon small-molecule transport – yet the extent to which the complexity of the solute, and the competition between different solutes, influence transport mechanisms have not been explored. Here we report molecular dynamics simulations that demonstrate that a metal salt (LiNO 3 ) can be transported via a protrusion mechanism that is remarkably similar to that reported for H 2 O by tri-butyl phosphate (TBP), a process that involves dimeric assemblies. Yet the LiNO 3 out-competes H 2 O for a bridging position between the extracting TBP dimer, which in-turn changes the preferred transport pathway of H 2 O. Examining the electrolyte concentration dependence on ion-pair transport unexpectedly reveals an inverse correlation with the extracting surfactant concentration. As [LiNO 3 ] increases, surface adsorbed TBP becomes a limiting reactant in correlation with an increased negative surface charge induced by excess interfacial NO 3 – , however the rate of transport is enhanced. Within the highly dynamic interfacial environment, we hypothesize that this unique cooperative effect may be due to perturbed surface organization that either decreases the energy of formation of transporting protrusion motifs or makes it easier for these self-assembled species to disengage from the surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Defect chemistry and doping of BiCuSeO

While p-type BiCuSeO is a well-known mid-temperature oxide thermoelectric (TE) material, computations predict that superior TE performance can be realized through n-type doping. In this study, we use first-principles defect calculations to show that Cu vacancies are responsible for the native p-type self doping; yet, we find that BiCuSeO is n-type dopable under Cu-rich growth conditions, where the formation of Cu vacancies is suppressed. We computationally survey a broad suite of 23 dopants and find that only Cl and Br are effective n-type dopants. Therefore, we recommend that future experimental doping efforts utilize phase boundary mapping to optimize the electron concentration and resolve the anomalous p–n–p transitions observed in halogen-doped BiCuSeO. The prospect of n-type doping, as revealed by our defect calculations, paves the path for rational design of BiCuSeO chemical analogues with similar doping behavior and even better TE performance.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Dielectric Properties Of Pb(In{sub 1/2}Nb{sub 1/2})O{sub 3}-PbTiO{sub 3} Solid Solution Synthesized By Solid State Reaction Route

Phase pure (1-x)Pb(In{sub 1/2}Nb{sub 1/2})O{sub 3}-x PbTiO{sub 3} ceramics near morphotrophic phase boundary (x = 0.35) are prepared by conventional solid state reaction route, by adding 2 mol.% MgO. The dielectric properties of lead indium niobate-lead titanate ceramic are studied as a function of both temperature and frequency. For this composition the dielectric constant for 100 Hz increases from 1944 at room temperature to 1510 at Curie temperature(304 deg. C). The saturation polarization, measured at room temperature, is found to be 23.9 {mu}C/cm{sup 2} for 40 kV/cm.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Reduction in anti-ferromagnetic interactions in ion-beam deposited Fe{sub 3}O{sub 4} thin films

Phase pure Fe{sub 3}O{sub 4} thin films of thickness {approx}42 nm have been prepared on the Si(100) substrate by reactive ion beam sputtering in the growth temperature range of 150-250 deg. C. A high degree of phase purity in the 175 deg. C sample has been confirmed by the XRD, Raman shift, and R-T measurements. The polycrystalline films show a sharp Verway transition as supported by temperature dependent resistivity, AC susceptibility, and coercivity behavior. The significant feature of these films is the early saturation of their room temperature magnetization at {approx}400 mT, indicating the presence of low anti-ferromagnetic competitions in sharp contrast to most of the previous reports. The noticeable reduction of anti-phase boundaries and its dependence on growth temperature has been correlated with the energetic ion-beam deposition process, and explained in terms of the of ionic vacancy migration approach of Eerenstein et al.[Phys. Rev. B 68, 014428 (2003)]. The electronic conduction of these films is governed by near-neighbor hopping above 240 K and Shklovskii-Efros variable range hopping below this transition temperature.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Electromechanical strain in Bi(Zn{sub 1/2}Ti{sub 1/2})O{sub 3}-(Bi{sub 1/2}Na{sub 1/2})TiO{sub 3}-(Bi{sub 1/2}K{sub 1/2})TiO{sub 3} solid solutions

Solid solutions ceramics of the Bi(Zn{sub 0.5}Ti{sub 0.5})O{sub 3}-(Bi{sub 0.5}K{sub 0.5})TiO{sub 3}-(Bi{sub 0.5}Na{sub 0.5})TiO{sub 3} ternary system for <20 mol. % BZT were created and confirmed to be single phase using x-ray diffraction. The dielectric dispersion showed decreasing T{sub max} of the dielectric spectrum with a broadening of the transition with increasing BZT content. At 2.5BZT-40BKT-57.5BNT, a secondary transition commonly observed for morphotropic phase boundary (MPB) BNT-BKT was observed. The ferroelectric behavior of the system was characterized by a transition where the polarization hysteresis showed a severe pinching effect on remanent polarization (20.8 {mu}C/cm{sup 2} at 2.5% BZT) as BZT contents was increased (P{sub r}= 2.3 {mu}C/cm{sup 2} at 20% BZT). Similarly, as the temperature increased to 175 deg. C, the remanent polarization of the 2.5% BZT composition significantly reduced to 2.1 {mu}C/cm{sup 2}. The onset of this transition corresponds to the lower temperature frequency dispersion observed in the dielectric spectrum. The strain hysteresis experienced analogous transition to the polarization, with a change in shape from typical ferroelectric butterfly to a complete loss of negative strain as BZT concentration increased. Maximum strain values of 0.33% were observed at 5-40-55 accompanied by a large d{sub 33}{sup *}=547pm/V.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A statistical model approximation for perovskite solid-solutions: a Raman study of lead-zirconate- titanate single crystal

Lead titanate (PbTiO3) is a classical example of a ferroelectric perovskite oxide illustrating a displacive phase transition accompanied by a softening of a symmetry-breaking mode. The underlying assumption justifying the soft-mode theory is that the crystal is macroscopically sufficiently uniform so that a meaningful free energy function can be formed. In contrast to PbTiO3, experimental studies show that the phase transition behaviour of lead-zirconate-titanate solid solution (PZT) is far more subtle. Most of the studies on the PZT system have been dedicated to ceramic or powder samples, in which case an unambiguous soft-mode study is not possible, as modes with different symmetries appear together. Our Raman scattering study on titanium-rich PZT single crystal shows that the phase transitions in PZT cannot be described by a simple soft-mode theory. In strong contrast to PbTiO3, splitting of transverse E-symmetry modes reveals that there are different locally-ordered regions. The role of crystal defects, random distribution of Ti and Zr at the B- cation site and Pb ions shifted away from their ideal positions, dictates the phase transition mechanism. A statistical model explaining the observed peak splitting and phase transformation to a complex state with spatially varying local order in the vicinity of the morphotropic phase boundary is given.

Frantti, Johannes↗
DOE OSTI2013

Enhanced piezoelectric performance of (0.98-x)Bi(Sc{sub 3/4}In{sub 1/4})O{sub 3}-xPbTiO{sub 3}-0.02Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3} ternary high temperature piezoelectric ceramics

(0.98-x)Bi(Sc{sub 3/4}In{sub 1/4})O{sub 3}-xPbTiO{sub 3}-0.02Pb(Zn{sub 1/3}Nb{sub 2/3})O{sub 3} (BSI-PT-PZN) high temperature piezoelectric ceramics were prepared by traditional solid-state reaction method. Combining X-ray diffraction results with piezoelectric data, it was found that the morphotropic phase boundary (MPB) occurred at x = 0.575. The piezoelectric constant d{sub 33}, curie temperature T{sub c}, and electromechanical coupling factor k{sub p} of BIS-PT-PZN ceramics with MPB composition were 427 pC/N, 412 Degree-Sign C, and 0.51, respectively. Furthermore, the strain of BIS-PT-PZN ceramics reached up to 0.25% under the electric field of 40 kV/cm. Temperature-dependent electromechanical coupling coefficient for MPB composition was stable from room temperature up to 350 Degree-Sign C. The piezoelectric properties of BIS-PT-PZN ceramics were comparable to that of 0.36BiScO{sub 3}-0.64PbTiO{sub 3} (BS-PT) ceramics, and the piezoelectric constant d{sub 33} of BIS-PT-PZN ceramics was about twice that of our previous reported 0.4Bi(Sc{sub 3/4}In{sub 1/4})O{sub 3}-0.6PbTiO{sub 3} (BSI-PT) ceramics. The reduction in the expensive Sc{sub 2}O{sub 3} content and comparable piezoelectric properties with BS-PT ceramics indicated that BIS-PT-PZN ceramics were promising for commercial applications as high temperature actuators and sensors.

36 MATERIALS SCIENCE↗
DOE OSTI2013

An (ultra) high-vacuum compatible sputter source for oxide thin film growth

A miniaturised CF-38 mountable sputter source for oxide and metal thin film preparation with enhanced high-vacuum and ultra-high-vacuum compatibility is described. The all home-built sputtering deposition device allows a high flexibility also in oxidic sputter materials, suitable deposition rates for preparation of films in the nm- and the sub-monolayer regime and excellent reliability and enhanced cleanliness for usage in UHV chambers. For a number of technologically important – yet hardly volatile – materials, the described source represents a significant improvement over thermal deposition techniques like electron-beam- or thermal evaporation, as especially the latter are no adequate tool to prepare atomically clean layers of refractory oxide materials. Furthermore, it is superior to commercially available magnetron sputter devices, especially for applications, where highly reproducible sub-monolayer thin film preparation under very clean UHV conditions is required (e.g., for studying phase boundary effects in catalysis). The device in turn offers the usage of a wide selection of evaporation materials and special target preparation procedures also allow the usage of pressed oxide powder targets. To prove the performance of the sputter-source, test preparations with technologically relevant oxide components, comprising ZrO{sub 2} and yttrium-stabilized ZrO{sub 2}, have been carried out. A wide range of characterization methods (electron microscopy, X-ray photoelectron spectroscopy, low-energy ion scattering, atomic force microscopy, and catalytic testing) were applied to demonstrate the properties of the sputter-deposited thin film systems.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Time-dependence of the alpha to epsilon phase transformation in iron

Here, iron was ramp-compressed over timescales of 3 ≤ t(ns) ≤ 300 to study the time-dependence of the α→ε (bcc→hcp) phase transformation. Onset stresses (σ α→ε ) for the transformation ~14.8-38.4 GPa were determined through laser and magnetic ramp-compression techniques where the transition strain-rate was varied between 10 6 ≤ $\dot{μ}$ α→ε (s ₋1 ) ≤ 5×10 8 . We find σ α→ε = 10.8 + 0.55 ln($\dot{μ}$ α→ε ) for $\dot{μ}$ α→ε < 10 6 /s and σ α→ε = 1.15($\dot{μ}$ α→ε ) 0.18 for $\dot{μ}$ α→ε > 10 6 /s. This $\dot{μ}$ response is quite similar to recent results on incipient plasticity in Fe suggesting that under high rate ramp compression the α→ε phase transition and plastic deformation occur through similar mechanisms, e.g., the rate limiting step for $\dot{μ}$ > 10 6 /s is due to phonon scattering from defects moving to relieve strain. We show that over-pressurization of equilibrium phase boundaries is a common feature exhibited under high strain-rate compression of many materials encompassing many orders of magnitude of strain-rate.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Dependence of the mechanical behavior of alloys on their electron work function—An alternative parameter for materials design

In this article, we demonstrate that the electron work function (EWF) as an intrinsic parameter can provide information or clues in a simple or straightforward way for material design, modification, and development. A higher work function of a material represents a more stable electronic state, which consequently generates a higher resistance to any attempt of changing the electronic state and other corresponding states, e.g., changes in structure or microstructure caused by mechanical and electrochemical actions. Using Cu-Ni alloy as an example, we demonstrate the correlation between the EWF and Young's modulus of the material as well as its hardness. The properties of a material can be modified using elements with appropriate work functions. This is also applicable for tailoring inter-phase boundaries or interfaces.

36 MATERIALS SCIENCE↗