Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “angle control”

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 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Subtle Molecular Changes Largely Modulate Chiral Helical Assemblies of Achiral Conjugated Polymers by Tuning Solution-State Aggregation

Understanding the solution-state aggregate structure and the consequent hierarchical assembly of conjugated polymers is crucial for controlling multiscale morphologies during solid thin-film deposition and the resultant electronic properties. However, it remains challenging to comprehend detailed solution aggregate structures of conjugated polymers, let alone their chiral assembly due to the complex aggregation behavior. Herein, we present solution-state aggregate structures and their impact on hierarchical chiral helical assembly using an achiral diketopyrrolopyrrole-quaterthiophene (DPP-T4) copolymer and its two close structural analogues wherein the bithiophene is functionalized with methyl groups (DPP-T2M2) or fluorine atoms (DPP-T2F2). Combining in-depth small-angle X-ray scattering analysis with various microscopic solution imaging techniques, we find distinct aggregate in each DPP solution: (i) semicrystalline 1D fiber aggregates of DPP-T2F2 with a strongly bound internal structure, (ii) semicrystalline 1D fiber aggregates of DPP-T2M2 with a weakly bound internal structure, and (iii) highly crystalline 2D sheet aggregates of DPP-T4. These nanoscopic aggregates develop into lyotropic chiral helical liquid crystal (LC) mesophases at high solution concentrations. Intriguingly, the dimensionality of solution aggregates largely modulates hierarchical chiral helical pitches across nanoscopic to micrometer scales, with the more rigid 2D sheet aggregate of DPP-T4 creating much larger pitch length than the more flexible 1D fiber aggregates. Combining relatively small helical pitch with long-range order, the striped twist-bent mesophase of DPP-T2F2 composed of highly ordered, more rigid 1D fiber aggregate exhibits an anisotropic dissymmetry factor (g-factor) as high as 0.09. This study can be a prominent addition to our knowledge on a solution-state hierarchical assembly of conjugated polymers and, in particular, chiral helical assembly of achiral organic semiconductors that can catalyze an emerging field of chiral (opto)electronics.

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

Approaching disorder-tolerant semiconducting polymers

Doping has been widely used to control the charge carrier concentration in organic semiconductors. However, in conjugated polymers, n-doping is often limited by the tradeoff between doping efficiency and charge carrier mobilities, since dopants often randomly distribute within polymers, leading to significant structural and energetic disorder. Here, we screen a large number of polymer building block combinations and explore the possibility of designing n-type conjugated polymers with good tolerance to dopant-induced disorder. We show that a carefully designed conjugated polymer with a single dominant planar backbone conformation, high torsional barrier at each dihedral angle, and zigzag backbone curvature is highly dopable and can tolerate dopant-induced disorder. With these features, the designed diketopyrrolopyrrole (DPP)-based polymer can be efficiently n-doped and exhibit high n-type electrical conductivities over 120 S cm -1 , much higher than the reference polymers with similar chemical structures. This work provides a polymer design concept for highly dopable and highly conductive polymeric semiconductors.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Phase evolution during conventional and reactive flash sintering of (Mg,Ni,Co,Cu,Zn)O via in situ X-ray diffraction

Reactive flash sintering (RFS) enables the simultaneous synthesis and sintering of ceramics and has been shown to affect the reaction pathway of different materials. Herein, in situ synchrotron X-ray diffraction (XRD) is used to investigate the (Mg,Ni,Co,Cu,Zn)O entropy-stabilized oxide formation during: (i) conventional heating and (ii) RFS under current rate-controlled mode. The same reaction pathway is verified in both instances: the starting rock-salt (RS), spinel (Co 3 O 4 ), tenorite (CuO), and wurtzite (ZnO) phases transform into a single RS phase with a (1 1 1) to (2 0 0) intensity ratio of 0.67, consistent with a random distribution of the cations into the structure. Pt lattice peak shift from the XRD patterns is used as standard to monitor the sample surface temperature, revealing a strong endothermic reaction during the RS single-phase formation (Pt peaks shift toward higher angles while increasing sample temperature/current density). Furthermore, in RFS, the single-phase RS structure is formed in just 60 s at a furnace temperature of 600°C and a current rate of 220 mA mm -2 /min. Therefore, RFS greatly accelerates the synthesis of (Mg,Ni,Co,Cu,Zn)O, however, it does not play a role in the reaction pathway for this material formation.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Altering apparent optical properties with an array of semitransparent mesoscale structures

The ability to control and optimize interactions between light and matter has much utility in engineering design. A well-researched way to achieve optical property modulation is via the use of optical metamaterials, which feature sub-wavelength scale surface structures. In this work, an alternative approach for modulating optical properties is presented using a composite surface modified with a periodic array of semitransparent hemispherical shell mesoscale structures which are larger than the incident light wavelength. A ray-tracing simulation approach is used to predict the optical behavior for an arrayed surface. At oblique angles of incidence, significant increases and decreases in apparent absorptance are achieved via the use of optically thick and thin shells, respectively. Additionally, a potential application to solar cells is described with optimal spectral behavior achieved via the use of semitransparent external structures.

Kucuktas, Onur A.↗
DOE OSTI2021

Supermolecular structures of recrystallized starches with amylopectin side chains modified by amylosucrase to different chain lengths

Understanding the supermolecular structures of recrystallized starches is imperative to manufacture novel starches with controllable physicochemical properties enabling novel applications. In this study, native amylopectin (AP) from maize was modified to different chain lengths using amylosucrase from Neisseria polysaccharea. Native AP granules showed well-organized lamellar structures with a periodicity of ca. 9.0 nm whereas modified starches formed heterogeneous structures with the average crystallite size ranging from 19.77 to 29.88 nm. Acidic treatments eroded amorphous domains in both native AP granules and modified starch particles, producing nanocrystals composed of double helices. A-type nanocrystals (~40 nm) from native AP granules showed quadrangular shape with an acute angle of ca. 60°, while irregular B-type nanocrystals were observed for the modified starches. Molecular characterizations suggested that the nanocrystals had relatively uniform chain lengths (DP 16.5–25.2), and the helix length (the thickness of nanocrystals) was positively correlated to the thermal stability of starches.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2020

Effects of lithium intercalation in twisted bilayer graphene

In this work, we investigate the effects of lithium intercalation in twisted bilayers of graphene, using first-principles electronic structure calculations. To model this system we employ commensurate supercells that correspond to twist angles of 7.34° and 2.45°. From the energetics of lithium absorption we demonstrate that for low Li concentration the intercalants cluster in the AA regions with double the density of a uniform distribution. The charge donated by the Li atoms to the graphene layers results in modifications to the band structure that can be qualitatively captured using a continuum model with modified interlayer couplings in a region of parameter space that has yet to be explored either experimentally or theoretically. Thus, the combination of intercalation and twisted layers simultaneously provides the means for spatial control over material properties and an additional knob with which to tune moiré physics in twisted bilayers of graphene, with potential applications ranging from energy storage and conversion to quantum information.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Flat Bands and Chiral Optical Response of Moiré Insulators

Here, we present a low-energy model describing the reconstruction of the electronic spectrum in twisted bilayers of honeycomb crystals with broken sublattice symmetry. The resulting moiré patterns are classified into two families with different symmetry. In both cases, flat bands appear at relatively large angles without any magic-angle condition. Transitions between them give rise to sharp resonances in the optical absorption spectrum at frequencies well below the gap of the monolayer. Owing to their chiral symmetry, twisted bilayers display circular dichroism, that is, different absorption of left and right circularly polarized light. This optical activity is a nonlocal property determined by the stacking. In hexagonal boron nitride, sensitivity to the stacking leads to strikingly different circular dichroism in the two types of moirés. Our calculations exemplify how subtle properties of the electronic wave functions, encoded in current correlations between the layers, control physical observables of moiré materials.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Interfacial and Activation Energies of Environmentally Abundant Heterogeneously Nucleated Iron(III) (Hydr)oxide on Quartz

Poorly crystalline iron(III) (hydr)oxide nanoparticles are ubiquitous in environmental systems and play a crucial role in controlling the fate and transport of contaminants. Yet, the thermodynamic and kinetic parameters, e.g., the effective interfacial (α^') and apparent activation (E a ) energies, of iron(III) (hydr)oxide nucleation on earth-abundant mineral surfaces have not been determined, which hinders an accurate prediction of iron(III) (hydr)oxide formation and its interactions with other toxic or reactive ions. Here, for the first time, we report experimentally obtained α^' and E a for iron(III) (hydr)oxide nucleation on quartz mineral surfaces, by employing a flow-through, time-resolved grazing incidence small angle X-ray scattering (GISAXS). GISAXS enabled the in situ detection of iron(III) (hydr)oxide nucleation rates under different supersaturations (σ, achieved by varying pH 3.3-3.6) and temperatures (12-35ºC). By quantitative analyses based on classical nucleation theory, α^' was obtained to be 34.6 mJ/m 2 and E a was quantified as 32.8 kJ/mol. The fundamental thermodynamic and kinetic parameters obtained here will advance our fundamental understanding of the surface chemistry and nucleation behavior of iron(III) (hydr)oxides in subsurface and water treatment systems, as well as their effects on the fate and transport of pollutants in natural and engineered water systems. The in situ flow-through GISAXS method can also be adapted to quantify thermodynamic and kinetic parameters at interfaces for many important solid–liquid environmental systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Antivesiculation and Complete Unbinding of Tail-Tethered Lipids

Here, we report the effect of tail-tethering on vesiculation and complete unbinding of bilayered membranes. Amphiphilic molecules of a bolalipid, resembling the tail-tethered molecular structure of archaeal lipids, with two identical zwitterionic phosphatidylcholine headgroups self-assemble into a large flat lamellar membrane, in contrast to the multilamellar vesicles (MLVs) observed in its counterpart, monopolar nontethered zwitterionic lipids. The antivesiculation is confirmed by small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cyro-TEM). With the net charge of zero and higher bending rigidity of the membrane (confirmed by neutron spin echo (NSE) spectroscopy), the current membrane theory would predict that membranes should stack with each other (aka “bind”) due to dominant van der Waals attraction, while the outcome of the nonstacking (“unbinding”) membrane suggests that the theory needs to include entropic contribution for the nonvesicular structures. This report pioneers an understanding of how the tail-tethering of amphiphiles affects the structure, enabling better control over the final nanoscale morphology.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electron-Beam Induced Emergence of Mesoscopic Ordering in Layered MnPS 3

Ordered mesoscale structures in 2D materials induced by small misorientations have allowed for a wide variety of electronic, ferroelectric, and quantum phenomena to be explored. Until now, the only mechanism to induce this periodic ordering was via mechanical rotations between the layers, with the periodicity of the resulting moiré pattern being directly related to twist angle. Here we report a fundamentally distinct mechanism for emergence of mesoscopic periodic patterns in multilayer sulfur-containing metal phosphorus trichalcogenide, MnPS3, induced by the electron beam. The formation under the beam of periodic hexagonal patterns with several characteristic length scales, nucleation and transitions between the phases, and local dynamics are demonstrated. The associated mechanisms are attributed to the relative contraction of the layers caused by beam-induced sulfur vacancy formation with subsequent ordering and lattice parameter change. As a result, the plasmonic response of the system is locally altered, suggesting an element of control over plasmon resonances by electron beam patterning. To conclude, we pose that harnessing this phenomenon provides both insight into fundamental physics of quantum materials and enables device applications by enabling controlled periodic potentials on the atomic scale.

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

Electron-induced massive dynamics of magnetic domain walls

We study the dynamics of domain walls (DWs) in a metallic, ferromagnetic nanowire, focusing on inertial effects on the DW due to interaction with a conduction electron bath. In this work, we develop a Keldysh collective coordinate technique to describe the effect of conduction electrons on rigid magnetic structures. The effective Lagrangian and Langevin equations of motion for a DW are derived microscopically, including the full response kernel which is nonlocal in time. The DW dynamics is described by two collective degrees of freedom: position and tilt angle. The coupled Langevin equations therefore involve two correlated noise sources, leading to a generalized fluctuation-dissipation theorem (FDT). The DW response kernel due to electrons contains two parts: one related to dissipation via FDT and another reactive part. We prove that the latter term leads to a mass for both degrees of freedom, even though the intrinsic bare mass is zero. The electron-induced mass is present even in a clean system without pinning or specifically engineered potentials. The resulting equations of motion contain rich dynamical solutions and point toward a way to control domain wall motion in metals via the electronic system properties. We discuss two observable consequences of the mass, hysteresis in the DW dynamics, and resonant response to ac current.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

ORBIT simulations of fast ion power loads on the wall of the Divertor Tokamak Test

Abstract Neutral beam injection in tokamaks produces a population of fast ions, which interact with 3D magnetic fields in a variety of ways, often resulting in energetic particle losses in very short times to the wall. Careful design of neutral beams and active control of error fields helps to keep these losses to a minimum. Nevertheless, past experience in tokamaks in the 1980s and detailed simulations for future machines, such as International Thermonuclear Experimental Reactor, suggest that very localized fast ion losses (‘hot spots’) can be present, even if the overall losses are low. In this paper, we discuss this issue in the Divertor Tokamak Test (DTT) project, and we show that in the standard single-null full-power scenario of the DTT, fast ions produce two hot spots, corresponding approximately to the beam injection and exit toroidal angles: the former being mainly due to prompt losses/passing particles, while the latter is due to trapped ions. However, the maximum power load in these spots is of the order ∼ 63 kW m −2 , below the tolerance of plasma-facing components of the machine.

Physics↗
DOE OSTI2024

Growth and characterization of α-Sn thin films on In- and Sb-rich reconstructions of InSb(001)

α-Sn thin films can exhibit a variety of topologically nontrivial phases. Both studying the transitions between these phases and making use of these phases in eventual applications requires good control over the electronic and structural quality of α-Sn thin films. α-Sn growth on InSb often results in out-diffusion of indium, a p-type dopant. By growing α-Sn via molecular beam epitaxy on the Sb-rich c(4×4) surface reconstruction of InSb(001) rather than the In-rich c(8×2), we demonstrate a route to substantially decrease and minimize this indium incorporation. The reduction in indium concentration allows for the study of the surface and bulk Dirac nodes in α-Sn via angle-resolved photoelectron spectroscopy without the common approaches of bulk doping or surface dosing, simplifying topological phase identification. In this study, the lack of indium incorporation is verified in angle-resolved and angle-integrated ultraviolet photoelectron spectroscopy as well as in clear changes in the Hall response.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Control of wetting and uniformity via ZrSi x formation in ceramic-to-metal joints fabricated using Ag-Zr brazes

The deposition of a 2.0 µm SiO 2 film on the alumina surface in Kovar TM /94% alumina joints enables the formation of a silicide reaction layer on the alumina during brazing with 97Ag2Zr1Cu. Additionally, the average and standard deviation of joint thickness decrease from 50 to 15 and 29 to 4 µm, respectively compared to joints without added SiO 2 . Finally, the average failure stress of these braze joints was 45 MPa, while that of similar joints without added SiO 2 was 90 MPa. Sessile drop experiments of 98Ag2Zr on SiO 2 and 99.6% Al 2 O 3 substrates show that the braze wets and spreads to 3x its original area on SiO 2 with a wetting angle near 0°, but remains the same area on 99.6% Al 2 O 3 with a wetting angle of 106.6°. Focused-ion-beam scanning electron microscopy analysis of a cross-section of the 98Ag2Zr sessile drop on the SiO 2 substrate has shown that Zr reacts with SiO 2 to form Zr oxide and silicide layers. Scanning transmission electron microscopy diffraction and energy dispersive X-ray spectroscopy analysis indicate this silicide layer contains tetragonal Zr 5 Si 4 . In conclusion, analysis shows the silicide layer enhances wetting and joint uniformity while unreacted SiO 2 embrittles the joint and degrades strength.

alumina↗
DOE OSTI2021

Structure and Shape of Surface-Mediated Assembly of Surfactants

Achieving controls on the self-assembly of cationic and block copolymer micelles has significant implications for advancing novel material systems for energy, environmental, and biological applications and for tuning fluid flow behavior in subsurface geologic environments. While it is known that the aggregation of micelles is influenced by the composition of the surrounding fluid, the influence of a solid interface has been less explored. In this study, we probe the organization of cetyltrimethylammonium bromide (CTAB) micelles in the absence and presence of the Pluronic P123 block copolymer and quartz substrate using transmission and grazing-incidence small-angle X-ray scattering measurements and classical molecular dynamics (MD) simulations. In the absence of the quartz interface, CTAB with and without P123 molecules assemble as ellipsoid core–shell micelles. Densification of the core on adding P123 is noted from the decrease in the core radius from 15.9 to 14.6 Å. Here, the presence of a quartz substrate causes the micelles to elongate, which is noted by the emergence of a power-law slope in the low q region (<0.02 Å –1 ). Moreover, in the presence of both P123 and the quartz substrate, the micelle shape changes from ellipsoid core–shell to cylindrical core–shell, and a significantly higher number of aggregates are formed. The higher number of aggregates, and faster aggregation kinetics are linked to the organization of the solvent structures as noted from the MD simulations. These findings demonstrate the effects of adding a block copolymer and including a quartz substrate on the self-assembly of cationic (CTAB) micelles, which can be used to inform the design of functional material systems that harness surfactant chemistries.

42 ENGINEERING↗
DOE OSTI2021

Temporal coherent control of resonant two-photon double ionization of the hydrogen molecule via doubly excited states

Here, we use time-delayed, counter-rotating, circularly polarized few-cycle attosecond nonoverlapping pulses to study the temporal coherent control of the resonant process of two-photon double ionization (TPDI) of hydrogen molecule via doubly excited states for pulse propagation direction along $\hat k$ either parallel or perpendicular to the molecular axis $\hat R$. For $\hat k$∥ $\hat R$ and a pulse carrier frequency of 36 eV resonantly populating the Q 2 1 Π$^+_u$ (1) doubly excited state as well as other 1 Π$^+_u$ doubly excited states, we find that the indirect ionization pathway through these doubly excited states changes the character of the kinematical vortex-shaped momentum distribution produced by the two direct ionization pathways from fourfold to twofold rotational symmetry. This result is similar to what found in TPDI of the He atom involving 1 P$^ o_ {±1}$ doubly excited states; however, angular distributions exhibiting a quantum beat effect between the ground state and a doubly excited state seen for the He atom are observed here for its molecular counterpart with an anomaly in shape and magnitude, not in frequency. The sixfold differential probability integrated over the azimuthal angle of the photoelectron pair shows that this anomaly is due to autoionization decays and quantum beats between doubly excited states. For $\hat k$⟂$\hat R$ and a broadband pulse carrier frequency of 30 eV populating the Q 1 1 Π$^+_u$(1), Q 1 1 Σ$^+_u$(1), Q 2 1 Π$^+_u$(1) , and Q 1 1 Σ$^+_u$ (2) doubly excited states, the momentum distribution is shown to exhibit dynamical electron vortices with four spiral arms, which originates from the interplay between the 1 Δ$^+_ g$ , 1 Π$^+_ g$, and 1 Σ$^+_ g$ dynamical ionization amplitudes. Our treatment within either the adiabatic-nuclei approximation or fixed-nuclei approximation shows that the latter provides a very good account for this correlated process.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Transient Symmetry Controls Photo Dynamics near Conical Intersections

Excited-state chemistry lacks generalised symmetry rules. With many femtochemistry studies focused on individual cases, it is hard to build up the same level of chemical intuition for excited-states as exists for ground states. Here, we unravel the degrees of freedom involved in ultrafast internal conversion (IC) by mapping the vibrational coherence of the initial wavepacket, and the dependence on molecular symmetry in various cyclic tertiary amines. Molecular symmetry plays an important role in the preservation of vibrational coherence in the transit from one electronic state to another. We show here that it is sufficient for the molecule to simply have the possibility of a more symmetric structure to achieve the preservation of vibrational coherence. It can be transient and still lead to preservation. Furthermore, this finding provides an additional angle on how symmetry influences electronic transitions and an additional piece to the puzzle of establishing symmetry-based selection rules for excited-state processes.

74 ATOMIC AND MOLECULAR PHYSICS↗