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At least 703 records · Page 39

Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films

Two-dimensional coordination polymers (2DCPs) have been predicted to exhibit exotic properties such as superconductivity, topological insulating behavior, catalytic activity, and superior ion transport for energy applications; experimentally, these materials have fallen short of their expectation due to the lack of synthesis protocols that yield continuous, large crystallite domains, and highly ordered thin films with controllable physical and chemical properties. Herein, the fabrication of large-area, highly ordered 2DCP thin films with large crystallite domains using chemical vapor deposition (CVD) approaches is described. It is demonstrated that defects and the packing motifs of 2DCP thin films may be controlled by adjusting the vapor–vapor and vapor–solid interactions of the metal and organic linker precursors during the CVD fabrication process. Such control allows for the fabrication of defects-controlled 2DCP thin films that show either semiconducting or metallic behavior. The findings provide the first demonstration of tuning the electrical properties of sub 100 nm-thick continuous 2DCP thin films by controlling their electronic landscape through defect engineering. As such, it is determined that large-area, highly ordered 2DCP thin films may undergo a semiconducting to metallic transition that is correlated to changes in morphology, crystalline domain sizes, crystallite orientation, defect interactions, and electronic structure.

2D coordination polymers↗

Ultrahigh-Capacity Rocksalt Cathodes Enabled by Cycling-Activated Structural Changes

Mn-redox-based oxides and oxyfluorides are considered the most promising earth-abundant high-energy cathode materials for next-generation lithium-ion batteries. While high capacities are obtained in high-Mn content cathodes such as Li- and Mn-rich layered and spinel-type materials, local structure changes and structural distortions ( often lead to voltage fade, capacity decay, and impedance rise, resulting in unacceptable electrochemical performance upon cycling. In the present study, structural transformations that exploit the high capacity of Mn-rich oxyfluorides while enabling stable cycling, in stark contrast to commonly observed structural changes that result in rapid performance degradation, are reported. Here, it is shown that upon cycling of a cation-disordered rocksalt (DRX) cathode (Li 1.1 Mn 0.8 Ti 0.1 O 1.9 F 0.1 , an ultrahigh capacity of ≈320 mAh g –1 (energy density of ≈900 Wh kg –1 ) can be obtained through dynamic structural rearrangements upon cycling , along with a unique voltage profile evolution and capacity rise. At high voltage, the presence of Mn 4+ and Li + vacancies promotes local cation ordering, leading to the formation of domains of a “δ phase” within the disordered framework. On deep discharge, Mn 4+ reduction, along with Li + insertion transform the structure to a partially ordered DRX phase with a β'-LiFeO 2 -type arrangement. At the nanoscale, domains of the in situ formed phases are randomly oriented, allowing highly reversible structural changes and stable electrochemical cycling. These new insights not only help explain the superior electrochemical performance of high-Mn DRXbut also provide guidance for the future development of Mn-based, high-energy density oxide, and oxyfluoride cathode materials.

25 ENERGY STORAGE↗

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗

Non-volatile magnon transport in a single domain multiferroic

Antiferromagnets have attracted significant attention in the field of magnonics, as promising candidates for ultralow-energy carriers for information transfer for future computing. The role of crystalline orientation distribution on magnon transport has received very little attention. In multiferroics such as BiFeO 3 the coupling between antiferromagnetic and polar order imposes yet another boundary condition on spin transport. Thus, understanding the fundamentals of spin transport in such systems requires a single domain, a single crystal. We show that through Lanthanum (La) substitution, a single ferroelectric domain can be engineered with a stable, single-variant spin cycloid, controllable by an electric field. The spin transport in such a single domain displays a strong anisotropy, arising from the underlying spin cycloid lattice. Our work shows a pathway to understanding the fundamental origins of magnon transport in such a single domain multiferroic.

30 DIRECT ENERGY CONVERSION↗

Field-tuned ferroquadrupolar quantum phase transition in the insulator TmVO 4

We report results of low-temperature heat-capacity, magnetocaloric-effect, and neutron-diffraction measurements of TmVO 4 , an insulator that undergoes a continuous ferroquadrupolar phase transition associated with local partially filled 4 f orbitals of the thulium (Tm 3 + ) ions. The ferroquadrupolar transition, a realization of Ising nematicity, can be tuned to a quantum critical point by using a magnetic field oriented along the c axis of the tetragonal crystal lattice, which acts as an effective transverse field for the Ising-nematic order. In small magnetic fields, the thermal phase transition can be well described by using a semiclassical mean-field treatment of the transverse-field Ising model. However, in higher magnetic fields, closer to the field-tuned quantum phase transition, subtle deviations from this semiclassical behavior are observed, which are consistent with expectations of quantum fluctuations. Although the phase transition is driven by the local 4 f degrees of freedom, the crystal lattice still plays a crucial role, both in terms of mediating the interactions between the local quadrupoles and in determining the critical scaling exponents, even though the phase transition itself can be described via mean field. In particular, bilinear coupling of the nematic order parameter to acoustic phonons changes the spatial and temporal fluctuations of the former in a fundamental way, resulting in different critical behavior of the nematic transverse-field Ising model, as compared to the usual case of the magnetic transverse-field Ising model. Our results establish TmVO 4 as a model material and electronic nematicity as a paradigmatic example for quantum criticality in insulators.

36 MATERIALS SCIENCE↗

Compression behavior of dense H 2 -He mixtures up to 160 GPa

We have studied the compression behavior of H 2 -He mixtures in comparison with pure H 2 and He using powder synchrotron x-ray diffraction and present the pressure-volume (PV) compression data of H 2 -He mixtures to 160 GPa. The results indicate that both H 2 and He in H 2 -He mixtures remain in hcp to the maximum pressure studied, yet develop a substantial level of lattice distortion in the (100) plane, most profound in He-rich solids and below 66 GPa. The measured PV data also indicate softening of He (or H 2 )-rich lattice upon increasing the level of the guest H 2 (or He) concentration. We suggest that the observed softening and lattice distortion are due to a substitutional incorporation of H2 (guest) molecules into the basal plane of hcp-He (host) lattice and, thereby, reflect the miscibility between H 2 and He in H 2 -He mixtures. Interestingly, solid He exhibits a lesser degree of preferred orientation in H2-He mixtures than in pure He, likely due to the presence of solid H 2 disturbing the crystalline ordering of He-rich solids. Finally, the present PV compression data of H 2 -rich and He-rich solids to 160 GPa deviate from those of pure H 2 and pure He above ~70 and 45 GPa respectively, providing new constraints for development of the EOS for H 2 -He mixtures for planetary models.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Theoretical and observational analysis of spacecraft fields

In order to investigate the nondipolar contributions of spacecraft magnetic fields a simple magnetic field model is proposed. This model consists of randomly oriented dipoles in a given volume. Two sets of formulas are presented which give the rms-multipole field components, for isotropic orientations of the dipoles at given positions and for isotropic orientations of the dipoles distributed uniformly throughout a cube or sphere. The statistical results for an 8 cu m cube together with individual examples computed numerically show the following features: Beyond about 2 to 3 m distance from the center of the cube, the field is dominated by an equivalent dipole. The magnitude of the magnetic moment of the dipolar part is approximated by an expression for equal magnetic moments or generally by the Pythagorean sum of the dipole moments. The radial component is generally greater than either of the transverse components for the dipole portion as well as for the nondipolar field contributions.

Neubauer, F. M.↗

Cosmogenic nuclides in football-sized rocks.

The activity of long- and short-lived isotopes in a series of samples from a vertical column through the center of rock 14321 was measured. Rock 14321 is a 9 kg fragmental rock whose orientation was photographically documented on the lunar surface. Also investigated was a sample from the lower portion of rock 14310, where, in order to study target effects, two different density fractions (mineral separates) were analyzed. A few nuclides in a sample from the comprehensive fines 14259 were measured. This material has been collected largely from the top centimeter of the lunar soil. The study of the deep samples of 14321 and 14310 provided values for the activity of isotopes at points where only effects produced by galactic cosmic rays are significant.

Wahlen, M.↗

Jupiter's decametric rotation period and the source-A emission beam

Determinations of the average decametric rotation period for the planet Jupiter are discussed. Mean rotation periods for a twelve year span are plotted as a function of the mean epochs. Two lesser peaks in the longitude histograms were resolved in addition to the main peak. The three peaks, which are believed to result from emission beams oriented in different directions relative to the corotating magnetic field of the planet, are designated Sources A, B, and C in decreasing order of prominence at frequencies in the vicinity of 18 MHz.

Carr, T. D.↗

Anisotropies of galactic cosmic rays outside the orbit of earth measured on Pioneer 10

Preliminary results of observations of the directional distribution of cosmic rays being conducted by the University of Chicago experiment on the Pioneer 10 spacecraft are presented. The unusual geometry of the directional scan is described and some features of the response of a bidirectional coincidence telescope are discussed. Selected periods free from the presence of low-energy solar particles exhibit transient deviations from uniform directional distributions for the bidirectional flux of nuclei greater than 67 MeV/nucleon. These deviations are typically 2 to 4 (plus or minus 1) percent and are oriented very roughly in a N-S direction. Such nonuniformities observed with a bidirectional detector can only be due to even order terms in the angular distribution function.

Lentz, G. A.↗

Improved ultrasonic standard reference blocks

A program to improve the quality, reproducibility and reliability of nondestructive testing through the development of improved ASTM-type ultrasonic reference standards is described. Reference blocks of aluminum, steel, and titanium alloys are to be considered. Equipment representing the state-of-the-art in laboratory and field ultrasonic equipment was obtained and evaluated. RF and spectral data on ten sets of ultrasonic reference blocks have been taken as part of a task to quantify the variability in response from nominally identical blocks. Techniques for residual stress, preferred orientation, and micro-structural measurements were refined and are applied to a reference block rejected by the manufacturer during fabrication in order to evaluate the effect of metallurgical condition on block response. New fabrication techniques for reference blocks are discussed and ASTM activities are summarized.

Eitzen, D. G.↗

Nonlinear beam kinematics for small strains and finite rotations

A simple matrix expression is obtained for the strain components of a beam in which the magnitudes of neither beam displacements nor rotations are explicitly restricted. The only kinematical restrictions are that: (1) strains are small compared to unity and (2) components of local rotation, a newly identified kinematical quantity, are of the order of the strains to a fractional power equal to at least one half. Local rotations are defined as the change of orientation of material elements off the beam reference axis relative to those on the beam reference axis. Local rotations appear explicitly in the resulting strain expressions, facilitating the treatment of both open- and closed-section beams in applications of the theory. The resulting strain components are expressed in a local Cartesian coordinate system and can be calculated directly in that way. Thus, one can use a curvilinear coordinate system that is natural to the beam problem without the complications that usually surround such an approach. Examples show the simplicity and the generality of the present approach as well as why previously published results differ among themselves concerning tension-torsion coupling.

Hodges, Dewey H.↗

Solar flare gamma-ray and hard x ray imaging with the GRID-on-a-balloon

A primary scientific objective for solar flare research during the rapidly approaching maximum in solar activity is the imaging of gamma-ray and hard x ray sources of solar flare emissions. These goals will be pursued by the Gamma Ray Imaging Device (GRID) instrument, one of three instruments recently selected for NASA's Max '91 Solar Balloon Program. The GRID instrument is based on the technique of Fourier transform imaging and utilizes scanning modulation grid collimator optics to provide full-Sun imaging with 1.9-arcsecond resolution over the energy range from 20 to 700 keV at time resolutions from 0.1 to 2 s. The GRID telescope will employ 32 subcollimators, each composed of a matched pair of high-Z collimator grids separated by 5.2 meters and a phoswich scintillation spectrometer detector having no spatial resolution. The subcollimators and integrally-mounted fine aspect system are contained within a telescope canister which will be pointed to 0.1 degree accuracy and cyclically scanned to produce source modulation. The 32 subcollimators provide a uniform distribution of grid slit orientations and a logarithmic distribution of slit spacings corresponding to angular dimensions of 1.9 arcseconds to several arcminutes. The instrument is several orders of magnitude more sensitive than the HXIS instrument on the Solar Maximum Mission (SMM) and nearly 10 times more sensitive than any similar instrument scheduled to fly during the next solar maximum. The payload, designed for long-duration high-altitude balloon capability, is scheduled for its first science flight (8 to 14 days duration) from the Antarctic in January of 1992.

Orwig, Larry E.↗

Accelerated Strength Testing of Thermoplastic Composites

Constant ramp strength tests on unidirectional thermoplastic composite specimens oriented in the 90 deg. direction were conducted at constant temperatures ranging from 149 C to 232 C. Ramp rates spanning 5 orders of magnitude were tested so that failures occurred in the range from 0.5 sec. to 24 hrs. (0.5 to 100,000 MPa/sec). Below 204 C, time-temperature superposition held allowing strength at longer times to be estimated from strength tests at shorter times but higher temperatures. The data indicated that a 50% drop in strength might be expected for this material when the test time is increased by 9 orders of magnitude. The shift factors derived from compliance data applied well to the strength results. To explain the link between compliance and strength, a viscoelastic fracture model was investigated. The model, which used compliance as input, was found to fit the strength data only if the critical fracture energy was allowed to vary with temperature reduced stress rate. This variation in the critical parameter severely limits its use in developing a robust time-dependent strength model. The significance of this research is therefore seen as providing both the indication that a more versatile acceleration method for strength can be developed and the evidence that such a method is needed.

Reeder, J. R.↗

Interfacial control of oxygen vacancy doping and electrical conduction in thin film oxide heterostructures

Systems and methods of reversibly controlling the oxygen vacancy concentration and distribution in oxide heterostructures consisting of electronically conducting In2O3 films grown on ionically conducting Y2O3-stabilized ZrO2 substrates. Oxygen ion redistribution across the heterointerface is induced using an applied electric field oriented in the plane of the interface, resulting in controlled oxygen vacancy (and hence electron) doping of the film and possible orders-of-magnitude enhancement of the film's electrical conduction. The reversible modified behavior is dependent on interface properties and is attained without cation doping or changes in the gas environment in contact with the sample.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Toward Realistic Dynamics of Rotating Orbital Debris, and Implications for Lightcurve Interpretation

Optical observations of rotating space debris near GEO contain important information on size, shape, composition, and rotational states, but these aspects are difficult to extract due to data limitations and the high number of degrees of freedom in the modeling process. For tri-axial rigid debris objects created by satellite fragmentations, the most likely initial rotation state has a large component of initial angular velocity directed along the intermediate axis of inertia, leading to large angular reorientations of the body on the timescale of the rotation period. This lends some support to the simplest possible interpretation of light curves -- that they represent sets of random orientations of the objects of study. However, effects of internal friction and solar radiation are likely to cause significant modification of rotation states within a time as short as a few orbital periods. In order to examine the rotational dynamics of debris objects under the influences of these effects, a set of seven first-order coupled equations of motion were assembled in state form: three are Euler equations describing the rates of change of the components of angular velocity in the body frame, and four describe the rates of change of the components of the unit quaternion. Quaternions are a four-dimensional extension of complex numbers that form a seamless, singularity-free representation of body orientation on S3. The Euler equations contain explicit terms describing torque from solar radiation in terms of spherical harmonics, and terms representing effects of a prescribed rate of internal friction. Numerical integrations of these equations of motion are being performed, and results will be presented. Initial tests show that internal friction without solar radiation torque leads to rotation about the maximum principal axis of inertia, as required, and solar radiation torque is expected to lead to spin-up of objects. Because the axis of maximum rotational inertia tends to be roughly coincident with the normal to the largest projected cross-sectional area, internal friction is expected to lead to reduced variation of light curve amplitudes at a given phase angle, but a large dependence of the same on phase angle. At a given phase angle, databases are generated which contain reflected intensities for comprehensive sets of equally-likely orientations, represented as unit quaternions. When projected onto three dimensions (S2) and color-coded by intensity, the set is depicted as points within a solid, semi-transparent unit sphere, within which all possible reflected intensities for an object at a given phase angle may be inspected simultaneously. Rotational sequences are represented by trajectories through the sphere. Databases are generated for each of a set of phase angles separately, forming a comprehensive dataset of reflected intensities spanning all object orientations and solar phase angles. Symmetries in the problem suggest that preferred rotation states are likely, defined relative to the object-sun direction in inertial space and relative to the maximum principal axis of inertia in the body coordinate system. Such rotation states may greatly simplify the problem of light curve interpretation by reducing the number of degrees of freedom in the problem.

Ojakangas, Gregory W.↗

Testing for pair density wave order in La 1.875 Ba 0.125 CuO 4

We report charge order is commonly believed to compete with superconducting order. An intertwined form of a superconducting wave function, known as pair density wave (PDW) order, has been proposed; however, direct evidence, theoretical or experimental, that it forms the ground state of any cuprate superconductor is lacking. As a test case, we consider La 2-x Ba x CuO 4 with x = 1/8, where charge and spin stripe orders within the CuO 2 planes compete with three-dimensional superconducting order. We report measurements of the superconducting critical current perpendicular to the planes in the presence of an in-plane magnetic field. The variation of the critical current with orientation of the field is inconsistent with a theoretical prediction specific to the PDW model. It appears, instead, that the orientation dependence of the critical-current density might be determined by a minority phase of d-wave superconductivity that is present as a consequence of doped-charge inhomogeneity.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Implementation of Field-Oriented Control in Joint Actuator Electronics for Satellite-Servicing Robotics

NASA’s OSAM-1 (On-orbit Servicing, Assembly, and Manufacturing 1) is a robotic spacecraft designed to extend the life of a satellite. Launching in 2026, the OSAM-1 servicer will use a robotic arm to grasp, refuel, and relocate Landsat 7. In order to accomplish the various servicing operations, including the critical auto-grapple capturing operation, the robot arm uses active compliance and visual servo control loops. These sophisticated control algorithms are enabled by the high performance Joint Control Boards (JCBs). At the core of the robot arm control architecture, the JCBs employ field-oriented control (FOC) to accurately commutate and efficiently control joint actuator torque. FOC offers numerous benefits over other current control methods, allowing the JCBs to achieve the high bandwidth and performance required by the outer control loops. As an added benefit, a torque feed-forward term allows the FOC loop to simulate microgravity actuator performance during ground testing. In this paper, a FOC implementation for space robotics applications and an end-to-end actuator calibration process are discussed.

Sam Zhao↗