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At least 37 records · Page 2

Phase-Controlled Synthesis of Pd–Sn Nanocrystal Catalysts of Defined Size and Shape

Bimetallic Pd-based nanoparticles (NPs) are of interest as electrocatalysts for formic acid electrooxidation (FAEO) because of their higher initial catalytic activity and CO tolerance when compared to Pt. Intermetallic NPs (i-NPs) with specific geometric and electronic structures generally exhibit superior catalytic activity, selectivity, and durability when compared to their disordered (random alloy) counterparts; however, the colloidal synthesis of i-NPs remains a challenge. Here, a one-pot method was demonstrated as a facile route to obtain monodisperse Pd–Sn NPs with phase control, including intermetallic hexagonal Pd 3 Sn 2 (P6 3 /mmc), intermetallic orthorhombic Pd 2 Sn (Pnma), and alloy cubic Pd 3 Sn (FCC, Fm 3 ¯m) as size-controlled NPs with quasi-spherical shapes. Initial metal precursor ratios and reaction temperature were critical parameters to achieving phase control. Also, slight modifications of synthetic conditions resulted in either Pd 2 Sn nanorhombohedra or nanorods with tunable aspect ratios. A systematic evaluation of the Pd–Sn NPs for FAEO showed that most presented higher specific activities when compared to commercial Pd/C, in which Pd 2 Sn quasi-spheres and nanorhombohedra showed the highest catalytic activity for FAEO. Furthermore, these results highlight the benefits of phase-controlled Pd-based nanocatalysts with defined nanocrystal size and shape, with use of trioctylphospine (TOP) and oleic acid (OA) central to shape and size control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Position control of redundant manipulators using an adaptive error-based control scheme

A Cartesian-space control scheme is developed to control the motion of kinematically redundant manipulators with 7 degrees of freedom (DOF). The control scheme consists mainly of proportional derivative (PD) controllers whose gains are adjusted by an adaptation law driven by the errors between the desired and actual trajectories. The adaptation law is derived using the concept of model reference adaptive control (MRAC) and Lyapunov direct method under the assumption that the manipulator performs non-compliant and slowly-varying motions. The developed control scheme is computationally efficient because its implementation does not require the computation of the manipulator dynamics. Computer simulation performed to evaluate the control scheme performance is presented and discussed.

Nguyen, Charles C.↗

A single-axis testbed for slewing control experiments

A simple single-axis testbed is described, and initial experimental results are presented to illustrate collocated and noncollocated control for this structure. The testbed is made up of a pair of single-axis flexible beams attached to a DC servo motor. An optical encoder and strain gauges provide hub and beam position information, respectively. The system is driven by an IBM PC system; with a motor controller, a programmable digital filter processes position error information through user-selected gains and pole-zero configurations. A 25-kHz data acquisition system provides the necessary interface between processor and motor. The control approaches currently being investigated include collocated PD control and noncollocated phase compensation.

Hamilton, Jonathan↗

A computationally efficient error-based adaptive control scheme for kinematically redundant manipulators

A Cartesian-space control scheme is developed to control the motion of kinematically redundant manipulators with 7 degrees of freedom (DOF). The control scheme consists mainly of proportional-derivative (PD) controllers whose gains are adjusted by an adaptation law driven by the errors between the desired and actual trajectories. The adaptation law is derived using the concept of model reference adaptive control (MRAC) and Liapunov direct method under the assumption that the manipulator performs noncompliant and slowly-varying motions. The developed control scheme is computationally efficient because its implementation does not require the computation of the manipulator dynamics. Computer simulation performed to evaluate the control scheme performance is presented and discussed.

Nguyen, Charles C.↗

Solvent manipulation of the pre-reduction metal–ligand complex and particle-ligand binding for controlled synthesis of Pd nanoparticles

Understanding how to control the nucleation and growth rates is crucial for designing nanoparticles with specific sizes and shapes. Herein, we show that the nucleation and growth rates are correlated with the thermodynamics of metal–ligand/solvent binding for the pre-reduction complex and the surface of the nanoparticle, respectively. To obtain these correlations, we measured the nucleation and growth rates by in situ small angle X-ray scattering during the synthesis of colloidal Pd nanoparticles in the presence of trioctylphosphine in solvents of varying coordinating ability. The results show that the nucleation rate decreased, while the growth rate increased in the following order, toluene, piperidine, 3,4-lutidine and pyridine, leading to a large increase in the final nanoparticle size (from 1.4 nm in toluene to 5.0 nm in pyridine). Using density functional theory (DFT), complemented by 31 P nuclear magnetic resonance and X-ray absorption spectroscopy, we calculated the reduction Gibbs free energies of the solvent-dependent dominant pre-reduction complex and the solvent-nanoparticle binding energy. The results indicate that lower nucleation rates originate from solvent coordination which stabilizes the pre-reduction complex and increases its reduction free energy. At the same time, DFT calculations suggest that the solvent coordination affects the effective capping of the surface where stronger binding solvents slow the nanoparticle growth by lowering the number of active sites (not already bound by trioctylphosphine). The findings represent a promising advancement towards understanding the microscopic connection between the metal–ligand thermodynamic interactions and the kinetics of nucleation and growth to control the size of colloidal metal nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental investigation of adaptive control of a parallel manipulator

The implementation of a joint-space adaptive control scheme used to control non-compliant motion of a Stewart Platform-based Manipulator (SPBM) is presented. The SPBM is used in a facility called the Hardware Real-Time Emulator (HRTE) developed at Goddard Space Flight Center to emulate space operations. The SPBM is comprised of two platforms and six linear actuators driven by DC motors, and possesses six degrees of freedom. The report briefly reviews the development of the adaptive control scheme which is composed of proportional-derivative (PD) controllers whose gains are adjusted by an adaptation law driven by the errors between the desired and actual trajectories of the SPBM actuator lengths. The derivation of the adaptation law is based on the concept of model reference adaptive control (MRAC) and Lyapunov direct method under the assumption that SPBM motion is slow as compared to the controller adaptation rate. An experimental study is conducted to evaluate the performance of the adaptive control scheme implemented to control the SPBM to track a vertical and circular paths under step changes in payload. Experimental results show that the adaptive control scheme provides superior tracking capability as compared to fixed-gain controllers.

Nguyen, Charles C.↗

Dynamic control modification techniques in teleoperation of a flexible manipulator

The objective of this research is to reduce the end-point vibration of a large, teleoperated manipulator while preserving the usefulness of the system motion. A master arm is designed to measure desired joint angles as the user specifies a desired tip motion. The desired joint angles from the master arm are the inputs to an adaptive PD control algorithm that positions the end-point of the manipulator. As the user moves the tip of the master, the robot will vibrate at its natural frequencies which makes it difficult to position the end-point. To eliminate the tip vibration during teleoperated motions, an input shaping method is presented. The input shaping method transforms each sample of the desired input into a new set of impulses that do not excite the system resonances. The method is explained using the equation of motion for a simple, second-order system. The impulse response of such a system is derived and the constraint equations for vibrationless motion are presented. To evaluate the robustness of the method, a different residual vibration equation from Singer's is derived that more accurately represents the input shaping technique. The input shaping method is shown to actually increase the residual vibration in certain situations when the system parameters are not accurately specified. Finally, the implementation of the input shaping method to a system with varying parameters is shown to induce a vibration into the system. To eliminate this vibration, a modified command shaping technique is developed. The ability of the modified command shaping method to reduce vibration at the system resonances is tested by varying input perturbations to trajectories in a range of possible user inputs. By comparing the frequency responses of the transverse acceleration at the end-point of the manipulator, the modified method is compared to the original PD routine. The control scheme that produces the smaller magnitude of resonant vibration at the first natural frequency is considered the more effective control method.

Magee, David Patrick↗

WE-G-BRF-09: Force- and Image-Adaptive Strategies for Robotised Placement of 4D Ultrasound Probes

Purpose: To allow continuous acquisition of high quality 4D ultrasound images for non-invasive live tracking of tumours for IGRT, image- and force-adaptive strategies for robotised placement of 4D ultrasound probes are developed and evaluated. Methods: The developed robotised ultrasound system is based on a 6-axes industrial robot (adept Viper s850) carrying a 4D ultrasound transducer with a mounted force-torque sensor. The force-adaptive placement strategies include probe position control using artificial potential fields and contact pressure regulation by a PD controller strategy. The basis for live target tracking is a continuous minimum contact pressure to ensure good image quality and high patient comfort. This contact pressure can be significantly disturbed by respiratory movements and has to be compensated. All measurements were performed on human subjects under realistic conditions. When performing cardiac ultrasound, rib- and lung shadows are a common source of interference and can disrupt the tracking. To ensure continuous tracking, these artefacts had to be detected to automatically realign the probe. The detection is realised by multiple algorithms based on entropy calculations as well as a determination of the image quality. Results: Through active contact pressure regulation it was possible to reduce the variance of the contact pressure by 89.79% despite respiratory motion of the chest. The results regarding the image processing clearly demonstrate the feasibility to detect image artefacts like rib shadows in real-time. Conclusion: In all cases, it was possible to stabilise the image quality by active contact pressure control and automatically detected image artefacts. This fact enables the possibility to compensate for such interferences by realigning the probe and thus continuously optimising the ultrasound images. This is a huge step towards fully automated transducer positioning and opens the possibility for stable target tracking in ultrasoundguided radiation therapy requiring contact pressure of 5–10 N. This work was supported by the Graduate School for Computing in Medicine and Life Sciences funded by Germany's Excellence Initiative [DFG GSC 235/1].

60 APPLIED LIFE SCIENCES↗

Design of an adaptive controller for a telerobot manipulator

The design of a joint-space adaptive control scheme is presented for controlling the slave arm motion of a dual-arm telerobot system developed at Goddard Space Flight Center (GSFC) to study telerobotic operations in space. Each slave arm of the dual-arm system is a kinematically redundant manipulator with 7 degrees of freedom (DOF). Using the concept of model reference adaptive control (MRAC) and Lyapunov direct method, an adatation algorithm is derived which adjusts the PD controller gains of the control scheme. The development of the adaptive control scheme assumes that the slave arm motion is non-compliant and slowly-varying. The implementation of the derived control scheme does not need the computation of the manipulator dynamics, which makes the control scheme sufficiently fast for real-time applications. Computer simulation study performed for the 7-DOF slave arm shows that the developed control scheme can efficiently adapt to sudden change in payloads while tracking various test trajectories such as ramp or sinusoids with negligible position errors.

Nguyen, Charles C.↗

Joint-space Lyapunov-based direct adaptive control of a kinematically redundant telerobot manipulator

This paper presents the design of a joint-space adaptive control scheme for controlling the slave arm motion of a dual-arm telerobot system developed at Goddard Space Flight Center (GSFC) to study telerobotic operations in space. Each slave arm of the dual-arm system is a kinematically redundant manipulator with seven degrees of freedom (DOF). Using the concept of model reference adaptive control (MRAC) and Liupunov direct method, we derive an adaptation algorithm that adjusts the PD controller gains of the control scheme. The development of the adaptive control scheme assumes that the slave arm motion is non-compliant and slowly varying. The implementation of the derived control scheme does not require the computation of manipulator dynamics which makes the control scheme sufficiently fast for real-time applications. Computer simulation study performed for the 7-DOF slave arm shows that the developed control scheme can efficiently adapt to sudden change in payload while tracking various test trajectories such as ramp or sinusoids with negligible position errors.

Nguyen, Charles C.↗

Regulating the Catalytic Activity of Pd Nanoparticles by Confinement in Ordered Mesoporous Supports

Studying structure-sensitive reactions requires the synthesis of catalytic nanoparticles with precisely controlled sizes. Here we demonstrate the facile production of size controlled Pd nanoparticles by confinement in the pores of mesoporous silica nanoparticles (MSN). We show that Pd particles 2.1 nm in size have a higher catalytic activity than larger nanoparticles for the Suzuki-Miyaura cross coupling between 4’-bromoacteophenone and phenyl boronic acid and for the hydrogenation of phenol in aqueous phase. The enhanced activity can be explained in terms of increased number of coordinatively unsaturated sites and higher back donation capacity of the small nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Determination of Site Occupancy in the M–Pd–Zn (M = Cu, Ag, and Au) γ-Brass Phase by CALculation of PHAse Diagrams Modeling and Rietveld Refinement

The Pd–Zn γ-brass phase provides exciting opportunities for synthesizing site-isolated catalysts with precisely controlled Pd active site ensembles. Introducing a third metallic element into the γ-brass lattice further perturbs the catalytic active site ensembles. Here, in this work, we introduce coinage metallic elements M (M = Cu, Ag, and Au) into the Pd–Zn γ-brass phase and investigate the site occupation factors of each element in the γ-brass lattice. The CALculation of PHAse Diagrams (CALPHAD) modeling approach supported by energetics predicted by the density functional theory and X-ray and neutron diffraction with Rietveld refinement were used to identify the SOF on each Wyckoff site for various M amounts alloyed into the Pd–Zn γ-brass phase. The present analysis unveils the strong preference for Pd occupying the outer tetrahedral (OT) site in the γ-brass lattice, while the coinage metallic elements tend to substitute for Zn on the octahedral (OH) site. The determination of site occupancy in the bulk M–Pd–Zn γ-brass phase provides opportunities to investigate and tailor potential catalytically active site ensembles in the γ-brass phase materials.

36 MATERIALS SCIENCE↗

Robust tuning of robot control systems

The computed torque control problem is examined for a robot arm with flexible, geared, joint drive systems which are typical in many industrial robots. The standard computed torque algorithm is not directly applicable to this class of manipulators because of the dynamics introduced by the joint drive system. The proposed approach to computed torque control combines a computed torque algorithm with torque controller at each joint. Three such control schemes are proposed. The first scheme uses the joint torque control system currently implemented on the robot arm and a novel form of the computed torque algorithm. The other two use the standard computed torque algorithm and a novel model following torque control system based on model following techniques. Standard tasks and performance indices are used to evaluate the performance of the controllers. Both numerical simulations and experiments are used in evaluation. The study shows that all three proposed systems lead to improved tracking performance over a conventional PD controller.

Minis, I.↗

Control-structure interaction in precision pointing servo loops

The control-structure interaction problem is addressed via stability analysis of a generic linear servo loop model. With the plant described by the rigid body mode and a single elastic mode, structural flexibility is categorized into one of three types: (1) appendage, (2) in-the-loop minimum phase, and (3) in-the-loop nonminimum phase. Closing the loop with proportional-derivative (PD) control action and introducing sensor roll-off dynamics in the feedback path, stability conditions are obtained. Trade studies are conducted with modal frequency, modal participation, modal damping, loop bandwidth, and sensor bandwidth treated as free parameters. Results indicate that appendage modes are most likely to produce instability if they are near the sensor rolloff, whereas in-the-loop modes are most dangerous near the loop bandwidth. The main goal of this paper is to provide a fundamental understanding of the control-structure interaction problem so that it may benefit the design of complex spacecraft and pointing system servo loops. In this framework, the JPL Pathfinder gimbal pointer is considered as an example.

Spanos, John T.↗

Synthesis of Supported Pd 0 Nanoparticles from a Single-Site Pd 2+ Surface Complex by Alkene Reduction

Here, a surface metal–organic complex, (-AlO x )Pd(acac) (acac = acetylacetonate), is prepared by chemically grafting the precursor Pd(acac) 2 onto γ-Al 2 O 3 in toluene at 25 °C. The resulting surface complex is characterized by inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), and dynamic nuclear polarization surface-enhanced solid-state nuclear magnetic resonance spectroscopy (DNP SENS). This surface complex is a precursor in the direct synthesis of size-controlled Pd nanoparticles under mild reductive conditions and in the absence of additional stabilizers or pretreatments. Indeed, upon exposure to gaseous ethylene or liquid 1-octene at 25 °C, the Pd 2+ species is reduced to form Pd 0 nanoparticles with a mean diameter of 4.3 ± 0.6 nm, as determined by scanning transmission electron microscopy (STEM). These nanoparticles are catalytically relevant using the aerobic 1-phenylethanol oxidation as a probe reaction, with rates comparable to a conventional Pd/Al 2 O 3 catalyst but without an induction period. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reaction mass spectrometry (TPR-MS) reveal that the surface complex reduction with ethylene coproduces H 2 , acetylene, and 1,3-butadiene. This process reasonably proceeds via an olefin activation/coordination/insertion pathway, followed by β-hydride elimination to generate free Pd 0 . Lastly, the well-defined nature of the single-site supported Pd 2+ precursor provides direct mechanistic insights into this unusual and likely general reductive process.

36 MATERIALS SCIENCE↗

Space Shuttle Upgrades Advanced Hydraulic Power System

Three Auxiliary Power Units (APU) on the Space Shuttle Orbiter each provide 145 hp shaft power to a hydraulic pump which outputs 3000 psi hydraulic fluid to 41 hydraulic actuators. A hydrazine fuel powered APU utilized throughout the Shuttle program has undergone many improvements, but concerns remain with flight safety, operational cost, critical failure modes, and hydrazine related hazards. The advanced hydraulic power system (AHPS), also known as the electric APU, is being evaluated as an upgrade to replace the hydrazine APU. The AHPS replaces the high-speed turbine and hydrazine fuel supply system with a battery power supply and electric motor/pump that converts 300 volt electrical power to 3000 psi hydraulic power. AHPS upgrade benefits include elimination of toxic hydrazine propellant to improve flight safety, reduction in hazardous ground processing operations, and improved reliability. Development of this upgrade provides many interesting challenges and includes development of four hardware elements that comprise the AHPS system: Battery - The battery provides a high voltage supply of power using lithium ion cells. This is a large battery that must provide 28 kilowatt hours of energy over 99 minutes of operation at 300 volts with a peak power of 130 kilowatts for three seconds. High Voltage Power Distribution and Control (PD&C) - The PD&C distributes electric power from the battery to the EHDU. This 300 volt system includes wiring and components necessary to distribute power and provide fault current protection. Electro-Hydraulic Drive Unit (EHDU) - The EHDU converts electric input power to hydraulic output power. The EHDU must provide over 90 kilowatts of stable, output hydraulic power at 3000 psi with high efficiency and rapid response time. Cooling System - The cooling system provides thermal control of the Orbiter hydraulic fluid and EHDU electronic components. Symposium presentation will provide an overview of the AHPS upgrade, descriptions of the four hardware elements, and a summary of development results to date.

Source record↗

A balancing act: manipulating reactivity of shape-controlled metal nanocatalysts through bimetallic architecture

Manipulating the electronic structure of metal nanocrystals is one way of altering their catalytic activities. This ability is demonstrated by introducing a Au interior to shape-controlled Pd nanocrystals, producing core@shell Au@Pd nanoparticles with varying shell thicknesses. As revealed by X-ray photoelectron spectroscopy, the electronic structure of the Pd shell depends on its thickness. These core@shell nanocrystals were used to catalyze two model reactions: selective hydrogenation of 2-hexyne and oxidation of formic acid, where different reactivities were found also as a function of shell thickness. The comparison of particles with varying bimetallic architecture but identical geometric features provides insight into how electronic regulation in a catalytic reaction can be achieved. Finally, it is concluded that a balance in binding interaction between the molecular substrate and catalyst surface is necessary to design an efficient catalyst and can be achieved with shape-controlled core@shell nanocrystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Colloidal Synthesis of Palladium Nanocluster‐Decorated Cs 3 Sb 2 Cl 9 Perovskite Heterostructural Nanorods for Enhanced CO 2 Photoreduction

Developing efficient and sustainable photocatalysts for CO 2 reduction remains a significant challenge, particularly with environmentally benign materials. Here, in this study, we report the first one-step synthesis of metal–lead-free perovskite heterostructural nanocrystals by decorating Cs 3 Sb 2 Cl 9 perovskite nanorods with size-controlled Pd nanoclusters via a one-step hot-injection method. The resulting Pd-Cs 3 Sb 2 Cl 9 heteronanorods (HNRs) exhibit strong interfacial electronic coupling, enhanced charge separation, and excellent colloidal stability. Transient absorption spectroscopy and DFT calculations reveal a built-in electric field that drives directional electron transfer from the perovskite host to the Pd domains. Under UV irradiation, the Pd-Cs 3 Sb 2 Cl 9 HNRs demonstrate excellent CO 2 photoreduction activity with high CH 4 selectivity, achieving a record apparent quantum yield (AQY) of 2.62% among halide perovskite nanocrystal-based systems with a large electronic yield of 689.3 ± 12.2 µmol·g cat −1 . In situ spectroscopic monitoring and Gibbs free energy analysis further unveil a Pd-facilitated reaction pathway involving stabilization of key intermediates. This work introduces a new class of lead-free perovskite-based heterostructures through a facile one-step synthesis strategy and offers a new design principle for next-generation photocatalysts for solar fuel production.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗