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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

WBG-Enabled Current-Source Inverters for Integrated PM Motor Drives

This project takes advantage of the special capabilities of wide-bandgap (WBG) power semiconductor devices to develop innovative power electronics in the form of new current-source inverters (CSIs) that offer promising advantages over the dominant voltage-source inverter (VSI) topology. These CSIs, in turn, are extremely well-suited for integration into the housings of permanent magnet synchronous machines (PMSMs) to form integrated motor drives (IMDs). These new IMDs offer great promise for achieving major energy savings in a wide variety of applications that benefit from adjustable-speed control, including air conditioners, laundry appliances, industrial pumps/compressors, electric vehicles, and aerospace drives. WBG devices play a critical enabling role in these new IMDs because of their transformative features including much higher switching frequencies, lower losses, and compatibility with high operating temperatures. When incorporated into new CSI-based IMDs with PM machines, these WBG switches open the door to achieving major increases in power density, drive system efficiency, and fault tolerance, as well as substantial reductions in electromagnetic interference (EMI), manufacturing cost, and temperature-induced failures. The higher operating temperature capability of WBG devices compared to conventional silicon power devices is very appealing in IMD applications because the power electronics is mounted in close proximity to the motors which typically operate at temperatures well above the maximum limits of today’s silicon-based power electronics. This project has succeeded in designing, building, and testing multiple prototype versions of this CSI-IMD that have overcome many technical challenges in order to demonstrate the impressive performance improvements that can be achieved by the WBG-enabled CSI-IMD. The preliminary demo and bench-top versions of the current-source inverter developed during the first two years of the project were critical to laying the technical foundations for the 3 kW prototype CSI-IMD unit that was successfully built and tested during the third year. This prototype CSI-IMD unit was designed to fit within the housing envelope of the original permanent magnet (PM) synchronous machine in order to meet the demanding power density requirements that were set at the beginning of the project. All of the remaining performance objectives set for the prototype CSI-IMD unit including efficiency and electromagnetic interference (EMI) were also met. The last 18 months of the project were devoted to developing further enhancements of the WBG-enabled CSI-IMD technology that better prepare it for commercial production. More specifically, an upgraded version of the prototype CSI-IMD unit was developed that moved the power electronics into the same machine housing chamber as the motor, substantially raising the thermal demands on the power electronics. Tests with five different combinations of motor enclosure types and air cooling configurations were evaluated. Importantly, this work confirmed that the power electronics can deliver its full rated power and still operate well within its maximum temperature limits even for worst-case conditions when the housing is “totally-enclosed” without any openings for air to enter or exit the enclosure, and no blower/fan is provided to blow air over the outside surface of the enclosure. Reaching the full performance and energy-savings potential of this disruptive CSI-IMD motor drive technology is highly consistent with ARPA-E’s stated mission to “enhance the economic and energy security of the United States” while also supporting its commitment to “ensure that the U.S. maintains a technological lead in developing and deploying advanced energy technologies”. Follow-on projects are under way to explore the scalability of WBG-enabled CSI-IMD technology to 100 kW (peak) electric vehicle traction drives and fault-tolerant modular motor drives for future electrified aircraft propulsion applications.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2021

Improvements to the Powder Processing of near-Final Shape alnico Magnets

Alnico permanent magnets (PMs), a recent PM system of interest as an attractive rare earth-free PM alternative, have advantageous high operating temperature and magnetic saturation with the potential for utilization in electric machines, e.g. interior-PM motors found in electric vehicles, if current directional solidification methods can be replaced by a true mass production approach. Recently, two unique alnico compositions, termed Full-Co and Co-lean, with improved coercivity, were gas atomized, compression molded, and vacuum sintered (4h at 1240°C) to high densities of 97.8% and 99.3%, respectively. However, the Co-lean remained fine grained isotropic magnets and the Full-Co grains were not textured, lowering magnetic strength in spite of attempts to grow large textured grains by a stress-biased solid state grain alignment method to convert them to high energy anisotropic magnets. It was hypothesized that oxidation during de-binding in air left many prior particle boundary oxides within the sintered microstructure that hindered grain growth and texturing during the stress-biased texturing procedure and prevented the desired abnormal grain growth (AGG). Here we explored a vacuum de-binding step that was linked (in-place) to vacuum sintering and found that the Co-lean exhibited faster uniform grain growth that doubled the average grain size (40 μm to 80 μm). Linked vacuum de-binding and sintering of Full-Co produced some AGG after only 1 h of 1240°C sintering. A new direction for promoting AGG (and stress-biased texturing) in alnico is being explored that utilizes a fundamental analysis of systems with second phase particles that either inhibit or boost grain growth. This effort explores the influence of vacuum de-binding linked to a series of lower sintering temperatures at a fixed time (4h) to see if oxide particle size and volume fraction can be changed to promote AGG conditions in alnico. Surprising qualitative results indicate that AGG may be promoted for vacuum sintering at less than 1200°C.

Rinko, Emily↗
NASA NTRS1999

Deleterious Phase Formation in Next- Generation Nickel-Base Superalloys Predicted

Nickel- (Ni-) base superalloy single crystals represent the state-of-the-art for turbine engine airfoil applications because they offer the best balance of properties under the high operating temperatures required for efficient engine operation. Current trends in alloy design take advantage of improved creep rupture strength with the addition of higher levels of refractory elements. In particular, the addition of significantly higher levels of rhenium in third-generation superalloys is key for both microstructural stability and creep rupture strength. Although refractories provide strength benefits, alloys tend to be unstable when their refractory content is high because of topologically close-packed (TCP) phases. The formation of these phases in sufficient amount is detrimental to the performance of these alloys because of their brittle nature and because they deplete the Nirich matrix of potent solid-solution strengthening elements.

Ritzert, Frank J.↗
NASA NTRS1987

Joining of ceramics for high temperature applications

Summarized is a literature survey of the methods for joining ceramics to ceramics or ceramics to metals for high temperature applications. Also mechanical properties and potential applications of the joints are considered. The joining of ceramics is usually carried out by brazing or diffusion bonding. Especially the latter has been found useful, increasing the application of bonded ceramics. The possibility of using electron beam and laser beam welding for joining ceramics has also recently been investigated. The bonding of ceramics has found numerous applications typical for high operating temperatures, i.e., sensors and thermocouples.

Vilpas, Martti↗
NASA NTRS2008

Extreme High and Low Temperature Operation of the Silicon-On-Insulator Type CHT-OPA Operational Amplifier

A new operational amplifier chip based on silicon-on-insulator technology was evaluated for potential use in extreme temperature environments. The CHT-OPA device is a low power, precision operational amplifier with rail-to-rail output swing capability, and it is rated for operation between -55 C and +225 C. A unity gain inverting circuit was constructed utilizing the CHT-OPA chip and a few passive components. The circuit was evaluated in the temperature range from -190 C to +200 C in terms of signal gain and phase shift, and supply current. The investigations were carried out to determine suitability of this device for use in space exploration missions and aeronautic applications under wide temperature incursion. Re-restart capability at extreme temperatures, i.e. power switched on while the device was soaked at extreme temperatures, was also investigated. In addition, the effects of thermal cycling under a wide temperature range on the operation of this high performance amplifier were determined. The results from this work indicate that this silicon-on-insulator amplifier chip maintained very good operation between +200 C and -190 C. The limited thermal cycling had no effect on the performance of the amplifier, and it was able to re-start at both -190 C and +200 C. In addition, no physical degradation or packaging damage was introduced due to either extreme temperature exposure or thermal cycling. The good performance demonstrated by this silicon-on-insulator operational amplifier renders it a potential candidate for use in space exploration missions or other environments under extreme temperatures. Additional and more comprehensive characterization is, however, required to establish the reliability and suitability of such devices for long term use in extreme temperature applications.

Patterson, Richard↗
NASA NTRS2008

Silicon-On-Insulator (SOI) Devices and Mixed-Signal Circuits for Extreme Temperature Applications

Electronic systems in planetary exploration missions and in aerospace applications are expected to encounter extreme temperatures and wide thermal swings in their operational environments. Electronics designed for such applications must, therefore, be able to withstand exposure to extreme temperatures and to perform properly for the duration of the missions. Electronic parts based on silicon-on-insulator (SOI) technology are known, based on device structure, to provide faster switching, consume less power, and offer better radiation-tolerance compared to their silicon counterparts. They also exhibit reduced current leakage and are often tailored for high temperature operation. However, little is known about their performance at low temperature. The performance of several SOI devices and mixed-signal circuits was determined under extreme temperatures, cold-restart, and thermal cycling. The investigations were carried out to establish a baseline on the functionality and to determine suitability of these devices for use in space exploration missions under extreme temperatures. The experimental results obtained on selected SOI devices are presented and discussed in this paper.

Patterson, Richard↗
NASA NTRS2022

NASA Utilization of Space Nuclear Systems for Robotic and Human Exploration Missions: Response to EO 13972: Promoting Small Nuclear Reactors for National Defense and Space Exploration

Space Nuclear Systems (SNS) technology development offers a wide range of capabilities to support NASA’s current and future missions. Executive Order (EO) 13972, “Promoting Small Modular Reactors for National Defense and Space Exploration” [1], issued 5 January 2021, directs NASA to define requirements for NASA utilization of nuclear energy systems for human and robotic exploration missions through 2040 and analyze the costs and benefits of such requirements.” Although it is premature to define requirements and cost for future exploration missions that have not yet been formulated, this report describes planned objectives and missions by 2040 that are enabled or enhanced by nuclear systems while taking into account a number of unique considerations for nuclear energy in the space environment. Nuclear energy systems are enabling for space missions and critical capabilities where conventional forms of energy production are impractical or impossible due to mass constraints, mission duration, or distance from the Sun. Space nuclear technologies available or in development for use by 2040 utilize radioisotope decay or nuclear fission and fall into three categories: heat, power, and propulsion. Current applications utilize radioisotope power systems that provide consistent and reliable performance in the sub-kilowatt power range. More advanced SNS can enable new mission objectives where high energy density solutions are critical, or where access to solar solutions is prohibitive. Higher power radioisotope and fission systems are under development within NASA for a wide variety of human exploration and science mission applications. Planned missions designed to use radioisotope systems include Dragonfly, a rotorcraft that will explore the surface of Titan, and Persephone, a mission concept for a Pluto orbiter. Nuclear fission systems have the key advantage of providing significantly higher power, lower mass solutions from tens to even thousands of kilowatts. Fission power is enabling to a sustained human presence on the Moon and developing a robust lunar economy. Fission propulsion is enabling for missions within and beyond cis-lunar space. This report examines NASA-envisioned mission applications and associated performance needs for SNS over the next twenty years leading to 2040 along with the unique technical considerations posed by space nuclear technology development. This includes engineering and operational logistics for ground handling, thermal management, survival of the space environment, operational safety, power requirements, and service longevity. Safety to the public, the NASA work force, and agency assets remains a top priority for NASA and particular attention is given to this aspect in the design, hardware assembly, ground operation, launch, and mission operation of an SNS. NASA relies on the Department of Energy as nuclear authority and its legacy of rigorous safety procedures as standards for ground development, test, transportation, and launch site operation. The principal concern is preventing unintended radiological release to the public or environment. Radioisotope system experience has established processes, including ground operation, transportation, and launch, that are considered directly applicable to emerging fission systems; however, fission systems have unique design needs that impact the safety and performance requirements. High efficiency power conversion from both fission and radioisotope systems requires high operating temperatures necessitating both passive and active thermal management to maintain safe and nominal operating conditions. Effective cooling and waste heat rejection have special considerations for space applications, whether in zero-g or reduced gravity. Fluid and heat transfer within the reactor system is not anticipated to be impacted by reduced or zero-g environments. Cryogenic working fluids and propellant supplies utilized in some space nuclear applications will need low mass, high capacity cryocoolers to meet the long-term storage and near zero-boiloff needs. Integrated, high power density SNS capable of being packaged in a single vehicle is a key consideration for NASA. Due to concerns for complexity and reliability, in space reactor assembly and reactor refueling are not current design considerations. Expanding into a new era for space exploration depends on mass-efficient, high-energy solutions to power deep-space vehicles, operate in harsh environments, and increase mission flexibility. NASA nuclear technology investments are targeting power for surface operations and propulsion for fast-transit, deep-space missions, all with the ability to reliably operate without the need for repair or refueling. NASA’s goals, enabled by nuclear technologies, provide for exciting advances in scientific objectives and human exploration, ushering in a new space age that enables a human presence on bodies beyond our Earth.

nuclear↗
DOE OSTI2013

World first in high level waste vitrification - A review of French vitrification industrial achievements

AREVA has more than 30 years experience in operating industrial HLW (High Level radioactive Waste) vitrification facilities (AVM - Marcoule Vitrification Facility, R7 and T7 facilities). This vitrification technology was based on borosilicate glasses and induction-heating. AVM was the world's first industrial HLW vitrification facility to operate in-line with a reprocessing plant. The glass formulation was adapted to commercial Light Water Reactor fission products solutions, including alkaline liquid waste concentrates as well as platinoid-rich clarification fines. The R7 and T7 facilities were designed on the basis of the industrial experience acquired in the AVM facility. The AVM vitrification process was implemented at a larger scale in order to operate the R7 and T7 facilities in-line with the UP2 and UP3 reprocessing plants. After more than 30 years of operation, outstanding record of operation has been established by the R7 and T7 facilities. The industrial startup of the CCIM (Cold Crucible Induction Melter) technology with enhanced glass formulation was possible thanks to the close cooperation between CEA and AREVA. CCIM is a water-cooled induction melter in which the glass frit and the waste are melted by direct high frequency induction. This technology allows the handling of highly corrosive solutions and high operating temperatures which permits new glass compositions and a higher glass production capacity. The CCIM technology has been implemented successfully at La Hague plant.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS2009

Assessment of the State of the Art of Ultra High Temperature Ceramics

Ultra High Temperature Ceramics (UHTCs) are a family of materials that includes the borides, carbides and nitrides of hafnium-, zirconium- and titanium-based systems. UHTCs are famous for possessing some of the highest melting points of known materials. In addition, they are very hard, have good wear resistance, mechanical strength, and relatively high thermal conductivities (compared to other ceramic materials). Because of these attributes, UHTCs are ideal for thermal protection systems, especially those that require chemical and structural stability at extremely high operating temperatures. UHTCs have the potential to revolutionize the aerospace industry by enabling the development of sharp hypersonic vehicles or atmospheric entry probes capable of the most extreme entry conditions.

Johnson, Sylvia↗
DOE OSTI2025

Active and Stable PtPd Diesel Oxidation Catalysts under Industry‐Defined Test Protocols

Nanoparticle-supported Pt and Pd catalysts are employed industrially to convert CO and hydrocarbon residue from incomplete diesel fuel combustion into more environmentally-benign products. However, these catalysts deactivate over time due to sintering, especially for Pt nanoparticles which readily generate volatile species under high operating temperatures. Here, we turned the detrimental vapor-mediated sintering of Pt into an advantage by using a physical mixture of Pt and Pd catalysts prepared using a raspberry-colloid-templating (RCT) method. The RCT method produced Pt/Al 2 O 3 and Pd/Al 2 O 3 catalysts with partially embedded NPs to inhibit surface-mediated sintering pathways. As validated using an industry-defined emission control test protocol, aging a physical mixture of Pt/Al 2 O 3 and Pd/Al 2 O 3 at high temperature produced an alloyed PtPd/Al 2 O 3 catalyst that outperformed the fresh catalyst mixture and both individual catalysts for hydrocarbon conversion, while exhibiting high catalytic stability and resistance to sintering and to SO 2 poisoning. X-ray photoelectron spectroscopy revealed that in the aged catalyst mixture, half of the Pd content existed in the more active metallic state, compared to the less active oxide forms in the fresh mixture and both individual catalysts, explaining the unusual activity enhancement. Our results represent a practical approach to producing active and stable PtPd/Al 2 O 3 diesel oxidation catalysts for emission control applications.

Lim, Kang Rui Garrick [Harvard University, Cambrid↗
DOE OSTI2015

Fabrication of superconducting nanowires from ultrathin MgB{sub 2} films via focused ion beam milling

High quality superconducting nanowires were fabricated from ultrathin MgB{sub 2} films by a focused ion beam milling technique. The precursor MgB{sub 2} films in 10 nm thick were grown on MgO substrates by using a hybrid physical-chemical vapor deposition method. The nanowires, in widths of about 300-600 nm and lengths of 1 or 10 μm, showed high superconducting critical temperatures (T{sub c}’s) above 34 K and narrow superconducting transition widths (ΔT{sub c}’s) of 1-3 K. The superconducting critical current density J{sub c} of the nanowires was above 5 × 10{sup 7} A/cm{sup 2} at 20 K. The high T{sub c}, narrow ΔT{sub c}, and high J{sub c} of the nanowires offered the possibility of making MgB{sub 2}-based nano-devices such as hot-electron bolometers and superconducting nanowire single-photon detectors with high operating temperatures at 15-20 K.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Understanding failure in austenitic steels: Key considerations for molten salt storage in CSP applications

Owing to their excellent properties, austenitic stainless steels are extensively used in boilers, furnaces, molten salt tanks, and other applications that are subjected to extreme mechanical loads and high-temperature conditions. Their high corrosion and creep resistance make them suitable for high-temperature operating environments. Additionally, good fatigue resistance and favorable mechanical and visual properties are essential. However, the premature failure of several components at elevated temperatures has been previously reported. Although the failure analysis of components in service is complex, processes such as cold work and welding have been identified as contributing factors to the performance degradation of these steels. This study aims to analyze the various documented failure modes and mechanisms in austenitic steels, including creep, cracking, stress relaxation cracking, and fatigue, to better understand the multi-objective design requirements for these alloys as structural materials for high-temperature molten salt tanks in Concentrating Solar Power (CSP) plants. Stabilized austenitic grades, such as AISI 347H, demonstrate superior resistance to creep and corrosion-related degradation when compared to non-stabilized grades like AISI 316L at temperatures relevant to concentrated solar power (CSP) applications. In contrast, nickel-based alloys offer enhanced corrosion resistance, albeit at a higher cost. This review underscores that creep, stress relaxation cracking, and thermo-mechanical fatigue are the predominant long-term failure risks in CSP hot tanks.

14 SOLAR ENERGY↗
NASA NTRS2021

Ambient Performance Testing of the CubeSat Infrared Atmospheric Sounder (CIRAS)

Hyperspectral infrared measurements of Earth’s atmosphere from space have proven their value for weather forecasting, climate science and atmospheric composition. The CubeSat Infrared Atmospheric Sounder (CIRAS) instrument will demonstrate a fully functional infrared temperature, water vapor and carbon monoxide sounder in a CubeSat sized volume for at least an order of magnitude lower cost than legacy systems. Design for a CubeSat significantly reduces cost of access to space and enables flight in a constellation to reduce revisit time and enable new measurements including 3D winds. A technology demonstration of CIRAS is currently under development at JPL. The effort has completed integration and ambient testing of a high fidelity brassboard, complete with the flight configured optics assembly developed by Ball Aerospace with a JPL Immersion Grating and Black Silicon Entrance Slit. The brassboard includes a flight-configured High Operating Temperature Barrier Infrared Detector (HOT-BIRD) mounted in an Integrated Dewar Cryocooler Assembly (IDCA), enabling testing in the ambient environment. Ambient testing included radiometric testing of the system to characterize the instrument operability and NEdT. Spatial testing was performed to characterize the system line spread function (LSF) in two axes and report FWHM of the LSF. Spectral testing involved an air path test to characterize the spectral/spatial transformation matrix, and an etalon was used to measure the Spectral Response Functions (SRFs). Results of the testing show the CIRAS performs exceptionally well and meets the key performance required of the system. The end result of testing is the CIRAS instrument now meets TRL 4 with confidence in a brassboard configuration ready for thermal vacuum (TVac) testing necessary to achieve TRL 5 for the system.

Wilson, Robert C.↗
DOE OSTI2021

High performance protonic ceramic fuel cell systems for distributed power generation

The technology landscape around distributed generation continues to evolve in response to increasing demand for high-efficiency, low-emission, low-cost power generation. While emerging distributed power technologies, such as solid oxide fuel cells (SOFCs), continue to advance, they still face challenges due to their high capital costs, and shorter lifetimes that typically arise from electrochemical stack performance degradation at high operating temperatures (>750 °C). Recent advancements in protonic ceramic fuel cells (PCFCs) offer the potential to mitigate drawbacks of their higher temperature SOFC counterparts by enabling lower operating temperatures (550 °C–600 °C) with acceptable power densities. Here the present work leverages the recent progress in protonic ceramic cell and stack technology development to generate viable system configurations and evaluate the energetic performance potential of PCFC-based systems for stationary power generation. Process system engineering of two water-neutral system concepts, which provide 25 kW of electric power and process hot water, are presented and evaluated through sensitivity studies. Stack design parameters are altered and used to gauge the effect on system performance characteristics, including fuel cell stack and balance-of-plant sizing requirements, and electric and cogeneration efficiencies. The study finds that the potentially high per-pass fuel utilization capability of PCFC stacks could enable unprecedented electric efficiencies approaching 70% without hybridization with other prime movers.

25 ENERGY STORAGE↗
DOE OSTI2024

Fabrication of neutron absorbing metal hydride entrained ceramic matrix shield composites

With significant improvement in High Temperature Superconductors (HTS), several projects are adopting HTS technology for fusion power systems. Compact HTS tokamaks offer potential advantages including lower plant costs, enhanced plasma control, and ultimately lower cost of electricity. However, as compact reactors have a reduced radial build to accommodate shielding, HTS degradation due to radiation damage or heating is a significant and potentially design limiting issue. Shielding must mitigate threats to the superconducting coils: neutron cascade damage, heat deposition and potentially organic insulator damage due x-rays. Unfortunately, there are currently no hi-performance shielding materials to enable the potential performance enhancement offered by HTS. In this work, we present a manufacturing method to fabricate a new class of composite shields that are high performance, high operating temperature, and simultaneously neutron absorbing and neutron moderating. The composite design consists of an entrained metal-hydride phase within a radiation stable MgO ceramic host matrix. We discuss the fabrication, characterization, and thermophysical performance data for a series of down-selected composite materials inspired by future fusion core designs and their operational performance metrics. To our knowledge these materials represent the first ceramic composite shield materials containing significant metal hydrides.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1987

High-temperature electronics

In recent years, there was a growing need for electronics capable of sustained high-temperature operation for aerospace propulsion system instrumentation, control and condition monitoring, and integrated sensors. The desired operating temperature in some applications exceeds 600 C, which is well beyond the capability of currently available semiconductor devices. Silicon carbide displays a number of properties which make it very attractive as a semiconductor material, one of which is the ability to retain its electronic integrity at temperatures well above 600 C. An IR-100 award was presented to NASA Lewis in 1983 for developing a chemical vapor deposition process to grow single crystals of this material on standard silicon wafers. Silicon carbide devices were demonstrated above 400 C, but much work remains in the areas of crystal growth, characterization, and device fabrication before the full potential of silicon carbide can be realized. The presentation will conclude with current and future high-temperature electronics program plans. Although the development of silicon carbide falls into the category of high-risk research, the future looks promising, and the potential payoffs are tremendous.

Seng, Gary T.↗
DOE OSTI2017

The Influence of Phosphor and Binder Chemistry on the Aging Characteristics of Remote Phosphor Products

The influence of phosphor and binder layer chemistries on the lumen maintenance and color stability of remote phosphor disks were examined using wet high-temperature operational lifetime testing (WHTOL). As part of the experimental matrix, two different correlated color temperature (CCT) values, 2700 K and 5000 K, were studied and each had a different binder chemistry. The 2700 K samples used a urethane binder whereas the 5000 K samples used an acrylate binder. Experimental conditions were chosen to enable study of the binder and phosphor chemistries and to minimize photo-oxidation of the polycarbonate substrate. Under the more severe WHTOL conditions of 85°C and 85% relative humidity (RH), absorption in the binder layer significantly reduced luminous flux and produced a blue color shift. The milder WHTOL conditions of 75°C and 75% RH, resulted in chemical changes in the binder layer that may alter its index of refraction. As a result, lumen maintenance remained high, but a slight yellow shift was found. The aging of remote phosphor products provides insights into the impact of materials on the performance of phosphors in an LED lighting system.

Davis, Lynn↗
DOE OSTI2024

Ferromagnetic Exchange and Slow Magnetic Relaxation in Cobalt Bis(1,2-dithiolene)-Bridged Dilanthanide Complexes

The construction of multinuclear lanthanide-based molecules with significant magnetic exchange interactions represents a key challenge in the realization of single-molecule magnets with high operating temperatures. Here, we report the synthesis and magnetic characterization of two series of heterobimetallic compounds, (Cp* 2 Ln) 2 (μ-Co(pdt) 2 ) (Ln = Y 3+ , Gd 3+ , Dy 3+ ; pdt 2– = 1,2-diphenylethylenedithiolate) and [K(18-crown-6)][(Cp* 2 Ln) 2 (μ-Co(pdt) 2 )] (Ln = Y 3+ , Gd 3+ ), featuring two lanthanide centers bridged by a cobalt bis(1,2-dithiolene) complex. Dc magnetic susceptibility data collected for the Gd congeners indicate significant Gd–Co ferromagnetic exchange interactions with fits affording J = +11.5 and +7.33 cm –1 , respectively. Magnetization decay and ac magnetic susceptibility measurements carried out on the single-molecule magnet (Cp* 2 Dy) 2 (μ-Co(pdt) 2 ) reveal full suppression of quantum tunneling and open-loop hysteresis persisting up to 3.5 K. These results, along with those of high-field EPR spectroscopy, suggest that transition metalloligands can enforce strong exchange interactions with adjacent lanthanide centers while maintaining a geometry that preserves molecular anisotropy. Furthermore, the magnetic properties of [K(18-crown-6)][(Cp* 2 Gd) 2 (μ-Co(pdt) 2 )] show that increasing the spin of the ground state of the bridging complex may be a viable alternative to increasing J in obtaining well-isolated, strongly coupled magnetic ground states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗