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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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

High-Temperature-Performance Cyanate Ester Composites with Carboranes

Cyanate ester (CE) is an important class of materials among high-temperature performance thermosets. It is used in aerospace launch vehicles, heat sinks, booms, and trusses of satellites etc. due to its high glass transition temperatures (>220°C), excellent thermal stability, and low flammability. Current approaches to improve the thermal stability of CE include incorporation of siloxanes or phosphorus- based flame retardants (PFRs). In this work, we have explored boron-based hydroxy (PD) and epoxy (EP) functionalized carborane additives to improve the thermal properties of CE. Carborane fillers were solvent blended at various mass loadings in the resin and cured to study their effect on thermal properties. PD and EP carboranes react with CE to form iminocarbonate and oxazolidinone linkages respectively. Cure kinetics studies at different wt% loadings explained that carboranes catalyze the curing reaction by reducing curing activation energy by about 54% and 26% for 10 wt% loadings of PD and EP carboranes respectively. In addition, carborane-filled cyanate ester (CE) nanocomposites demonstrate an exceptionally high thermal stability as compared to the pristine resin in air and inert environment. Our thermogravimetric analysis (TGA) experiments show that the ultimate char yield of the resin can be increased from 0% to as high as 76% and 82% with 30 wt% PD and EP carborane loading respectively at 1000 °C in air. The initial degradation temperature T d;5 of the composites decreased with increasing carborane loadings in both air and argon. For instance, T d;5 for CE was 465 and 471.6 °C in argon and air while that for P20 was 437.4 and 452.1 °C. Modulated TGA studies gave evidence of the effect of carboranes on degradation kinetics and the mechanism of the resin in air and inert environment. The effect of bonding between carboranes and CE at various loadings on the thermal expansion of the matrix was also studied using Thermomechanical Analyzer (TMA). PD carborane reduced the T g for P20 to about 225 °C while CE had T g >350 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The Explosive Hazards of Icosahedral Carboranes and Dodecaborate with Common Oxidizers and Salts

Carboranes find use in a wide variety of applications ranging from specialty catalysts to medicinal uses. Certain functionalized carboranes are described as explosive materials, although their nonfunctionalized precursors are regarded as inherently stable and not explosive. Herein, we report new findings on the sensitization of nonfunctionalized 12-vertex ortho-, meta-, and para-carboranes as well as dodecaborate in physical mixtures with several common inorganic salts. These mixtures were evaluated for explosive properties with drop hammer impact tests, friction tests, and differential scanning calorimetry thermal gravimetric analysis (DSC-TGA). Results indicate explosive sensitization to mechanical stimuli for the nonfunctionalized carboranes tested with a wide variety of inorganic salts, especially oxidizers. Sensitization of these compounds has not previously been reported, and raising awareness to the broader scientific community on this matter is warranted, especially as several of the mixtures evaluated are more sensitive to mechanical stimuli than primary explosives such as lead azide or pentaerythritol tetranitrate.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A Carborane-Derived Proton-Coupled Electron Transfer Reagent

Reagents capable of concerted proton–electron transfer (CPET) reactions can access reaction pathways with lower reaction barriers compared to stepwise pathways involving electron transfer (ET) and proton transfer (PT). To realize reductive multielectron/proton transformations involving CPET, one approach that has shown recent promise involves coupling a cobaltocene ET site with a protonated arylamine Brønsted acid PT site. This strategy colocalizes the electron/proton in a matter compatible with a CPET step and net reductive electrocatalysis. To probe the generality of such an approach a class of C,C'-diaryl-ocarboranes is herein explored as a conceptual substitute for the cobaltocene subunit, with an arylamine linkage still serving as a colocalized Brønsted base suitable for protonation. The featured ocarborane (PhCbPh N ) can be reduced and protonated to generate an N–H bond with a weak effective bond dissociation free energy (BDFE eff ) of 31 kcal/mol, estimated with measured thermodynamic data. This N–H bond is among the lowest measured element–H bonds for analyzed nonmetal compounds. Distinct solid-state crystal structures of the one- and two-electron reduced forms of diaryl-o-carboranes are disclosed to gain insight into their well-behaved redox characteristics. The singly reduced, protonated form of the diaryl-o-carborane can mediate multi-ET/PT reductions of azoarenes, diphenylfumarate, and nitrotoluene. In contrast to the aforementioned cobaltocene system, available mechanistic data disclosed herein support these reactions occurring by a rate-limiting ET step and not a CPET step. A relevant hydrogen evolution reaction (HER) reaction was also studied, with data pointing to a PT/ ET/PT mechanism, where the reduced carborane core is itself highly stable to protonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Extreme Thermal Stabilization of Carborane–Cyanate Composites via B–N Dative-Bonded Boroxine Barriers

Enhancing the thermal stability of cyanate ester (CE) resins is crucial for high-temperature aerospace applications. This study elucidates the degradation mechanisms of CE composites reinforced with carborane additives, focusing on the formation of boron–nitrogen (B–N) dative bonds and their role in improving thermal resistance. Using thermogravimetric analysis, we examined char formation and evolved gases at multiple degradation stages. Reaction sequences and char products were characterized via Fourier transform infrared spectroscopy (FTIR), solid-state 13C and 11B NMR, and evolved gas analysis using mass spectrometry and FTIR. The solid-state 11B NMR was instrumental in detecting various boron oxidation states and the formation of B–N dative bonds during decomposition. These bonds facilitate cross-linking in the char phase, enhancing material integrity at elevated temperatures. However, in inert environments, the volatility of boron additives like carborane limits their effectiveness. These findings advance the understanding of CE composite degradation mechanisms and offer critical insights for developing high-temperature-resistant materials for aerospace applications.

Fourier transform infrared spectroscopy↗
NASA NTRS1983

Synthesis and thermal stability of carborane containing phosphazenes

Carborane substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl penta chlorocyclotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring chain equilibrium processes of decomposition.

Fewell, L. L.↗
NASA NTRS1983

Synthesis and thermal stability of carborane-containing phosphazenes

Carborane-substituted polyphosphazenes were prepared by the thermal polymerization of phenyl-carboranyl pentachlorocylotriphosphazene. Successive isothermal vacuum pyrolyses were conducted on the polymer and examined for structural changes by infrared spectroscopy. The degradation products were ascertained by gas chromatography-mass spectrometric analysis. It was found that the presence of the carborane group improves the thermal stability of the polymer by retarding the ring-chain equilibrium processes of decomposition. Previously announced in STAR as A83-21034

Fewell, L. L.↗
NASA NTRS1986

Phosphazene Polymers Containing Carborane

Addition of carborane increases thermal stability. Carborane-substituted polyphosphazenes prepared by thermal polymerization of phenylcarbonyl-pentachlorocyclotriphosphazene followed by reaction with sodium trifluoroethoxide to replace remaining chlorine atoms with trifluoroethoxy groups. Improved polymers offer high char yields and resistance to hydrolysis.

Fewell, L. L.↗
DOE OSTI2023

Selective heterogeneous capture and release of actinides using carborane-functionalized electrodes

Here we report the heterogenization of molecular, electrochemically switchable ortho-substituted carboranes ( PO Cb, PO Cb-Pyr) for selective metal capture. Films of PO Cb and PO Cb-Pyr on glassy carbon and carbon fiber (CF) electrodes demonstrated heterogeneous electrochemical behaviour that was enhanced by the inclusion of single-walled carbon nanotubes (CNTs). Galvanostatically charged CF|CNT| PO Cb and CF|CNT| PO Cb-Pyr electrodes selectively captured and released actinides (Th 4+ , UO 2 2+ ) from mixed solutions containing alkali (Cs + ), lanthanide (Nd 3+ , Sm 3+ ) and actinide (Th 4+ , UO 2 2+ ) metal ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

The use of carboranes as oxidation inhibitors for carbon-carbon composites

Carbon-carbon composites have many beneficial properties for use in aerospace applications, including their high specific strength and modulus at elevated temperatures. However, they share with all carbon based substances a strong tendency to burn when heated in air. In order to exploit their good qualities, it is necessary to slow or prevent their oxidation during use. Molecular inhibiters offer protection with the advantage of being able to form a homogeneous solution with the resin. Since boron oxides are known to provide the desired kind of protection, molecular compounds based on boron seem reasonable candidates to test as inhibitors. Performance tests indicated that carboranes are excellent materials for obtaining high uniform loadings of boron inhibitors in glassy carbon materials and thus reducing their rates of oxidation. Further, there is evidence that the use of substituted derivatives could provide more complete and thorough forms of protection.

Petty, John T.↗
DOE OSTI2024

Competing Intermolecular and Molecule–Surface Interactions: Dipole–Dipole-Driven Patterns in Mixed Carborane Self-Assembled Monolayers

Carboranedithiol isomers adsorbing with opposite orientations of their dipoles on surfaces are self-assembled together to form mixed monolayers where both lateral dipole–dipole and lateral thiol–thiolate (S–H···S) interactions provide enhanced stability over single-component monolayers. Here, we demonstrate the first instance of the ability to map individual isomers in a mixed monolayer using the model system carboranedithiols on Au{111}. The addition of methyl groups to one isomer provides both an enhanced dipole moment and extra apparent height for differentiation via scanning tunneling microscopy (STM). Associated computational investigations rationalize favorable interactions of mixed pairs and the associated stability changes that arise from these interactions. Both STM images and Monte Carlo simulations yield similarly structured mixed monolayers, where approximately 10% of the molecules have reversed dipole moment orientations but no direct chemical attachment to the surface, leading to homogeneous monolayers with no apparent phase separation. Deprotonating the thiols by depositing the molecules under basic conditions eliminates the lateral S–H···S interactions while accentuating the dipole–dipole forces. The molecular system investigated is composed of isomeric molecules with opposite orientations of dipoles and identical surface packing, which enables the mapping of individual molecules within the mixed monolayers and enables analyses of the contributions of the relatively weak lateral interactions to the overall stability of the assemblies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗