Varma, Arvind | Search NASA

DOE OSTI2021

Direct methane activation by atomically thin platinum nanolayers on two-dimensional metal carbides

We report efficient and direct conversion of methane to value-added products has been a long-term challenge in shale gas applications. Here, we show that atomically thin nanolayers of Pt with a single or double atomic layer thickness, supported on a two-dimensional molybdenum titanium carbide (MXene), catalyse non-oxidative coupling of methane to ethane/ethylene (C 2 ). Kinetic and theoretical studies, combined with in-situ spectroscopic and microscopic characterizations, demonstrate that Pt nanolayers anchored at the hexagonal close-packed sites of the MXene support can activate the first C–H bond of methane to form methyl radicals that favour desorption over further dehydrogenation and thus suppress coke deposition. At 750 °C and 7% methane conversion, the catalyst runs for 72 hours of continuous operation without deactivation and exhibits >98% selectivity towards C 2 products, with a turnover frequency of 0.2–0.6 s -1 . Our findings provide insights into the design of highly active and stable catalysts for methane activation and create a platform for developing atomically thin supported metal catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS2004

Nickel-Coated Aluminum Particles: A Promising Fuel for Mars Missions

Combustion of metals in carbon dioxide is a promising source of energy for propulsion on Mars. This approach is based on the ability of some metals (e.g. Mg, Al) to burn in CO2 atmosphere and suggests use of the Martian carbon dioxide as an oxidizer in jet or rocket engines. Analysis shows that CO2/metal propulsion will reduce significantly the mass of propellant transported from Earth for long-range mobility on Mars and sample return missions. Recent calculations for the near-term missions indicate that a 200-kg ballistic hopper with CO2/metal rocket engines and a CO2 acquisition unit can perform 10-15 flights on Mars with the total range of 10-15 km, i.e. fulfill the exploration program typically assigned for a rover. Magnesium is currently recognized as a candidate fuel for such engines owing to easy ignition and fast burning in CO2. Aluminum may be more advantageous if a method for reducing its ignition temperature is found. Coating it by nickel is one such method. It is known that a thin nickel layer of nickel on the surface of aluminum particles can prevent their agglomeration and simultaneously facilitate their ignition, thus increasing the efficiency of aluminized propellants. Combustion of single Ni-coated Al particles in different gas environments (O2, CO2, air) was studied using electrodynamic levitation and laser ignition. It was shown that the combustion mechanisms depend on the ambient atmosphere. Combustion in CO2 is characterized by the smaller size and lower brightness of flame than in O2, and by phenomena such as micro-flashes and fragment ejection. The size and brightness of flame gradually decrease as the particle burns.

Shafirovich, Evgeny↗

NASA NTRS2004

Nickel-coated Aluminum Particles: A Promising Fuel for Mars Missions

Combustion of metals in carbon dioxide is a promising source of energy for propulsion on Mars. This approach is based on the ability of some metals (e.g. Mg, Al) to burn in CO2 atmosphere and suggests use of the Martian carbon dioxide as an oxidizer in jet or rocket engines. Analysis shows that CO2/metal propulsion will reduce significantly the mass of propellant transported from Earth for long-range mobility on Mars and sample return missions. Recent calculations for the near-term missions indicate that a 200-kg ballistic hopper with CO2/metal rocket engines and a CO2 acquisition unit can perform 10-15 flights on Mars with the total range of 10-15 km, i.e. fulfill the exploration program typically assigned for a rover. Magnesium is currently recognized as a candidate fuel for such engines owing to easy ignition and fast burning in CO2. Aluminum may be more advantageous if a method for reducing its ignition temperature is found. Coating it by nickel is one such method. It is known that a thin nickel layer of nickel on the surface of aluminum particles can prevent their agglomeration and simultaneously facilitate their ignition, thus increasing the efficiency of aluminized propellants.

Shafirovich, Evgeny↗

NASA NTRS1997

The Effects of Gravity on Combustion and Structure Formation During Combustion Synthesis in Gasless Systems

There have been relatively few publications examining the role of gravity during combustion synthesis (CS), mostly involving thermite systems. The main goal of this research was to study the influence of gravity on the combustion characteristics of heterogeneous gasless systems. In addition, some aspects of microstructure formation processes which occur during gasless CS were also studied. Four directions for experimental investigation have been explored: (1) the influence of gravity force on the characteristic features of heterogeneous combustion wave propagation (average velocity, instantaneous velocities, shape of combustion front); (2) the combustion of highly porous mixtures (with porosity greater than that for loose powders), which cannot be obtained in normal gravity; (3) the effect of gravity on sample expansion during combustion, in order to produce highly porous materials under microgravity conditions; and (4) the effect of gravity on the structure formation mechanism during the combustion synthesis of poreless composite materials.

Varma, Arvind↗

NASA NTRS1995

The effect of gravity on the combustion synthesis of Ni-Al and Ni3Al-TiB2 composites from elements

Previous studies on the combustion synthesis of advanced materials indicate that combustion and structure formation mechanisms involve several stages including melting of reactants and products, spreading of the melt, droplet coalescence, diffusion and convection, buoyancy of solid particles, and densification of the liquid product. Most of these processes are affected by gravity. Conducting the combustion synthesis under microgravity conditions is expected to help elucidate the reaction mechanisms. Two systems were examined. The first involves Ni/AI cladded particles, which is an ideal system to examine the individual particle and liquid flow before combustion occurs. For comparison, elemental Ni and Al powders with the same stoichiometry as that of the cladded particles were also used in some experiments. The second system was the Ni3AITiB2 composite in which the Ni3AI (-delta H(sub f) = 153.1 kJ/mol) phase melts during reaction enabling us to examine settling of the liquid phase. The amount of liquid phase was controlled by varying the TiB2 (-delta H(sub f) = 323.8 kJ/mol) content which generates the additional heat. The overall reactions for the two systems can be expressed as follows. System 1: 4Ni + 2AI yields Ni3AI + NiA and System 2: 3Ni + Al + x (Ti + 2B) yields Ni3Al + x(TiB2). For the first system, pellets were pressed directly from the cladded particles, at green densities about 77 +/- 3% of theoretical value. For the second, the pellets were prepared by mixing the elemental reactant powders in the required stoichiometry by ball-milling and then pressing uniaxially at green densities about 70 +/- 3 percent of theoretical. The pellets were cylindrical in shape, 10 mm in diameter and length typically 20-30 mm. The pellet samples were reacted in UHP Argon (1 atm) using the experimental setup and procedure described previously. After reaction, the samples were sectioned axially in order to conduct the microstructural analysis in the longitudinal direction. The phase composition of the reacted product was determined by X-ray diffraction (XRD) and the microstructure was analyzed using scanning electron microscopy (SEM) along with energy dispersive X-ray spectrometry (EDX).

Varma, Arvind↗