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Leventis, Nicholas

Publications and source records attributed to Leventis, Nicholas.

At least 19 records

Surface modified aerogel monoliths

This invention comprises reinforced aerogel monoliths such as silica aerogels having a polymer coating on its outer geometric surface boundary, and to the method of preparing said aerogel monoliths. The polymer coatings on the aerogel monoliths are derived from polymer precursors selected from the group consisting of isocyanates as a precursor, precursors of epoxies, and precursors of polyimides. The coated aerogel monoliths can be modified further by encapsulating the aerogel with the polymer precursor reinforced with fibers such as carbon or glass fibers to obtain mechanically reinforced composite encapsulated aerogel monoliths.

Leventis, Nicholas

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas

Highly porous and mechanically strong ceramic oxide aerogels

Structurally stable and mechanically strong ceramic oxide aerogels are provided. The aerogels are cross-linked via organic polymer chains that are attached to and extend from surface-bound functional groups provided or present over the internal surfaces of a mesoporous ceramic oxide particle network via appropriate chemical reactions. The functional groups can be hydroxyl groups, which are native to ceramic oxides, or they can be non-hydroxyl functional groups that can be decorated over the internal surfaces of the ceramic oxide network. Methods of preparing such mechanically strong ceramic oxide aerogels also are provided.

Leventis, Nicholas

Strong, Lightweight, Porous Materials

A new class of strong, lightweight, porous materials has been invented as an outgrowth of an effort to develop reinforced silica aerogels. The new material, called X-Aerogel is less hygroscopic, but no less porous and of similar density to the corresponding unmodified aerogels. However, the property that sets X-Aerogels apart is their mechanical strength, which can be as much as two and a half orders of magnitude stronger that the unmodified aerogels. X-Aerogels are envisioned to be useful for making extremely lightweight, thermally insulating, structural components, but they may also have applications as electrical insulators, components of laminates, catalyst supports, templates for electrode materials, fuel-cell components, and filter membranes.

Leventis, Nicholas

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of C-13 CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Meador, Mary Ann B.

Structure-Property Relationships in Porous 3-D Nanostructures as a Function of Preparation Conditions: Isocyanate Cross-Linked Silica Aerogels

Sol-gel derived silica aerogels are attractive candidates for many unique thermal, optical, catalytic, and chemical applications because of their low density and high mesoporosity. However, their inherent fragility has restricted use of aerogel monoliths to applications where they are not subject to any load. We have previously reported cross-linking the mesoporous silica structure of aerogels with di-isocyanates, styrenes or epoxies reacting with amine decorated silica surfaces. These approaches have been shown to significantly increase the strength of aerogels with only a small effect on density or porosity. Though density is a prime predictor of properties such as strength and thermal conductivity for aerogels, it is becoming clear from previous studies that varying the silica backbone and size of the polymer cross-link independently can give rise to combinations of properties which cannot be predicted from density alone. Herein, we examine the effects of four processing parameters for producing this type of polymer cross-linked aerogel on properties of the resulting monoliths. We focus on the results of 13C CP-MAS NMR which gives insight to the size and structure of polymer cross-link present in the monoliths, and relates the size of the cross-links to microstructure, mechanical properties and other characteristics of the materials obtained.

Meador, Mary Ann B.

Protective Skins for Aerogel Monoliths

A method of imparting relatively hard protective outer skins to aerogel monoliths has been developed. Even more than aerogel beads, aerogel monoliths are attractive as thermal-insulation materials, but the commercial utilization of aerogel monoliths in thermal-insulation panels has been inhibited by their fragility and the consequent difficulty of handling them. Therefore, there is a need to afford sufficient protection to aerogel monoliths to facilitate handling, without compromising the attractive bulk properties (low density, high porosity, low thermal conductivity, high surface area, and low permittivity) of aerogel materials. The present method was devised to satisfy this need. The essence of the present method is to coat an aerogel monolith with an outer polymeric skin, by painting or spraying. Apparently, the reason spraying and painting were not attempted until now is that it is well known in the aerogel industry that aerogels collapse in contact with liquids. In the present method, one prevents such collapse through the proper choice of coating liquid and process conditions: In particular, one uses a viscous polymer precursor liquid and (a) carefully controls the amount of liquid applied and/or (b) causes the liquid to become cured to the desired hard polymeric layer rapidly enough that there is not sufficient time for the liquid to percolate into the aerogel bulk. The method has been demonstrated by use of isocyanates, which, upon exposure to atmospheric moisture, become cured to polyurethane/polyurea-type coats. The method has also been demonstrated by use of commercial epoxy resins. The method could also be implemented by use of a variety of other resins, including polyimide precursors (for forming high-temperature-resistant protective skins) or perfluorinated monomers (for forming coats that impart hydrophobicity and some increase in strength).

Leventis, Nicholas

Manufacture of Regularly Shaped Sol-Gel Pellets

An extrusion batch process for manufacturing regularly shaped sol-gel pellets has been devised as an improved alternative to a spray process that yields irregularly shaped pellets. The aspect ratio of regularly shaped pellets can be controlled more easily, while regularly shaped pellets pack more efficiently. In the extrusion process, a wet gel is pushed out of a mold and chopped repetitively into short, cylindrical pieces as it emerges from the mold. The pieces are collected and can be either (1) dried at ambient pressure to xerogel, (2) solvent exchanged and dried under ambient pressure to ambigels, or (3) supercritically dried to aerogel. Advantageously, the extruded pellets can be dropped directly in a cross-linking bath, where they develop a conformal polymer coating around the skeletal framework of the wet gel via reaction with the cross linker. These pellets can be dried to mechanically robust X-Aerogel.

Leventis, Nicholas

Clay Nanocomposite/Aerogel Sandwich Structures for Cryotanks

GRC research has led to the development of epoxy-clay nanocomposites with 60-70% lower gas permeability than the base epoxy resin. Filament wound carbon fiber reinforced tanks made with this nanocomposite had a five-fold lower helium leak rate than the corresponding tanks made without clay. More recent work has produced new composites with more than a 100-fold reduction in helium permeability. Use of these advanced, high barrier composites would eliminate the need for a liner in composite cryotanks, thereby simplifying construction and reducing propellant leakage. Aerogels are attractive materials for use as cryotank insulation because of their low density and low thermal conductivity. However, aerogels are fragile and have poor environmental stability, which have limited their use to certain applications in specialized environments (e.g., in certain types of nuclear reactors as Cerenkov radiation detectors, and as thermal insulators aboard space rovers on Mars). New GRC developed polymer crosslinked aerogels (X-Aerogels) retain the low density of conventional aerogels, but they demonstrate a 300-fold increase in their mechanical strength. Currently, our strongest materials combine a density of approx. 0.45 g/cc, a thermal conductivity of approx. 0.04 W/mK and a compressive strength of ~185 MPa. Use of these novel aerogels as insulation materials/structural components in combination with the low permeability of epoxy-clay nanocomposites could significantly reduce cryotank weight and improve durability.

Miller, Sandi

Chemical, Physical, and Mechanical Characterization of Isocyanate Cross-linked Amine-Modified Silica Aerogels

We describe a new mechanically strong lightweight porous composite material obtained by encapsulating the skeletal framework of amine-modified silica aerogels with polyurea. The conformal polymer coating preserves the mesoporous structure of the underlying silica framework and the thermal conductivity remains low at 0.041 plus or minus 0.001 W m(sup -1 K(sup -1). The potential of the new cross-linked silica aerogels for load-carrying applications was determined through characterization of their mechanical behavior under compression, three-point bending, and dynamic mechanical analysis (DMA). A primary glass transition temperature of 130 C was identified through DMA. At room temperature, results indicate a hyperfoam behavior where in compression cross-linked aerogels are linearly elastic under small strains (less than 4%) and then exhibit yield behavior (until 40% strain), followed by densification and inelastic hardening. At room temperature the compressive Young's modulus and the Poisson's ratio were determined to be 129 plus or minus 8 MPa and 0.18, respectively, while the strain at ultimate failure is 77% and the average specific compressive stress at ultimate failure is 3.89 x 10(exp 5) N m kg(sup -1). The specific flexural strength is 2.16 x 10(exp 4) N m kg(sup -1). Effects on the compressive behavior of strain rate and low temperature were also evaluated.

Katti, Atul

Mechanically Strong, Polymer Cross-linked Aerogels (X-Aerogels)

Aerogels comprise a class of low-density, high porous solid objects consisting of dimensionally quasi-stable self-supported three-dimensional assemblies of nanoparticles. Aerogels are pursued because of properties above and beyond those of the individual nanoparticles, including low thermal conductivity, low dielectric constant and high acoustic impedance. Possible applications include thermal and vibration insulation, dielectrics for fast electronics, and hosting of functional guests for a wide variety of optical, chemical and electronic applications. Aerogels, however, are extremely fragile materials, hence they have found only limited application in some very specialized environments, for example as Cerenkov radiation detectors in certain types of nuclear reactors, aboard spacecraft as collectors of hypervelocity particles (refer to NASA's Stardust program) and as thermal insulators on planetary vehicles on Mars (refer to Sojourner Rover in 1997 and Spirit and Opportunity in 2004). Along these lines, the X-Aerogel is a new NASA-developed strong lightweight material that has resolved the fragility problem of traditional (native) aerogels. X-Aerogels are made by applying a conformal polymer coating on the surfaces of the skeletal nanoparticles of native aerogels (see Scanning Electron Micrographs). Since the relative amounts of the polymeric crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by the templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by remplated casting of polymer on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralighweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the the thermal conductivity of styrofoam. X-Aerogels have been demonstrated with several polymers such as polyurethanes/polyureas, epoxies and polyolefins, while crosslinking of approximately 35 different oxide aerogels yields a range of dimensionally stable, porous lightweight materials with unique combinations of structural, magnetic and optical properties. The main theme in materials development for space exploration is multifunction. For example, use of one material for thermal insulation/structural component will free weight for useful payload. In that regard, X-aerogels are evaluated at NASA for cryogenic fuel storage tanks and for spacesuits. Along the same lines, major impact fro X-Aerogels is also expected in commercial applications for thermal/acoustic insulation, in catalytic reformers and converters, in filtration membranes and membranes for fuel cells, as platforms for optical, electrical and magnetic sensors, and as lightweight structural component for aircraft and satellites.

Leventis, Nicholas

Mechanically Strong, Lightweight Porous Materials Developed (X-Aerogels)

Aerogels are attractive materials for a variety of NASA missions because they are ultralightweight, have low thermal conductivity and low-dielectric constants, and can be readily doped with other materials. Potential NASA applications for these materials include lightweight insulation for spacecraft, habitats, and extravehicular activity (EVA) suits; catalyst supports for fuel cell and in situ resource utilization; and sensors for air- and water-quality monitoring for vehicles, habitats, and EVA suits. Conventional aerogels are extremely fragile and require processing via supercritical fluid extraction, which adds cost to the production of an aerogel and limits the sizes and geometries of samples that can be produced from these materials. These issues have severely hampered the application of aerogels in NASA missions.

Leventis, Nicholas

Crosslinking Amine-Modified Silica Aerogels with Epoxies: Mechanically Strong Lightweight Porous Materials

The mesoporous surfaces of TMOS-derived silica aerogels have been modified with amines by co-polymerization of TMOS with APTES. The amine sites have become anchors for crosslinking the nanoparticles of the skeletal backbone of the aerogel by attachment of di-, tri and tetra-functional epoxies. The resulting conformal coatings increase the density of the native aerogels by a factor of 2-3 but the strength of the resulting materials may increase by more than two orders of magnitude. Processing variables such as amount of APTES used to make the gels, the epoxy type and concentration used for crosslinking, as well as the crosslinking temperature and time were varied according to a multivariable design-of-experiments (DOE) model. It was found that while elastic modulus follows a similar trend with density, maximum strength is attained neither at the maximum density nor at the highest concentration of -NH2 groups, suggesting surface saturation effects. Aerogels crosslinked with the tri-functional epoxide always show improved strength compared with aerogels crosslinked with the other two epoxides under identical conditions. Solid C-13 NMR studies show residual unreacted epoxides, which condense with ne another by heating crosslinked aerogels at 150 C.

Meador, Mary Ann B.

Mechanically Strong Lightweight Materials for Aerospace Applications (x-aerogels)

The X-Aerogel is a new NASA-developed strong lightweight material made by reacting the mesoporous surfaces of 3-D networks of inorganic nanoparticles with polymeric crosslinkers. Since the relative amount of the crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by templated casting of polymeric precursors on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralightweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the thermal conductivity of styrofoam. XAerogels have been demonstrated with several polymers such as polyurethanes/polyureas, epoxies and polyolefins, while crosslinking of approximately 35 different oxide aerogels yields a wide variety of dimensionally stable, porous lightweight materials with interesting structural, magnetic and optical properties. X-Aerogels are evaluated for cryogenic rocket fuel storage tanks and for Advanced EVA suits, where they will play the dual role of the thermal insulator/structural material. Along the same lines, major impact is also expected by the use of X-Aerogels in structural components/thermal protection for small satellites, spacecrafts, planetary vehicles and habitats.

Leventis, Nicholas

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

In analogy to supramolecular assemblies, which are pursued because of properties above and beyond those of the individual molecules, self-standing monolithic three-dimensional assemblies of nanoparticles also have unique properties attributed to their structure. For example, ultra low-density 3-D assemblies of silica nanoparticles, known as silica aerogels, are characterized by large internal void space, high surface area and very low thermal conductivity. Aerogels, however, are also extremely fragile materials, limiting their application to a few specialized environments, e.g., in nuclear reactors as Cerenkov radiation detectors, in space (refer to NASA's Stardust Program) and aboard certain planetary vehicles (thermal insulators on Mars Rovers in 1997 and 2004). The fragility problem is traced to well-defined weak points in the aerogel skeletal framework, the interparticle necks. Using the surface functionality of the nanoparticle building blocks as a focal point, we have directed attachment of a conformal polymer coating over the entire framework, rendering all necks wider. Thus, although the bulk density may increase only by 3x, the mesoporosity (pores in the range 2-50 nm) remains unchanged, while the strength of the material increases by up to 300... Having addressed the fragility problem, aerogels are now robust materials, and a variety of applications, ranging from thermal/acoustic insulators to catalyst supports, to platform for sensors, and dielectrics are all within reach. Our approach employs molecular science to manipulate nanoscopic matter for achieving useful macroscopic properties, and in our view it resides at the core of what defines nanotechnology. In that spirit, this technology is expandable in three directions. Thus, we have already crosslinked successfully amine-modified silica, and we anticipate that more rich chemistry will be realized by been creative with the nanoparticle surface modifiers. On the other hand, although we do not expect orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Leventis, Nicholas

Protection of 2-(3-Thienyl)ethanol with 3-Thienylacetic Acid and Hard Cross- Linked Conducting Films by Electropolymerization of the Ester

The ester (compound 1) of 2-(3-thienyl)ethanol (T-etOH) with 3-thienylacetic acid was synthesized as a monomer whose two thiophene groups could be electropolymerized independently, becoming members of different polymer chains in a highly-crosslinked highly-insoluble polymer. Indeed, 1 was electropolymerized successfully alone and together with 3-methylthiophene (3MeT). Films of poly(1) are hard (3H, as opposed to less than 6B for poly(3MeT)), and the close proximity of the polymeric strands creates pi-stacking interactions. The behavior of 1 suggests that by: (a) limiting the potential used for the oxidation of monomeric esters of T-etOH at the foot of their oxidation waves (less than 1.8 V vs. Ag/AgCl); and, (b) compensating for the decrease in the electrogenerated radical concentration by increasing the monomer concentration, practically all esters of T-etOH should be electropolymerizable. This was confirmed by durable film formation from the archetypical ester of T-etOH, the 2-(3-thienyl)ethyl acetate (T-etOAc), whose homo-electropolymerization is reported for the first time.

Leventis, Nicholas

Synthesis and Near IR Photoluminescence of Os(II) Bis(2,2'-bipyridine) (3,8-Diarylethynyl-1,10-phemanthroline) Complexes: Anomalous Behavior of the 3,8-Dinitrophenylethynyl-substituted Homologue

A large bathochromic shift (50 nm) and emission in the near infrared is observed by attaching arylethynyl groups at the 3,8-positions of the 1,10-phenanthroline ligand (phen) of [Os(bipy)2(phen)]2+ (where bipy = 2,2'-bipyridine). Thus [Os(bipy)2(3,8-di-4-methoxyphenylethynyl-1,10-phenathroline)]2+ emits at 795 nm, while [Os(bipy)2(3,8-diphenylethynyl-1,10-phenanthroline)]2+ emits at 815 nm. According to this trend it would have been expected that [Os(bipy)2(3,8-di-4-nitrophenylethynyl-1,10-phenathroline)]2+ emits farther in the near infrared. Nevertheless, this complex is not photoluminescent because of intramolecular electron transfer quenching of the MLCT excited state by the nitroaromatic group. These results set structural and redox potential standards in the design of near infrared emitters based on [Os(bipy)2(phen)]2+ type complexes.

Yang, Jinhua

Mechanically Strong Aerogels Formed by Templated Growth of Polymer Cross- Linkers on Inorganic Nanoparticles

In the search for materials with better mechanical, thermal, and electrical properties, it is becoming evident that oftentimes dispersing ceramic nanoparticles in plastics improves performance. Along these lines, chemical bonding (both covalent and noncovalent) between a filler and a polymer improves their compatibility, and thus enhances certain properties of the polymeric matrix above and beyond what is accomplished by simple doping with the filler. When a similarly sized dopant and matrix are used, elementary building blocks may also have certain distinct advantages (e.g., in catalysis). In this context, researchers at the NASA Glenn Research Center reasoned that in the extreme case, where the dopant and the matrix (e.g., a filler and a polymer) are not only sized similarly, but their relative amounts are comparable, the relative roles of the dopant and matrix can be reversed. Then, if the "filler," or a certain form thereof, possesses desirable properties of its own, such properties could be magnified by cross-linking with a polymer. We at Glenn have identified silica as such a filler in its lowest-density form, namely the silica aerogel.

Leventis, Nicholas