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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
NASA NTRS2011

The Importance of Water for High Fidelity Information Processing and for Life

Is water an absolute prerequisite for life? Life depends on a variety of non-covalent interactions among molecules, the nature of which is determined as much by the solvent in which they occur as by the molecules themselves. Catalysis and information processing, two essential functions of life, require non-covalent molecular recognition with very high specificity. For example, to correctly reproduce a string consisting of 600,000 units of information (e.g ., 600 kilobases, equivalent to the genome of the smallest free living terrestrial organisms) with a 90% success rate requires specificity > 107 : 1 for the target molecule vs. incorrect alternatives. Such specificity requires (i) that the correct molecular association is energetically stabilized by at least 40 kJ/mol relative to alternatives, and (ii) that the system is able to sample among possible states (alternative molecular associations) rapidly enough to allow the system to fall under thermodynamic control and express the energetic stabilization. We argue that electrostatic interactions are required to confer the necessary energetic stabilization vs. a large library of molecular alternatives, and that a solvent with polarity and dielectric properties comparable to water is required for the system to sample among possible states and express thermodynamic control. Electrostatic associations can be made in non-polar solvents, but the resulting complexes are too stable to be "unmade" with sufficient frequency to confer thermodynamic control on the system. An electrostatic molecular complex representing 3 units of information (e.g., 3 base pairs) with specificity > 107 per unit has a stability in non-polar solvent comparable to that of a carbon-carbon bond at room temperature. These considerations suggest that water, or a solvent with properties very like water, is necessary to support high-fidelity information processing, and can therefore be considered a critical prerequisite for life.

Hoehler, Tori M.↗
NASA NTRS2014

Improved Composites Using Crosslinked, Surface-Modified Carbon Nanotube Materials

Individual carbon nanotubes (CNTs) exhibit exceptional tensile strength and stiffness; however, these properties have not translated well to the macroscopic scale. Premature failure of bulk CNT materials under tensile loading occurs due to the relatively weak frictional forces between adjacent CNTs, leading to poor load transfer through the material. When used in polymer matrix composites (PMCs), the weak nanotube-matrix interaction leads to the CNTs providing less than optimal reinforcement.Our group is examining the use of covalent crosslinking and surface modification as a means to improve the tensile properties of PMCs containing carbon nanotubes. Sheet material comprised of unaligned multi-walled carbon nanotubes (MWCNT) was used as a drop-in replacement for carbon fiber in the composites. A variety of post-processing methods have been examined for covalently crosslinking the CNTs to overcome the weak inter-nanotube shear interactions, resulting in improved tensile strength and modulus for the bulk sheet material. Residual functional groups from the crosslinking chemistry may have the added benefit of improving the nanotube-matrix interaction. Composites prepared using these crosslinked, surface-modified nanotube sheet materials exhibit superior tensile properties to composites using the as received CNT sheet material.

polymer matrix composite↗
NASA NTRS2016

Molecular Dynamics Modeling of Carbon Nanotube Composite Fracture Using ReaxFF

Carbon nanotube (CNT) fiber reinforced composites with specific tensile strengths and moduli approaching those of aerospace grade carbon fiber composites have recently been reported. This achievement was enabled by the emerging availability of high N/tex yarns in kilometer-scale quantities. While the production of this yarn is an impressive advance, its strength is still much lower than that of the individual CNTs comprising the yarn. Closing this gap requires understanding load transfer between CNTs at the nanometer dimensional scale. This work uses reactive molecular dynamics simulations to gain an understanding at the nanometer scale of the key factors that determine CNT nanocomposite mechanical performance, and to place more realistic upper bounds on the target properties. While molecular dynamics simulations using conventional force fields can predict elastic properties, the ReaxFF reactive forcefield can also model fracture behavior because of its ability to accurately describe bond breaking and formation during a simulation. The upper and lower bounds of CNT composite properties are investigated by comparing systems composed of CNTs continuously connected across the periodic boundary with systems composed of finite length CNTs. These lengths, effectively infinite for the continuous tubes and an aspect ratio of 13 for the finite length case, result from practical limitations on the number of atoms that can be included in a simulation. Experimentally measured aspect ratios are typically on the order of 100,000, so the calculated results should represent upper and lower limits on experimental mechanical properties. Finally, the effect of various degrees of covalent crosslinking between the CNTs and amorphous carbon matrix is considered to identify the amount of CNT-matrix covalent bonding that maximizes overall composite properties.

Jensen, Benjamin D.↗
NASA NTRS2018

Is Water Necessary for Life?

The universality of water as the solvent for life is usually justified by its role in supporting the rich organic chemistry. It has been pointed out, however, that even richer synthetic chemistry is possible in other organic solvents. Does it mean that water is not necessary for life? Here, other, essential criteria for solvent for life that have not been sufficiently considered are discussed. In biological systems, complex molecules are not only constantly synthesized but also degraded. Solvent-mediated degradation is essential for regulating cell content, preventing overcrowding and allowing for recycling organic material. Achieving a balance between synthetic and degradative processes is facile in water, but not in many other organic liquids. Thus, the so-called “water paradox” according to which water is both necessary to life and toxic to biopolymer synthesis might not be paradoxical at all. The machinery of life is based on non-covalent interactions that do not involve making or breaking chemical bonds. Their strength needs to be properly tuned. If they are too weak, there might be undesired response to natural fluctuations of physical or chemical parameters. If they are too strong, the kinetics and energetics of cellular processes could adversely influenced. The solvent must allow for balancing these interactions, which provides strong, universal constraints on the medium for life. Water influences non-covalent interactions mainly by two mechanisms. First, it reduces strong, electrostatic interactions between molecules, chemical groups or atoms carrying electric charge or dipole. Second, it induces the hydrophobic effect, the tendency to remove non-polar (hydrophobic) molecules and groups from direct contact with aqueous solution and, instead, interact with each other. In living systems, the hydrophobic effect is largely responsible for self-organization of molecules to more complex structures, such as aggregation of lipid molecules to form biological membranes and protein folding. Water exists as stable liquid in a large temperature range, and the hydrophobic effects are a consequence of the temperature insensitivity of essential properties of its liquid state. In summary, water accomplishes an amazing feat – it reduces strong interactions between dissolved species and simultaneously increases the strength of weak interactions, bringing all of them to the right range. Once we consider not only synthetic capabilities but also other required traits of the solvent for life, no viable alternative to water is currently known.

Life↗
NASA NTRS2018

Associative Polymers to Control Formation of Particulate Matter from Ignitable Compositions and Related Compositions, Methods and Systems

Described herein are associative polymers capable of controlling formation of particulate matter from a non-polar ignitable composition upon ignition of the non-polar ignitable composition, alone or in combination with control of a physical and/or chemical property of the non-polar compositions and related compositions, methods and systems. Associative polymers herein described have a non-polar backbone and functional groups presented at ends of the non-polar backbone, with a number of the functional groups presented at the ends of the non-polar backbone formed by associative functional groups capable of undergoing an associative interaction with another associative functional group with an association constant (k) such that the strength of each associative interaction is less than the strength of a covalent bond between atoms and in particular less than the strength of a covalent bond between backbone atoms.

Kornfield, Julia A.↗
NASA NTRS2020

Effects of Texture and Silica Content on Crack Growth in Boron Nitrides

Boron nitride is used in applications such as crucibles for melting and casting glasses and metals, insulators for furnaces, molds for hot pressing, and neutron absorbers. Historically, various grades of hot pressed hexagonal boron nitride (BN) have been used. This study investigates the fracture toughness and slow crack growth parameters of several commercially available BN grades. Prior work revealed that some grades of BN absorb water and change strength, thus presenting a philosophical conundrum on crack growth test methods. The grades selected for this study are of interest because their available billet size is sufficient for large components, or because they have heritage in specific applications. Ultimately, the data will be used to perform material selection, system design and reliability analyses of components of interest. Boron nitrides exhibit limited slow crack growth in humidity, with an orientation dependence due to crystallographic texture: orientations with van der Waal bonds are insensitive to water whereas those with covalent bonds are sensitive. Fracture toughness is low, around that of glass, and is also a function of orientation (bond type), with fracture occurring more readily along van der Waal bonds between hexagonal BN platelets than at covalent bonds across platelets. Silica additions toughen BN, but increase slow crack growth susceptibility.

Salem, Jonathan A.↗
NASA NTRS2019

Toward Ultralight High Strength Structural Materials via Collapsed Carbon Nanotube Bonding

The growing commercial availability of carbon nanotube (CNT) macro-assemblies such as sheet and yarn is making their use in structural composite components increasingly feasible. However, the mechanical properties of these materials continue to trail those of state-of-the-art carbon fiber composites due to relatively weak inter-tube load transfer. Forming covalent links between adjacent CNTs promises to mitigate this problem, but it has proven difficult in practice to introduce them chemically within densified and aligned CNT materials due to their low permeability. To avoid this limitation, this work explores the combination of pulsed electrical current, temperature, and pressure to introduce inter-CNT bonds. Reactive molecular dynamics simulations identify the most probable locations, configurations, and conditions for inter-nanotube bonds to form. This process is shown to introduce covalent linkages within the CNT material that manifest as improved macroscale mechanical properties. The magnitude of this effect increases with increasing levels of prealignment of the CNT material, promising a new synthesis pathway to ultralight structural materials with specific strengths and stiffnesses exceeding 1 and 100 GPa/(g/cu.cm), respectively.

Jensen, Benjamin D.↗
NASA NTRSDate not supplied

Fracture Prediction of Epoxy Resin using Morse Bond Potential Embedded in GAFF using Molecular Dynamics Simulations

A generic method is developed to investigate the fracture behavior of an epoxy resin using atomistic molecular (MD) dynamics simulations. The epoxy system consisted of the stoichiometric mixture of tetra-/tri-functional epoxies and di-functional hardener molecules and was cured with a step-growth crosslinking algorithm. A hybrid force field (hFF) in which Morse bond function were added in second generation-general Amber Force Field (GAFF2) was used to capture bond breaking of the crosslinked epoxy system under uniaxial deformation. The Morse bond parameters for covalent bonds in the crosslinked backbone were fit to dissociation curves computed by CASPT2/6-311+G**. After the systems in various crosslink densities were obtained and equilibrated, the full length of stress-strain (𝜎-𝜀) curve was produced including initial elastic regime, yielding, plastic flow, strain hardening, and progressive failure. We found that the hFF was effective in studying the dissociation of crosslinked polymers and understanding the failure mechanism. In the results, the hFF delivered the same elastic property obtained from the unmodified force field GAFF. The stress-strain curve, however, began to be distinct in the plastic regime due to broken covalent bonds capable of altering the tensile behavior. Once the stress reached maximum, it progressively decreased until the ultimate failure (𝜎=0). Since hFF employed the existing GAFF functions with including a minimal change of its bond potential, this approach is easier to perform and computationally more efficient for unveiling the fracture behavior of polymer materials at the molecular level than other approaches with reactive force fields. We expect this approach will be utilized to accelerate the material-by-design process for thermosets by incorporate data from molecular models.

Changwoon Jang↗
NASA NTRS1970

High-temperature molding of pyrrones

High temperature pyrrones molding, discussing covalent organic bonds breakage and subsequent structural rearrangement of crosslinked polymer network

Bagley, E. B.↗
NASA NTRS1973

Radiolytic preparation of anhydrous tin (2) chloride

Anhydrous tin (2) chloride (SnCl2) is prepared by radiolysis with high energy electrons of a tin (4) chloride (SnCl4) solution in heptane. The SnCl4 is reduced to insoluble SNCl2. The energy yield, G(SnCl2), molecules of SnCl2, produced per 100 eV, increases with SnCl4 concentration from 1.6 at 0.15 M SnCl4 to 3.1 at 3.0 M SnCl4. Other parameters such as temperature total dose and beam current have little influence on G(SnCl2). The method may be used to prepare other metal halides if the higher valence, more covalent metal halide is soluble in aliphatic hydrocarbons and the lower more ionic metal halide is insoluble. The reaction mechanism is discussed; the radiolysis of both heptane and SnCl4 is involved. At high SnCl4 concentration G(SnCl2) appears to be limited by the yield of SnC13 radicals.

Philipp, W. H.↗
NASA NTRS1975

Adhesion and friction behavior of group 4 elements germanium, silicon, tin, and lead

Adhesion and friction studies were conducted with thin films of the group IV elements silicon, germanium, tin, and lead ion plated on the nickel (011) substrate. The mating surface was gold (111). Contacts were made for the elements in the clean state and with oxygen present. Adhesion and friction experiments were conducted at very light loads of 1 to 10 g. Sliding was at a speed of 0.7 mm/min. Friction results indicate that the more covalently bonded elements silicon and germanium exhibit lower adhesion and friction than the more metallic bonded tin and lead. The adhesion of gold to germanium was observed, and recrystallization of the transferred gold occurred. Plastic flow of germanium was seen with sliding. Oxygen reduced, but did not eliminate, the adhesion observed with germanium and silicon.

Buckley, D. H.↗
NASA NTRS1975

Hydrogen interactions with metals

Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

Mclellan, R. B.↗
NASA NTRS1976

Functional polymeric microspheres based on 2-hydroxyethyl methacrylate for immunochemical studies

Co gamma irradiation of 2-hydroxyethyl methacrylate in the presence or in the absence of other acrylic monomers was found to constitute an effective technique for the synthesis of hydrophilic functional microspheres in the size range of approximately 0.3 to 3 microns in diameter. The effect of monomer concentration, steric stabilization, and electrostatic interaction on the particle size was investigated. Experimental conditions were determined to obtain desired particle sizes of relatively narrow distribution. It was shown that particles may be formed without intermediate micelles, i.e., by homogeneous nucleation, and the rate of particle formation is affected primarily by the rate of particle coalescence in the initial stages of the reaction. When covalently bound to antibodies these microspheres were successfully used to label murine and human lymphocytes.

Rembaum, A.↗
NASA NTRS1976

On the ion-bombardment reduction mechanism

Recent laboratory studies of solar-wind reduction mechanisms on the lunar surface are discussed, emphasizing the effects of the electronic configurations of transition metals and the effects of covalent bonding. A series of experiments is described which involved argon ion bombardment of extremely thin targets consisting of simple halides and cyanides of first-row transition metals. Experimental results are summarized which imply that the cyanides generally have much higher reduction efficiencies than the halides. It is suggested that although reduction and sputtering take place concurrently under ion bombardment, they may actually be two independent processes.

Yin, L.↗
NASA NTRS1978

Polyglutaraldehyde - A new reagent for coupling proteins to microspheres and for labeling cell-surface receptors

Glutaraldehyde polymerized in basic aqueous solutions was found to react with low molecular weight amines, immunoglobulins and hemoglobin. The polyglutaraldehyde was covalently bound to hydrophilic microspheres. The rate of addition of proteins to the polyglutaraldehyde-derivatized microspheres was investigated spectrophotometrically as a function of pH and temperature. The reaction of polyglutaraldehyde was found to be faster than that of the monomer. The findings led to successful labeling of human lymphocyte subpopulations.

Rembaum, A.↗
NASA NTRS1978

Design of polymeric immunomicrospheres for cell labelling and cell separation

Synthesis of several classes of hydrophylic microspheres applied to cell labeling and cell separation is described. Five classes of cross-linked microspheres with functional groups such as carboxyl, hydroxyl, amide and/or pyridine groups were synthesized. These functional groups were used to bind covalently antibodies and other proteins to the surface of the microspheres. To optimize the derivatisation technique, polyglutaraldehyde immunomicrospheres were prepared and utilized. Specific populations of human and murine lymphocytes were labelled with microspheres synthesized by the emulsion of the ionizing radiation technique. The labelling of the cells by means of microspheres containing an iron core produced successful separation of B from T lymphocytes by means of a magnetic field.

Rembaum, A.↗
NASA NTRS1982

Theoretical studies of radiation effects in composite materials for space use

Tetraglycidyl 4,4'-diamino diphenyl methane epoxy cured with diamino diphenyl sulfone was used as a model compound. Computer programs were developed to calculate (1) energy deposition coefficients of protons and electrons of various energies at different depths of the material; (2) ranges of protons and electrons of various energies in the material; and (3) cumulative doses received by the composite in different geometric shapes placed in orbits of various altitudes and inclination. A preliminary study on accelerated testing was conducted and it was found that an elliptical equitorial orbit of 300 km perigee by 2750 km apogee can accumulate, in 2 years or less, enough radiation dose comparable to geosynchronous environment for 30 years. The local plasma model calculated the mean excitation energies for covalent and ionic compounds. Longitudinal and lateral distributions of excited species by electron and proton impact as well as the probability of overlapping of two tracks due to two charged particles within various time intervals were studied.

Chang, C. K.↗
NASA NTRS1983

Interatomic Auger transitions in maximal valent V and Cr compounds

The sensitivity of the intensities of the L(3)M(23)M(45) and L(3)M(45)M(45) Auger transitions toward the 3d character in the valence band has been demonstrated by using argon ion bombardment as a means of in situ reduction for the valence state of V and Cr in their maximal valent compounds. The selected V(5+) and Cr(6+) compounds were V2O5, NH4VO3, K2Cr2O7, K2CrO4, and CrO3. Auger and X-ray photoelectron spectra of fresh samples were obtained, and the samples were then subjected to ion bombardment of various durations. The subsequent spectra were recorded to monitor possible alterations due to the reduction of the cation valence state. The interatomic to intraatomic transitions of the Auger spectra transitions of the Auger spectra were observed dynamically and in situ. In particular, the intensity of the cation L(3)M(23)N(45) transitions was observed to increase dramatically with ion bombardment. The correlation between the interatomic Auger transition and covalency as well as the movements of the 3d electrons are discussed.

Yin, L. I.↗