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At least 109 records · Page 6

LaRC-TPI 1500 composites fabricated using an aqueous slurry process

Unidirectional composites from unsized carbon fiber and LaRC-TPI matrix material were fabricated using 'high flow' and'medium flow' grades of the LaRC-TPI 1500 series of polyimides. Prepreg was drum-wound from a slurry composed of the polyimide powder dispersed in an aqueous solution of LaRC-TPI poly(amide acid). The poly(amide acid) was found to be an effective binding agent in the prepregging process. Composite short beam shear and flexure properties were measured at room and elevated temperatures (to 177 C) with both dry and moisture-saturated specimens. The mechanical properties observed for composites fabricated from the high and medium flow materials were virtually identical. Additionally, double cantilever beam measurements showed nearly equivalent fracture toughness for the two composite materials.

Towell, Timothy W.↗

Synthesis and characterization of polyamide-imides

The synthesis and characterization of polyamide-imides (PAI) derived from four different dianhydrides and three isomers of diaminobenzanilide are discussed with emphasis on the effect of combining an amide linkage in the diamine portion with other bridging groups in the dianhydride portion of the polymer backbone. It is noted that all of the amide-imide polymers exhibit high-glass transition temperatures, high thermooxidative stability, and a relatively good solvent resistance. These aromatic PAIs are characterized by high thermal stability due to chain stiffness, crystallinity, and intermolecular hydrogen bonding, and are considered to be good candidates as high-temperature films, coatings, and fibers for aerospace applications.

Dezern, James F.↗

Enhancement of molecular weight build up in polyimides using ether solvents

Two linear polyimides were prepared in various ether and amide solvents. The inherent viscosity was then monitored as a function of time. The polymers made in the ether solvents consistently gave higher inherent viscosities, and thus molecular weights, than the same polymers made in the amide solvents. This molecular weight buildup is attributed to the unique solvation mechanism of the ether solvents which enhances the basicity of the amines via hydrogen bonding.

Egli, Annemarie H.↗

Processing and properties of fiber reinforced polymeric matrix composites: I. IM7/LARC(TM)-PETI-7 polyimide composites

A phenylethynyl terminated imide oligomer formed from the reaction of benzophenone tetracarboxylic acid dianhydride, an 75:25 molar ratio of 4,4'-oxydianiline and meta-phenylenediamine and 4-phenylethynylphthalic anhydride as the endcapper at a theoretical number average molecular weight (Mn) of approximately 3,700 g/mol was evaluated as a composite resin matrix. A glass transition temperature (Tg) of 315 deg C was reached after 250 deg C/1 hr annealing of the matrix resin. Unidirectional prepreg was made by coating an N-methylpyrrolidinone solution of the amide acid oligomer onto unsized IM7 graphite fibers. The thermal and rheological properties and the solvent/volatile depletion rates of the amide acid/NMP system were determined. This information was used to successfully design a molding cycle for composite fabrication. Composites molded under 800 Psi at 371 C consistently yielded good consolidation as measured by C-scan and optical photomicrography. The composite's short beam shear strength (SBS), longitudinal and transverse flexural strengths and moduli were measured at various temperatures. These composites exhibited excellent room temperature (RT) longitudinal flexural strength and modulus and RT SBS strength retention at 177 C.

Hou, Tan-Hung↗

Evaluation of Boundary-Enhancement Additives for Perfluoropolyethers

Six additives were synthesized and evaluated as boundary lubrication enhancers for perfluoropolyethers. These additives included a phosphonate, a thiophosphonate, a beta-diketone, a benzothiazole, an amide and a sulfite. These additives were evaluated in a vacuum four-ball apparatus, at a one weight percent concentration in a perfluoropolyether based on hexafluoropropene oxide. Tests were performed in vacuum (less than 5.0 x 10(exp 6) Torr), at room temperature (approx. 23 C), at an initial Hertzian stress of 3.5 GPa (200N load), and a sliding velocity of 28.8 mm/sec (100 rpm). Infrared (IR) and Raman spectroscopies were used to analyze the 440 C specimens after testing. Wear rates for each formulation were determined from the slope of wear volume as a function of sliding distance. All additives yielded reductions in mean wear rates of at least 55 percent, with the exception of the benzothiazole which had no effect. Two of the additives, an amide and a sulfite, reduced the mean wear rate by at least 80 percent. IR and Raman analysis indicated the severity of wear can be correlated to the amount of surface fluorinated polymeric acid species (R(sub f)COOH) and amorphous carbon, in and around the wear scar.

Shogrin, Bradley A.↗

Fabrication Of Carbon-Boron Reinforced Dry Polymer Matrix Composite Tape

Future generation aerospace vehicles will require specialized hybrid material forms for component structure fabrication. For this reason, high temperature composite prepregs in both dry and wet forms are being developed at NASA Langley Research Center (LaRC). In an attempt to improve compressive properties of carbon fiber reinforced composites, a hybrid carbon-boron tape was developed and used to fabricate composite laminates which were subsequently cut into flexural and compression specimens and tested. The hybrid material, given the designation HYCARB, was fabricated by modifying a previously developed process for the manufacture of dry polymer matrix composite (PMC) tape at LaRC. In this work, boron fibers were processed with IM7/LaRC(TradeMark)IAX poly(amide acid) solution-coated prepreg to form a dry hybrid tape for Automated Tow Placement (ATP). Boron fibers were encapsulated between two (2) layers of reduced volatile, low fiber areal weight poly(amide acid) solution-coated prepreg. The hybrid prepreg was then fully imidized and consolidated into a dry tape suitable for ATP. The fabrication of a hybrid boron material form for tow placement aids in the reduction of the overall manufacturing cost of boron reinforced composites, while realizing the improved compression strengths. Composite specimens were press-molded from the hybrid material and exhibited excellent mechanical properties.

Belvin, Harry L.↗

Composite Properties of Polyimide Resins Made From "Salt-Like" Solution Precursors

Recent work in high temperature materials at NASA Langley Research Center (LaRC (trademark)) have led to the development of new polyimide resin systems with very attractive properties. The majority of the work done with these resin systems has concentrated on determining engineering mechanical properties of composites prepared from a poly(amide acid) precursor. Three NASA Langley-developed polyimide matrix resins, LaRC (trademark) -IA, LaRC (trademark) -IAX, and LaRC (trademark) -8515, were produced via a salt-like process developed by Unitika Ltd. The 'salt-like' solutions (sixty-five percent solids in NMP) were prepregged onto Hexcel IM7 carbon fiber using the NASA LaRC Multipurpose Tape Machine. Process parameters were determined and composite panels fabricated. Mechanical properties are presented for these three intermediate modulus carbon fiber/polyimide matrix composites and compared to existing data on the same polyimide resin systems and IM7 carbon fiber manufactured via poly(amide acid) solutions (thirty-five percent solids in NMP). This work studies the effects of varying the synthetic route on the processing and mechanical properties of polyimide composites.

Cano, Roberto J.↗

Oxidative acylation using thioacids

Several important prebiotic reactions, including the coupling of amino acids into polypeptides by the formation of amide linkages, involve acylation. Theae reactions present a challenge to the understanding of prebiotic synthesis. Condensation reactions relying on dehydrating agents are either inefficient in aqueous solution or require strongly acidic conditions and high temperatures. Activated amino acids such as thioester derivatives have therefore been suggested as likely substrates for prebiotic peptide synthesis. Here we propose a closely related route to amide bond formation involving oxidative acylation by thioacids. We find that phenylalanine, leucine and phenylphosphate are acylated efficiently in aqueous solution by thioacetic acid and an oxidizing agent. From a prebiotic point of view, oxidative acylation has the advantage of proceeding efficiently in solution and under mild conditions. We anticipate that oxidative acylation should prove to be a general method for activating carboxylic acids, including amino acids.

Non-NASA Center↗

Fiber reinforced thermoplastic resin matrix composites

Polyimide polymer composites having a combination of enhanced thermal and mechanical properties even when subjected to service temperatures as high as 700.degree. F. are described. They comprise (a) from 10 to 50 parts by weight of a thermoplastic polyimide resin prepared from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and (b) from 90 to 50 parts by weight of continuous reinforcing fibers, the total of (a) and (b) being 100 parts by weight. Composites based on polyimide resin formed from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane and pyromellitic dianhydride and continuous carbon fibers retained at least about 50% of their room temperature shear strength after exposure to 700.degree. F. for a period of 16 hours in flowing air. Preferably, the thermoplastic polyimide resin is formed in situ in the composite material by thermal imidization of a corresponding amide-acid polymer prepared from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. It is also preferred to initially size the continuous reinforcing fibers with up to about one percent by weight of an amide-acid polymer prepared from 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane. In this way imidization at a suitable elevated temperature results in the in-situ formation of a substantially homogeneous thermoplastic matrix of the polyimide resin tightly and intimately bonded to the continuous fibers. The resultant composites tend to have optimum thermo-mechanical properties.

Jones, Robert J.↗

Fabrication of Polyimide-Matrix/Carbon and Boron-Fiber Tape

The term HYCARB denotes a hybrid composite of polyimide matrices reinforced with carbon and boron fibers. HYCARB and an improved process for fabricating dry HYCARB tapes have been invented in a continuing effort to develop lightweight, strong composite materials for aerospace vehicles. Like other composite tapes in this line of development, HYCARB tapes are intended to be used to build up laminated structures having possibly complex shapes by means of automated tow placement (ATP) - a process in which a computer-controlled multiaxis machine lays down prepreg tape or tows. The special significance of the present process for making dry HYCARB for ATP is that it contributes to the reduction of the overall cost of manufacturing boron-reinforced composite-material structures while making it possible to realize increased compression strengths. The present process for making HYCARB tapes incorporates a "wet to dry" process developed previously at Langley Research Center. In the "wet to dry" process, a flattened bundle of carbon fiber tows, pulled along a continuous production line between pairs of rollers, is impregnated with a solution of a poly(amide acid) in N-methyl-2-pyrrolidinone (NMP), then most of the NMP is removed by evaporation in hot air. In the present case, the polyamide acid is, more specifically, that of LaRC. IAX (or equivalent) thermoplastic polyimide, and the fibers are, more specifically, Manganite IM7 (or equivalent) polyacrylonitrile- based carbon filaments that have a diameter of 5.2 m and are supplied in 12,000-filament tows. The present process stands in contrast to a prior process in which HYCARB tape was made by pressing boron fibers into the face of a wet carbon-fiber/ poly(amide acid) prepreg tape . that is, a prepreg tape from which the NMP solvent had not been removed. In the present process, one or more layer(s) of side-by-side boron fibers are pressed between dry prepreg tapes that have been prepared by the aforementioned gwet to dry h process. The multilayer tape is then heated to imidize the matrix material and remove most of the remaining solvent, and is pressed to consolidate the multiple layers into a dense tape. For tests, specimens of HYCARB tapes and laminated composite panels made from HYCARB tape were prepared as follows: HYCARB tapes were fabricated as described above. Each panel was made by laying down ten layers of tape, containing, variously, one, two, or three boron-fiber plies and the remainder carbon- fiber-only plies (see figure). Each panel was made by laying down ten layers of tape. Each panel was then cured by heating to a temperature of 225 C for 15 minutes, then pressing at 200 psi (A1.4 MPa) while heating to 371 C, holding at 371 C for 1 hour, then continuing to hold pressure during cooling. Control specimens that were otherwise identical except that they did not contain boron fibers also were prepared. In room-temperature flexural tests, the HYCARB specimens performed comparably to the control specimens; in room-temperature, open-hole compression tests, the HYCARB specimens performed slightly better, by amounts that increased with boron content.

Belvin, Harry L.↗

Tholins as Coloring Agents on Pluto and Other Icy Solar System Bodies

Tholins are refractory organic solids of complex structure and high molecular weight, with a wide range of color ranging from yellow and orange to dark red, and through tan to black. They are made in the laboratory by energy deposition (photons or charged particles) in gases and ices containing the simple molecules (e.g., N2, CH4, CO) found in planetary atmospheres or condensed on planetary surfaces. They are widely implicated in providing the colors and albedos, particularly in the region 0.3-1.0 microns, of several outer Solar System bodies, including Pluto, as well as aerosols in planetary atmospheres such as Titan. Recent color images of Pluto with the New Horizons spacecraft show concentrations of coloring agent(s) in some regions of the surface, and apparent near-absence in other regions. Tholins that may to some degree represent surface chemistry on Pluto have been synthesized in the laboratory by energetic processing of mixtures of the ices (N2, CH4, CO) known on Pluto's surface, or the same molecules in the gas phase. Details of the composition and yield vary with experimental conditions. Chemical analysis of Pluto ice tholins shows evidence of amides, carboxylic acids, urea, carbodiimides, and nitriles. Aromatic/olefinic, amide, and other functional groups are identified in XANES analysis. The ice tholins produced by e- irradiation have a higher concentration of N than UV ice tholins, with N/C approx. 0.9 (versus approx. 0.5 for UV tholins) and O/C approx.0.2. Raman spectra of the electron tholin show a high degree of structural disorder, while strong UV fluorescence indicates a large aromatic content. EUV photolysis of a Pluto gaseous atmosphere analog yields pale yellow solids relatively transparent in the visual, and with aliphatic CH bonds prominent in IR spectra. This or similar material may be responsible for Pluto's hazes.

Tholins↗

Solvents and slurries comprising a poly(carboxylic acid) binder for silicon electrode manufacture

An silicon-containing electrode is formed by coating a silicon-containing slurry onto a conductive current collector. The slurry comprises a binder solution comprising a poly(carboxylic acid) binder dissolved in a mixed solvent system comprising an amide solvent of Formula I, as described herein, and a second solvent which can be water and/or an organic solvent. The binder preferably comprises poly(acrylic acid). The mixed solvent system comprises about 10 to about 99 vol % of the amide solvent of Formula I. The binder solution is utilized as a solvent for a slurry of silicon-containing particles for preparing the silicon-containing electrode. The slurries comprising the mixed solvent system have higher viscosity and are more stable than slurries containing the same concentrations of silicon particles, carbon particles, and binder in water as the sole solvent.

Zhang, Lu↗

Synthesis of Perdeuterated Alkyl Amines/Amides with Pt/C as Catalyst under Mild Conditions

A convenient method for the synthesis of perdeuterated alkyl amides/amines is disclosed. Perdeuterated acetyl amides can be achieved by a hydrogen–deuterium (H/D) exchange protocol with Pt/C as a catalyst and D 2 O as a deuterium source under mild conditions. Further, after removal or reduction of the acetyl group, this protocol can provide perdeuterated primary, secondary, and tertiary amines, which are difficult to achieve via other methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enantioselective Hydrodifluoroalkylation of Alkenes with Conformationally Tuned Peptidyl Hydrogen Atom Transfer Catalysts

Here, we report the enantioselective hydrodifluoroalkylation of alkenes proceeding via an asymmetric hydrogen atom transfer (HAT) event catalyzed by thiol-containing tetrapeptides. Photocatalytic generation of a difluoroacetyl radical followed by carbon–carbon bond formation results in a prochiral carbon-centered radical that engages with the chiral catalyst. A trialkylamine reductant is proposed to turn over the catalyst in this net-reductive transformation. Notably, incorporating an (S)-β-methyl-substituted cysteine as the N-terminal residue improved selectivity relative to that of the native N-terminal cysteine (Cys) residue, and X-ray crystallographic analysis supports the conformational underpinning of this effect. A range of enantioenriched γ-substituted amides were synthesized in up to a 96:4 enantiomeric ratio, demonstrating the broad functional group tolerance of this method. Models accounting for asymmetric induction are proposed with supporting DFT calculations.

08 HYDROGEN↗

Conductive Liquid Metal Vitrimer Composites for Reconfigurable and Recyclable Flexible Electronics

Liquid metal (LM) elastomer composites exhibit excellent functionality for stretchable electronics and wearables, but limited recycling and reuse pathways constrain their sustainable use. Here, to address these challenges amid growing concerns over electronic waste, a conductive LM–vitrimer composite is presented that enables recyclable and reconfigurable electronics. This soft and stretchable composite features uniformly distributed LM inclusions that enhance thermal conductivity by 6.53× and enable the formation of conductive traces with electrical self-healing, while the vitrimer provides structural restoration. The dynamic covalent bonds of the vitrimer matrix are leveraged for both reprocessing the composite and chemically recovering 94% of the LM. This liquid-state filler slightly reduces the vitrimer's stiffness to 2.63 MPa (≈20% lower), while maintaining its high stretchability (>135% strain) and thermal stability. It is further examined how ultrasonicated LM inclusions interact with the vitrimer matrix and demonstrate the composite's self-healing and recyclability through two distinct approaches: 1) thermomechanical reprocessing, which restores fragmented composites under heat and compression for circuit reconfiguration; and 2) chemical recycling, which recovers the embedded LM for reuse in fabricating new composites and redesigned circuitry. With the integration of recyclability and diverse functional capabilities, LM–vitrimer composites emerge as a promising material platform for sustainable, flexible electronics.

Han, Youngshang [Univ. of Washington, Seattle, WA ↗

Double Hydroxide Nanocatalysts for Urea Electrooxidation Engineered toward Environmentally Benign Products

Abstract Recent advancements in the electrochemical urea oxidation reaction (UOR) present promising avenues for wastewater remediation and energy recovery. Despite progress toward optimized efficiency, hurdles persist in steering oxidation products away from environmentally unfriendly products, mostly due to a lack of understanding of structure‐selectivity relationships. In this study, the UOR performance of Ni and Cu double hydroxides, which show marked differences in their reactivity and selectivity is evaluated. CuCo hydroxides predominantly produce N 2 , reaching a current density of 20 mA cm geo −2 at 1.04 V – 250 mV less than NiCo hydroxides that generate nitrogen oxides. A collection of in‐situ spectroscopies and scattering experiments reveal a unique in situ generated Cu (2‐x)+ ‐OO −• active sites in CuCo, which initiates nucleophilic substitution of NH 2 from the amide, leading to N‐N coupling between * NH on Co and Cu. In contrast, the formation of nitrogen oxides on NiCo is primarily attributed to the presence of high‐valence Ni 3+ and Ni 4+ , which facilitates N‐H activation. This process, in conjunction with the excessive accumulation of OH − ions on Jahn‐Teller (JT) distorted Co sites, leads to the generation of NO 2 − as the primary product. This work underscores the importance of catalyst composition and structural engineering in tailoring innocuous UOR products.

36 MATERIALS SCIENCE↗

Rational Design of Weakly‐Solvating Molecules for Salt‐In‐Pre‐Ionic‐Liquid Electrolytes for Li Metal Batteries

Lithium metal batteries (LMBs) promise step‐changes in energy densities but suffer from poor cycle life due to unstable electrolyte‐lithium interfaces. Conventional carbonate electrolytes exhibit excessive lithium‐ion solvation and low oxidative stability, leading to rapid capacity loss. Herein, we report a rationally designed weakly‐solvating cyclic sulfonamide, 1‐trifluoromethanesulfonyl)amide pyrrolidine (TFMSPyr), which integrates an electron‐withdrawing trifluoromethanesulfonyl functional group at pyrrolidinic‐N. TFMSPyr acts as a pre‐ionic‐liquid solvent that forms intrinsically localized, anion‐dominated solvation, coupling molecular architecture, solvation topology, and transport dynamics. As a result, LiFSI based salt‐in‐pre‐ionic‐liquid (SIPIL) electrolytes exhibit high lithium‐ion transference number, oxidative stability > 5 V versus Li/Li + and anion‐derived solid electrolyte interphases (SEI). Li||Cu cells with SIPIL deliver a first cycle Coulombic efficiency (CE) of ≈ 99% with average CE of 99.2% for 100 cycles, and lithium half‐cells with lithium iron phosphate (LFP) cathode exhibit 82% capacity retention after 400 cycles with CE of 99.98%. In anode‐free full cells, 95% of initial capacity is retained after 63 cycles with an average CE of 99.5%. These results demonstrate that molecular engineering of solvents offers a powerful pathway to stabilize lithium metal interfaces and enable practical Anodeless LMBs.

25 ENERGY STORAGE↗

Is a Malleable Active Site Loop the Key to High Substrate Promiscuity? Hybrid, Biocatalytic Route to Structurally Diverse Taxoid Side Chains with Remarkable Dual Stereocontrol

Abstract These studies reveal the first structure ofClostridium acetobutylicumalcohol dehydrogenase (CaADH), a protein exhibiting remarkable substrate promiscuity and stereochemical fidelity. The CaADH enzyme is utilized here for synthesizing 20 potential aryl isoserine side chains for the Taxotere family of tubulin‐binding chemotherapeutics. The approach involves dynamic reductive kinetic resolution (DYRKR) upon the corresponding α‐chloro‐β‐keto esters, showing high D‐synstereoselectivity, including those leading to the clinically relevant milataxel (Ar = 2‐furyl) and simotaxel (Ar = 2‐thienyl) side chains. Furthermore, various cross‐coupling chemistries performed on thep‐bromophenyl isoserine side chain significantly enhance the structural diversity of the taxoid side chain library obtained (16 additional taxoid side chains). The CaADH structure is notable: (i) the nicotinamide cofactor is bound in ananti‐conformation, with the amide carbonyl occupying the ketone binding pocket, and (ii) a flexible loop near the active site likely contributes to the remarkable substrate promiscuity observed in CaADH. We present our perspective on the dynamic nature of the CaADH active site through molecular dynamics simulation, proposing a halogen bonding model as a potential mechanism for the remarkable selectivity for an (S)‐configured C─Cl bond, in addition to the D‐facial selectivity, demonstrated across 20 diverse substrates by this remarkable short‐chain dehydrogenase enzyme.

Chemistry↗