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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

Effects of germination time on phenolics, antioxidant capacity, in vitro phenolic bioaccessibility and starch digestibility in sorghum

Summary The effects of germination time on phenolic, flavonoid, anthocyanin, antioxidant capacities, inhibition capacity of α‐amylase, bioaccessibility of phenolic and digestibility of starch in sorghum were evaluated in this study. The levels of total phenolic, flavonoid and anthocyanin in germinated sorghum for 48 h increased by 39.74%, 37.28% and 52.21%, respectively. Germination also increased the composition of phenolic, flavonoid and anthocyanin in sorghum, and their antioxidant capacity and inhibitory rates of α‐amylase. Additionally, in vitro digestion results showed that phenolic bioaccessibility increased by 10.18%, and digestibility of starch and expected glycaemic index (eGI) decreased by 13.87% and 5.26 in germinated sorghum for 48 h compared with the ungerminated sorghum. These results indicate that germination might be a green method to improve the nutritional quality of sorghum and promote the development of germinated whole‐grain food.

Li, Ren↗

Conversion of Phenolic Oil from Biomass Pyrolysis into Phenyl Esters

Bio-oil is among the most economical approaches for advanced biofuel production. However, bio-oil faces several challenges including high acidity and viscosity, poor storage, and thermal stability. This study focuses on the upgradation of lignocellulosic (corn stover and yellow pine) bio-oil derived phenolic oil (PO), produced by the autothermal fast pyrolysis, through acid-catalyzed esterification reaction. Our strategy exploits a little recognized chemistry: the Fischer esterification of PO and carboxylic acids into carboxylic acid phenyl esters (CAPE) using Dean Stark distillation. Analyses by the Folin–Ciocalteu method, Karl Fischer titration, gas chromatography flame ionization detector, and the molecular weight determination by gel permeation chromatography suggest the conversion of 50 wt% added phenolics to their corresponding CAPE. The Fourier transform infrared spectroscopy analysis confirmed the formation of new C=O and two C–O stretching bands and decrease in the intensity of phenolic-OH bands in the CAPE. The 13 C NMR analysis supports the formation of CAPE together with some unreacted precursors. A base-catalyzed ester hydrolysis experiment and mass balance calculation show an excellent agreement (within 5% range) of the equivalent weight between the produced ester and the phenyl hexanoate. Brookfield analysis indicates that CAPE has 330-fold lower viscosity than starting PO. Heating values of CAPE were higher than PO, from which they were derived (42.2 and 43.6%, respectively, for PO from pyrolysis of corn stover and yellow pine), while moisture content decreased by 98.3 and 98.7%, respectively. The CAPE, which is a phenolic analogue of methyl esters used in biodiesel, has improved stability compared to PO from which it was derived.

42 ENGINEERING↗

An evaluation of the interfacial bond properties between carbon phenolic and glass phenolic composites

The effects of moisture and surface finish on the mechanical and physical properties of the interfacial bond between the carbon/phenolic (C/P) and glass/phenolic (G/P) composite materials are presented. Four flat panel laminates were fabricated using the C/P and G/P materials. Of the four laminates, one panel was fabricated in which the C/P and G/P materials were cured simultaneously. It was identified as the cocure. The remaining laminates were processed with an initial simultaneous cure of the three C/P billets. Two surface finishes, one on each half, were applied to the top surface. Prior to the application and cure of the G/P material to the machined surface of the three C/P panels, each was subjected to the specific environmental conditioning. Types of conditioning included: (1) nominal fabrication environment, (2) a prescribed drying cycle, and (3) a total immersion in water at 160 F. Physical property tests were performed on specimens removed from the C/P materials of each laminate for determination of the specific gravity, residual volatiles and and resin content. Comparisons of results with shuttle solid rocket motor (SRM) nozzle material specifications verified that the materials used in fabricating the laminates met acceptance criteria and were representative of SRM nozzle materials. Mechanical property tests were performed at room temperature on specimens removed from the G/P, the C/P and the interface between the two materials for each laminate. The double-notched shear strength test was used to determine the ultimate interlaminar shear strength. Results indicate no appreciable difference in the C/P material of the four laminates with the exception of the cocure laminate, where 20 percent reduction in the strength was observed. The most significant effect and the ultimate strength was significantly reduced in the wet material. No appreciable variation was noted between the surface finishes in the wet laminate.

Jordan, Kelvin↗

Evaluation of the interfacial bond properties between carbon phenolic and glass phenolic composites

The effects of moisture and surface finish on the mechanical and physical properties of the interfacial bond between carbon/phenolic (C/P) and glass/phenolic (G/P) composite materials have been studied. Test results indicate that moisture substantially degrades the integrity of the interfacial bond between C/P and G/P materials. The apparent effect of the autoclave curing of the C/P material reduces the ultimate interlaminar shear length of the C/P material by 20 percent compared to the hydroclave curing of the C/P material. The variation in applied surface finishes is found to have no appreciable effect on the ultimate interlaminar shear strength of the interface in the wet laminate.

Jordan, K.↗

Characterizing Porous and Nonporous Phenolic Resins from Molecular Dynamics Simulations

Phenolic resins are an important component of many ablative heat shield materials, which protect spacecrafts from the extreme temperatures reached during atmospheric entry. Examples include the high-density Heritage Carbon Phenolic (HCP) used in the Pioneer-Venus and Galileo missions, as well as the low-density Phenolic Impregnated Carbon Ablator (PICA) used in the Mars Science Laboratory and Mars 2020 missions. Additionally, recent developments within NASA have produced the mid-density Heatshield for Extreme Entry Environment Technology (HEEET) and its derivative 3D Woven Mid-Density Carbon Phenolic (3MDCP). Unlike the nonporous phenolic in HCP, PICA and HEEET/3MDCP are fabricated by infusing preforms with diluted phenolic formulations to obtain a lower density porous matrix. Despite the importance of the phenolic phase to the material response during entry, the variation in properties of porous and nonporous phenolic is not well understood. Here, we present an investigation of porous and nonporous phenolic resins using molecular dynamics (MD) simulations. Resin cure is mimicked in the simulations through the inclusion of representative reaction templates to generate accurate models of the complex crosslinked structures. To create porous models, explicit solvent molecules are included during the cure simulations. We observe nanoscale separation of the phenolic and solvent phases, which results in significant differences in the final structures of porous and nonporous models. In addition to a quantitative assessment of the network structure and porosity, we elucidate the effects of the phenolic formulation on the final material properties. These results are compared with experimental data as appropriate.

phenolic↗

Modeling Novel Aqueous Particle and Cloud Chemistry Processes of Biomass Burning Phenols and Their Potential to Form Secondary Organic Aerosols

Phenols emitted from biomass burning contribute significantly to secondary organic aerosol (SOA) formation through the partitioning of semivolatile products formed from gas-phase chemistry and multiphase chemistry in aerosol liquid water and clouds. The aqueous-phase SOA (aqSOA) formed via hydroxyl radical (˙OH), singlet molecular oxygen ( 1 O 2 *), and triplet excited states of organic compounds ( 3 C*), which oxidize dissolved phenols in the aqueous phase, might play a significant role in the evolution of organic aerosol (OA). However, a quantitative and predictive understanding of aqSOA has been challenging. Here, we develop a stand-alone box model to investigate the formation of SOA from gas-phase ˙OH chemistry and aqSOA formed by the dissolution of phenols followed by their aqueous-phase reactions with ˙OH, 1 O 2 *, and 3 C* in cloud droplets and aerosol liquid water. Here, we investigate four phenolic compounds, i.e., phenol, guaiacol, syringol, and guaiacyl acetone (GA), which represent some of the key potential sources of aqSOA from biomass burning in clouds. For the same initial precursor organic gas that dissolves in aerosol/cloud liquid water and subsequently reacts with aqueous phase oxidants, we predict that the aqSOA formation potential (defined as aqSOA formed per unit dissolved organic gas concentration) of these phenols is higher than that of isoprene-epoxydiol (IEPOX), a well-known aqSOA precursor. Cloud droplets can dissolve a broader range of soluble phenols compared to aqueous aerosols, since the liquid water contents of aerosols are orders of magnitude smaller than cloud droplets. Further, our simulations suggest that highly soluble and reactive multifunctional phenols like GA would predominantly undergo cloud chemistry within cloud layers, while gas-phase chemistry is likely to be more important for less soluble phenols. But in the absence of clouds, the condensation of low-volatility products from gas-phase oxidation followed by their reversible partitioning to organic aerosols dominates SOA formation, while the SOA formed through aqueous aerosol chemistry increases with relative humidity (RH), approaching 40% of the sum of gas and aqueous aerosol chemistry at 95% RH for GA. Our model developments of biomass-burning phenols and their aqueous chemistry can be readily implemented in regional and global atmospheric chemistry models to investigate the aqueous aerosol and cloud chemistry of biomass-burning organic gases in the atmosphere.

09 BIOMASS FUELS↗

Explaining the structure sensitivity of Pt and Rh for aqueous-phase hydrogenation of phenol

Phenol is an important model compound to understand the thermocatalytic (TCH) and electrocatalytic hydrogenation (ECH) of biomass to biofuels. Although Pt and Rh are among the most studied catalysts for aqueous-phase phenol hydrogenation, the reason why certain facets are active for ECH and TCH is not fully understood. Herein, we identify the active facet of Pt and Rh catalysts for aqueous-phase hydrogenation of phenol and explain the origin of the size-dependent activity trends of Pt and Rh nanoparticles. Phenol adsorption energies extracted on the active sites of Pt and Rh nanoparticles on carbon by fitting kinetic data show that the active sites adsorb phenol weakly. We predict that the turnover frequencies (TOFs) for the hydrogenation of phenol to cyclohexanone on Pt(111) and Rh(111) terraces are higher than those on (221) stepped facets based on density functional theory modeling and mean-field microkinetic simulations. The higher activities of the (111) terraces are due to lower activation energies and weaker phenol adsorption, preventing high coverages of phenol from inhibiting hydrogen adsorption. We measure that the TOF for ECH of phenol increases as the Rh nanoparticle diameter increases from 2 to 10 nm at 298 K and -0.1 V vs the reversible hydrogen electrode, qualitatively matching prior reports for Pt nanoparticles. The increase in experimental TOFs as Pt and Rh nanoparticle diameters increase is due to a larger fraction of terraces on larger particles. These findings clarify the structure sensitivity and active site of Pt and Rh for the hydrogenation of phenol and will inform the catalyst design for the hydrogenation of bio-oils.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Phenolic Matrix Microcracking on the Structural Response of a 3-D Woven Thermal Protection System

The effect of microcracking in the phenolic matrix of a three-dimensional woven thermal protection system (TPS) and the resulting material stiffness reduction was studied via a comparison of finite element analysis results from a linear analysis and an iterative linear analysis. A TPS is necessary to protect space vehicles from the aerodynamic heating of planetary entry. The Heatshield for Extreme Entry Environment Technology (HEEET) project has developed a TPS for use in high heat-flux and pressure missions. The material is a dual-layer continuous dry weave, which is then infiltrated with a low-density phenolic resin matrix to form a rigid ablator. The phenolic resin matrix does not have structural load transfer requirements, and testing has shown that the phenolic resin can fully satisfy thermal requirements when the matrix contains microcracks. Due to high stresses in the through-the-thickness direction of the material, phenolic microcracks may form in the matrix material, which would result in a reduction of stiffness. An exploratory study was conducted to determine if reduction in material stiffness would change the load paths and/or decrease the structural margins. A comparison was performed between a linear finite element analysis that did not take into account phenolic microcracking and an iterative linear finite element analysis that accounted for propagation of phenolic microcracking. Four subcases using varying assumptions were analyzed and the results indicate that the assumed strength at which the phenolic microcracking propagates was the critical parameter for determining the extent of microcracking in the phenolic matrix. Phenolic microcracking does not have an adverse effect on the structural response of the test article and is not a critical failure.

Langston, Sarah L.↗

Quantifying the inhibitory impact of soluble phenolics on anaerobic carbon mineralization in a thawing permafrost peatland

The mechanisms controlling the extraordinarily slow carbon (C) mineralization rates characteristic of Sphagnum -rich peatlands (“bogs”) are not fully understood, despite decades of research on this topic. Soluble phenolic compounds have been invoked as potentially significant contributors to bog peat recalcitrance due to their affinity to slow microbial metabolism and cell growth. Despite this potentially significant role, the effects of soluble phenolic compounds on bog peat C mineralization remain unclear. We analyzed this effect by manipulating the concentration of free soluble phenolics in anaerobic bog and fen peat incubations using water-soluble polyvinylpyrrolidone (“PVP”), a compound that binds with and inactivates phenolics, preventing phenolic-enzyme interactions. CO 2 and CH 4 production rates (end-products of anaerobic C mineralization) generally correlated positively with PVP concentration following Michaelis-Menten (M.M.) saturation functions. Using M.M. parameters, we estimated that the extent to which phenolics inhibit anaerobic CO 2 production was significantly higher in the bog—62 ± 16%—than the fen—14 ± 4%. This difference was found to be more substantial with regards to methane production—wherein phenolic inhibition for the bog was estimated at 54 ± 19%, while the fen demonstrated no apparent inhibition. Consistent with this habitat difference, we observed significantly higher soluble phenolic content in bog vs. fen pore-water. Together, these findings suggest that soluble phenolics could contribute to bogs’ extraordinary recalcitrance and high (relative to other peatland habitats) CO 2 :CH 4 production ratios.

59 BASIC BIOLOGICAL SCIENCES↗

Biotransformation of Phenolics in Spent Liquor from Aqueous Ammonia Pretreatment

Spent liquors of biomass pretreatment provide a source for renewable chemical production. These liquors require treatment before being discharged; otherwise, they negatively impact the environment. Herein, spent liquors from aqueous ammonia pretreatment of poplar wood are characterized for phenolic content via liquid chromatography–mass spectrometry and nuclear magnetic resonance spectroscopy. The main phenolics are phenol, p-hydroxybenzamide (pHBAm), and p-hydroxybenzoic acid (pHBA), of which pHBAm and pHBA are produced from the ester-linked p-hydroxybenzoates in poplar wood. Phenol is produced from pHBA via decarboxylation. The potential biotransformation of the extracted phenolics into 2-pyrone-4,6-dicarboxylic acid (PDC) is assessed using an engineered strain of Novosphingobium aromaticivorans DSM12444 (PDC strain). Biotransformation of pHBAm to PDC is shown to be possible in the presence of pHBA, but not when pHBAm is the sole phenolic substrate, this is the first reported observation of N. aromaticivorans producing PDC from an aromatic amide. The phenol present is not transformed to PDC and does not inhibit PDC production. This study demonstrates that the phenolic amide in spent liquor from ammonia pretreatment can be valorized via biotransformation using N. aromaticivorans, which adds to the growing versatility of N. aromaticivorans as a microbial chassis for converting plant-derived compounds to useful products.

biomass↗

Evaluation of SRB phenolic TPS material made by an alternate vendor

Tests conducted to evaluate the adequacy of solid rocket booster (SRB) phenolic thermal protection system (TPS) material supplied by an alternate vendor chosen by United Space Boosters, Inc. (USBI), to replace the current phenolic TPS sections used thus far on the first four Shuttle flights. The phenolic TPS is applied mainly to the attach and kick rings of the solid rocket booster (SRB). Full-scale sectional models of both the attach and kick ring structure were made up with 0.0265 in. thick stainless steel thin skin covers with thermocouples on them to determine the heating rates. Such models were made up for both the forward and rear faces of the kick ring which has a different configuration on each side. The thin skins were replaced with the alternate phenolic TPS sections cut from flight hardware configuration phenolic parts as supplied by the new vendor. Two tests were performed for each configuration of the attach and kick rings and the samples were exposed to the flow for a duration that gave a heat load equivalent to that obtained in the series of runs made for the current line of phenolic TPS. The samples performed very well with no loss of any phenolic layers. The post-test samples looked better than those used to verify the current phenolic TPS.

Karu, Z. S.↗

Standardization of the carbon-phenolic materials and processes. Vol. 1: Experimental studies

Carbon-phenolic composite materials are used as ablative material in the solid rocket motor nozzle of the Space Shuttle. The nozzle is lined with carbon cloth-phenolic resin composites. The nominal effects of the completely consumed solid propellant on the carbon-phenolic material are given. The extreme heat and erosion of the burning propellant are controlled by the carbon-phenolic composite by ablation, the heat and mass transfer process in which a large amount of heat is absorbed by sacrificially removing material from the nozzle surface. Phenolic materials ablate with the initial formation of a char. The depth of the char is a function of the heat conduction coefficient of the composite. The char layer is a very poor heat conductor so it protects the underlying phenolic composite from the high heat of the burning propellant. The nozzle component ablative liners (carbon cloth-phenolic composites) are tape wrapped, hydroclave and/or autoclave cured, machined, and assembled. The tape consists of a prepreg broadcloth. The materials flow sheet for the nozzle ablative liners is shown. The prepreg is a three component system: phenolic resin, carbon cloth, and carbon filler. This is Volume 1 of two, Experimental Studies.

Hall, William B.↗

Standardization of the carbon-phenolic materials and processes. Vol. 2: Test methods and specifications

Carbon-phenolic composite materials are used in the ablation process in the nozzles of the Space Shuttle Main Engine. The nozzle is lined with carbon cloth-phenolic resin composites. The extreme heat and erosion of the burning propellant are controlled by the carbon-phenolic composite by means of ablation, a heat and mass transfer process in which a large amount of heat is dissipated by sacrificailly removing material from a surface. Phenolic materials ablate with the initial formation of a char. The depth of the char is a function of the heat conduction coefficient of the composite. The char layer is a poor conductor so it protects the underlying phenolic composite from the high heat of the burning propellant. The nozzle component ablative liners (carbon cloth-phenolic resin composites) are tape wrapped, hydroclave and/or autoclave cured, machined and assembled. The tape consists of prepreg broadcloth. The materials flow sheet for the nozzle ablative liners is given. The prepreg is a three component system: phenolic resin, carbon cloth, and carbon filler. This is Volume 2 of the report, Test Methods and Specifications.

Hall, William B.↗

ODC-Free Solvent Implementation for Phenolics Cleaning

During phenolic liner manufacture, resin-impregnated (pre-preg) bias tape of silica, glass, or carbon cloth is tape-wrapped, cured, machined, and then wiped with 1,1,1 tri-chloroethane (TCA) to remove contaminants that may have been introduced during machining and handling. Following the TCA wipe, the machined surface is given a resin wet-coat and over-wrapped with more prepreg and cured. A TCA replacement solvent for these wiping operations must effectively remove both surface contaminants, and sub-surface oils and greases while not compromising the integrity of this interface. Selection of a TCA replacement solvent for phenolic over-wrap interface cleaning began with sub-scale compatibility tests with cured phenolics. Additional compatibility tests included assessment of solvent retention in machined phenolic surfaces. Results from these tests showed that, while the candidate solvent did not degrade the cured phenolics, it was retained in higher concentrations than TCA in phenolic surfaces. This effect was most pronounced with glass and silica cloth phenolics with steep ply angles relative to the wiped surfaces.

Wurth, Laura↗

Phenols in hydrothermal petroleums and sediment bitumen from Guaymas Basin, Gulf of California

The aliphatic, aromatic and polar (NSO) fractions of seabed petroleums and sediment bitumen extracts from the Guaymas Basin hydrothermal system have been analyzed by gas chromatography and gas chromatography-mass spectrometry (free and silylated). The oils were collected from the interiors and exteriors of high temperature hydrothermal vents and represent hydrothermal pyrolyzates that have migrated to the seafloor by hydrothermal fluid circulation. The downcore sediments are representative of both thermally unaltered and thermally altered sediments. The survey has revealed the presence of oxygenated compounds in samples with a high degree of thermal maturity. Phenols are one class of oxygenated compounds found in these samples. A group of methyl-, dimethyl- and trimethyl-isoprenoidyl phenols (C27-C29) is present in all of the seabed NSO fractions, with the methyl- and dimethyl-isoprenoidyl phenols occurring as major components, and a trimethyl-isoprenoidyl phenol as a minor component. A homologous series of n-alkylphenols (C13-C33) has also been found in the seabed petroleums. These phenols are most likely derived from the hydrothermal alteration of sedimentary organic matter. The n-alkylphenols are probably synthesized under hydrothermal conditions, but the isoprenoidyl phenols are probably hydrothermal alteration products of natural product precursors. The suites of phenols do not appear to be useful tracers of high temperature hydrothermal processes.

Non-NASA Center↗

Comparison of Failure Modes in 2-D and 3-D Woven Carbon Phenolic Systems

NASA Ames Research Center is developing Woven Thermal Protection System (WTPS) materials as a new class of heatshields for entry vehicles (Stackpoole). Currently, there are few options for ablative entry heatshield materials, none of which is ideally suited to the planetary probe missions currently of interest to NASA. While carbon phenolic was successfully used for the missions Pioneer Venus and Galileo (to Jupiter), the heritage constituents are no longer available. An alternate carbon phenolic would need to be qualified for probe missions, which is most efficient at heat fluxes greater than those currently of interest. Additional TPS materials such as Avcoat and PICA are not sufficiently robust for the heat fluxes required. As a result, there is a large TPS gap between the materials efficient at very high conditions (carbon phenolic) and those that are effective at low-moderate conditions (all others). Development of 3D Woven TPS is intended to fill this gap, targeting mid-density weaves that could with withstand mid-range heat fluxes between 1100 W/sq cm and 8000 W/sq cm (Venkatapathy (2012). Preliminary experimental studies have been performed to show the feasibility of WTPS as a future mid-range TPS material. One study performed in the mARC Jet Facility at NASA Ames Research Center characterized the performance of a 3D Woven TPS sample and compared it to 2D carbon phenolic samples at ply angles of 0deg, 23.5deg, and 90deg. Each sample contained similar compositions of phenolic and carbon fiber volume fractions for experimental consistency. The goal of this study was to compare the performance of the TPS materials by evaluating resulting recession and failure modes. After exposing both samples to similar heat flux and pressure conditions, the 2D carbon phenolic laminate was shown to experience significant delamination between layers and further pocketing underneath separated layers. The 3D Woven TPS sample did not experience the delamination or pocketing failure modes because z-fibers in the through-thickness direction provided extra reinforcement to hold material layers together. Therefore, the benefit of using a 3D weave architecture was shown to alleviate failure modes experienced by a 2D laminate sample of similar material composition. In summary this poster reviews the thermal response performance comparisons drawn between a 3D Woven TPS sample and 2D Carbon Phenolic samples after performing rigorous heating experiments in the mARC facility at NASA Ames. Although the mARC Facility is still in its developmental stages, researchers expect similar trends in failure modes observed from large scale arc jet facilities. This work helps demonstrate the viability of 3D Woven TPSs as a new TPS option for future atmospheric entry missions.

Rossman, Grant A.↗