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At least 415 records · Page 23
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Molecular level characterization of wildfire aerosol induced changes to plant health and value

The potential impacts of wildfire smoke on plant health and value are of increasing concern, due both to increasing awareness, and more frequent wildfire events. Wildfires produce substantial amounts of atmospheric pollution in smoke and particulate matter which can travel thousands of miles. These smoke events can blanket entire agricultural regions and cause impacts to plant development. One notable example of this is ‘smoke taint’ in wine, where vines, exposed to smoke, absorb many small volatile phenolic (VP) compounds. These VPs can be metabolized (glycosylated) and transported throughout the plant. Later, during downstream processing (fermentation of the grape musts), these glycosylated VPs can be hydrolyzed to re-release and volatilize the aroma-active phenolic compounds. The final product, thus, smells of smoke. Despite the obvious commercial and general research interests here, the nature of wildfire impacts on plant health are incompletely understood. Using established metabolomics and organic matter (aerosol) characterization methods, the overall aim of this proposal is thus to study wildfire smoke impacts on plant health and value, in the context of a model system (V. vinifera). This project closed early, and this report reflects some of the limited work conducted prior to conclusions. Specifically, this report discusses some sample preparation and initial MALDI-mass spectrometry analysis.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Inexpensive and durable aerogel-based VIP cores

The goal of this project was development of low-cost aerogels to be used as cores of Vacuum Insulated Panels (VIP). The specific aims were: 1. Aerogels to be based on phenolic chemistry to minimize flammability. 2. Aerogels to be in monolithic form and to have mechanical properties sufficient to allow their use as cores of VIPs without collapsing after evacuation. 3. Aerogels to have a cost per kg lower than the cost of fumed silica, one of the most common VIP cores. The achievements are: 1. Phenolic aerogels have been fabricated in monolithic form with thermal conductivity of 0.023 W/m·K, density ~ 0.25 g/cm 3 and a modulus of compression > 10 MPa. The aerogels can withstand the stresses of VIP evacuation without any appreciable deformation. 2. Drying of aerogels was carried in the initial stages of the project via sublimation of frozen solvents, following the procedure described in M. F. Bertino and T. Selden, “Fabrication of Aerogels and Aerogel Composites by Ambient Pressure Sublimation of Frozen Solvents”, PCT/US20/39485. Monoliths as large as 30 x 30 x 2 cm can be fabricated with the proprietary ambient fabrication technique which are free of cracks and warping. 3. Cost analysis was carried out and refined multiple times, cost drivers were identified, and the fabrication procedure was streamlined. Our cost model yields an aerogel cost of $\$$5.78/kg, which compares well with the price of fumed silica ($\$$6.2/kg FOB New York as of March 2023). 4. The monoliths can be cut into custom shapes and used as VIP cores. Cores fabricated with our technique have a thermal conductivity λ = 0.011 W/m·K at a pressure >10 mbar. 5. A variant of the technology yielded fireproof materials, described in M. F. Bertino, T. Moon, G. Waller, J. Ko and D. Clifford, “Fireproof thermal insulation”, Provisional Patent Application 63/415,386. 6. A spin-off company was created (ThermaGel Innovations, Inc.) which licensed technologies developed under this award. PI Bertino is a board member of the newco which is now raising capital to build a pilot plant.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Organoboron Based Antioxidants

Earth’s environment can be considered especially harsh due to the cyclic exposure of heat, moisture, oxygen, and ultraviolet (UV) and visible light. Polymer-derived materials subjected to these conditions over time often exhibit symptoms of degradation and deterioration, ultimately leading to accelerated material failure. To combat this, chemical additives known as antioxidants are often used to delay the onset of weathering and oxidative degradation. Phenol-derived antioxidants have been used for decades due to their excellent performance and stability; unfortunately, concerns regarding their toxicity and leaching susceptibility have driven researchers to identify novel solutions to replace phenolic antioxidants. Herein, we report on the antioxidant efficacy of organoborons, which have been known to exhibit antioxidant activity in plants and animals. Four different organoboron molecules were formulated into epoxy materials at various concentrations and subsequently cured into thermoset composites. Their antioxidant performance was subsequently analyzed via thermal, colorimetric, and spectroscopic techniques. Generally, thermal degradation and oxidation studies proved inconclusive and ambiguous. However, aging studies performed under thermal and UV-intensive conditions showed moderate to extreme color changes, suggesting poor antioxidant performance of all organoboron additives. Infrared spectroscopic analysis of the UV aged samples showed evidence of severe material oxidation, while the thermally aged samples showed only slight material oxidation. Solvent extraction experiments showed that even moderately high organoboron concentrations show negligible leaching susceptibility, confirming previously reported results. This finding may have benefits in applications where additive leaching may cause degradation to sensitive materials, such as microelectronics and other materials science related areas.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Modification of plant cell walls with hydroxycinnamic acids by BAHD acyltransferases

In the last decade it has become clear that enzymes in the “BAHD” family of acyl-CoA transferases play important roles in the addition of phenolic acids to form ester-linked moieties on cell wall polymers. We focus here on the addition of two such phenolics—the hydroxycinnamates, ferulate and p -coumarate—to two cell wall polymers, glucuronoarabinoxylan and to lignin. The resulting ester-linked feruloyl and p-coumaroyl moities are key features of the cell walls of grasses and other commelinid monocots. The capacity of ferulate to participate in radical oxidative coupling means that its addition to glucuronoarabinoxylan or to lignin has profound implications for the properties of the cell wall – allowing respectively oxidative crosslinking to glucuronoarabinoxylan chains or introducing ester bonds into lignin polymers. A subclade of ~10 BAHD genes in grasses is now known to (1) contain genes strongly implicated in addition of p -coumarate or ferulate to glucuronoarabinoxylan (2) encode enzymes that add p -coumarate or ferulate to lignin precursors. Here, we review the evidence for functions of these genes and the biotechnological applications of manipulating them, discuss our understanding of mechanisms involved, and highlight outstanding questions for future research.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Mitigation of Gaseous Emissions from Swine Manure with the Surficial Application of Biochars

Environmental impact associated with odor and gaseous emissions from animal manure is one of the challenges for communities, farmers, and regulatory agencies. Microbe-based manure additives treatments are marketed and used by farmers for mitigation of emissions. However, their performance is difficult to assess objectively. Thus, comprehensive, practical, and low-cost treatments are still in demand. We have been advancing such treatments based on physicochemical principles. The objective of this research was to test the effect of the surficial application of a thin layer (¼ inches; 6.3 mm) of biochar on the mitigation of gaseous emissions (as the percent reduction, % R) from swine manure. Two types of biochar were tested: highly alkaline and porous (HAP) biochar made from corn stover and red oak (RO), both with different pH and morphology. Three 30-day trials were conducted with a layer of HAP and RO (2.0 & 1.65 kg∙m−2, respectively) applied on manure surface, and emissions of ammonia (NH3), hydrogen sulfide (H2S), greenhouse gases (GHG), and odorous volatile organic compounds (VOCs) were measured. The manure and biochar type and properties had an impact on the mitigation effect and its duration. RO significantly reduced NH3 (19–39%) and p-cresol (66–78%). H2S was mitigated (16~23%), but not significantly for all trials. The phenolic VOCs had relatively high % R in most trials but not significantly for all trials. HAP reduced NH3 (4~21%) and H2S (2~22%), but not significantly for all trials. Significant % R for p-cresol (91~97%) and skatole (74~95%) were observed for all trials. The % R for phenol and indole ranged from (60~99%) and (29~94%) but was not significant for all trials. The impact on GHGs, isobutyric acid, and the odor was mixed with some mitigation and generation effects. However, larger-scale experiments are needed to understand how biochar properties and the dose and frequency of application can be optimized to mitigate odor and gaseous emissions from swine manure. The lessons learned can also be applicable to surficial biochar treatment of gaseous emissions from other waste and area sources.

Meiirkhanuly, Zhanibek↗
DOE OSTI2024

An Engineered Laccase from Fomitiporia mediterranea Accelerates Lignocellulose Degradation

Laccases from white-rot fungi catalyze lignin depolymerization, a critical first step to upgrading lignin to valuable biodiesel fuels and chemicals. In this study, a wildtype laccase from the basidiomycete Fomitiporia mediterranea (Fom_lac) and a variant engineered to have a carbohydrate-binding module (Fom_CBM) were studied for their ability to catalyze cleavage of β-O-4′ ether and C–C bonds in phenolic and non-phenolic lignin dimers using a nanostructure-initiator mass spectrometry-based assay. Fom_lac and Fom_CBM catalyze β-O-4′ ether and C–C bond breaking, with higher activity under acidic conditions (pH < 6). The potential of Fom_lac and Fom_CBM to enhance saccharification yields from untreated and ionic liquid pretreated pine was also investigated. Adding Fom_CBM to mixtures of cellulases and hemicellulases improved sugar yields by 140% on untreated pine and 32% on cholinium lysinate pretreated pine when compared to the inclusion of Fom_lac to the same mixtures. Adding either Fom_lac or Fom_CBM to mixtures of cellulases and hemicellulases effectively accelerates enzymatic hydrolysis, demonstrating its potential applications for lignocellulose valorization. We postulate that additional increases in sugar yields for the Fom_CBM enzyme mixtures were due to Fom_CBM being brought more proximal to lignin through binding to either cellulose or lignin itself.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Valorisation of Wasted Immature Tomato to Innovative Fermented Functional Foods

In this study, the lactic fermentation of immature tomatoes as a tool for food ingredient production was evaluated as a circular economy-oriented alternative for valorising industrial tomatoes that are unsuitable for processing and which have wasted away in large quantities in the field. Two lactic acid bacteria (LAB) were assessed as starter cultures in an immature tomato pulp fermentation to produce functional food ingredients with probiotic potential. The first trial evaluated the probiotic character of Lactiplantibacillus plantarum (LAB97, isolated from immature tomato microbiota) and Weissella paramesenteroides (C1090, from the INIAV collection) through in vitro gastrointestinal digestion simulation. The results showed that LAB97 and C1090 met the probiotic potential viability criterion by maintaining 6 log10 CFU/mL counts after in vitro simulation. The second trial assessed the LAB starters’ fermentative ability. Partially decontaminated (110 °C/2 min) immature tomato pulp was used to prepare the individually inoculated samples (Id: LAB97 and C1090). Non-inoculated samples, both with and without thermal treatment (Id: CTR-TT and CTR-NTT, respectively), were prepared as the controls. Fermentation was undertaken (25 °C, 100 rpm) for 14 days. Throughout storage (0, 24, 48, 72 h, 7, and 14 days), all the samples were tested for LAB and Y&M counts, titratable acidity (TA), solid soluble content (SSC), total phenolic content (TPC), antioxidant capacity (AOx), as well as for organic acids and phenolic profiles, and CIELab colour and sensory evaluation (14th day). The LAB growth reached ca. 9 log10 CFU/mL for all samples after 72 h. The LAB97 samples had an earlier and higher acidification rate than the remaining ones, and they were highly correlated to lactic acid increments. The inoculated samples showed a faster and higher decrease rate in their SSC levels when compared to the controls. A nearly two-fold increase (p < 0.05) during the fermentation, over time, was observed in all samples’ AOx and TPC (p < 0.05, r = 0.93; similar pattern). The LAB97 samples obtained the best sensory acceptance for flavour and overall appreciation scores when compared to the others. In conclusion, the L. plantarum LAB97 starter culture was selected as a novel probiotic candidate to obtain a potential probiotic ingredient from immature tomato fruits.

Pereira, Nelson (ORCID:0000000345745615)↗
DOE OSTI2023

Mechanism for Utilization of the Populus-Derived Metabolite Salicin by a Pseudomonas—Rahnella Co-Culture

Pseudomonas fluorescens GM16 associates with Populus, a model plant in biofuel production. Populus releases abundant phenolic glycosides such as salicin, but P. fluorescens GM16 cannot utilize salicin, whereas Pseudomonas strains are known to utilize compounds similar to the aglycone moiety of salicin–salicyl alcohol. We propose that the association of Pseudomonas to Populus is mediated by another organism (such as Rahnella aquatilis OV744) that degrades the glucosyl group of salicin. In this study, we demonstrate that in the Rahnella–Pseudomonas salicin co-culture model, Rahnella grows by degrading salicin to glucose 6-phosphate and salicyl alcohol which is secreted out and is subsequently utilized by P. fluorescens GM16 for its growth. Using various quantitative approaches, we elucidate the individual pathways for salicin and salicyl alcohol metabolism present in Rahnella and Pseudomonas, respectively. Furthermore, we were able to establish that the salicyl alcohol cross-feeding interaction between the two strains on salicin medium is carried out through the combination of their respective individual pathways. The research presents one of the potential advantages of salicyl alcohol release by strains such as Rahnella, and how phenolic glycosides could be involved in attracting multiple types of bacteria into the Populus microbiome.

Pseudomonas↗
NASA NTRS1972

Demonstration of the range over which the Langley Research Center digital computer charring ablation program (CHAP) can be used with confidence: Comparisons of CHAP predictions and test data for three ablation materials

Comparisons of ablation calculations with the charring ablation computer code and ablation test data are presented over a wide range of environmental conditions in air for three materials: low-density nylon phenolic, Avcoat 5026-39HC/G, and a filled silicon elastomer. Heat fluxes considered range from over 500 Btu/sq ft-sec to less than 50 Btu/sq ft-sec. Pressures range from 0.5 atm to .004 atm. Enthalpies range from about 2000 Btu/lb to 18000 Btu/lb. Predictions of recession, pyrolysis penetration, and thermocouple responses are considered. Recession predictions for nylon phenolic are good as steady state is approached, but strongly transient cases are underpredicted. Pyrolysis penetrations and thermocouple responses are very well predicted. Recession amounts for Avcoat and silicone elastomer are less well predicted, although high heat flux cases near steady state are fairly satisfactory. Pyrolysis penetrations and thermocouple responses are very well predicted.

Moyer, C. B.↗
NASA NTRS1972

Flight and ground tests of a very low density elastomeric ablative material

A very low density ablative material, a silicone-phenolic composite, was flight tested on a recoverable spacecraft launched by a Pacemaker vehicle system; and, in addition, it was tested in an arc heated wind tunnel at three conditions which encompassed most of the reentry heating conditions of the flight tests. The material was composed, by weight, of 71 percent phenolic spheres, 22.8 percent silicone resin, 2.2 percent catalyst, and 4 percent silica fibers. The tests were conducted to evaluate the ablator performance in both arc tunnel and flight tests and to determine the predictability of the albator performance by using computed results from an existing one-dimensional numerical analysis. The flight tested ablator experienced only moderate surface recession and retained a smooth surface except for isolated areas where the char was completely removed, probably following reentry and prior to or during recovery. Analytical results show good agreement between arc tunnel and flight test results. The thermophysical properties used in the analysis are tabulated.

Olsen, G. C.↗
NASA NTRS1972

Thermal performance of 625-kg/cu m elastomeric ablative materials on spherically blunted 0.44-radian cones

Spherically blunted 0.44-radian (25 deg) half-angle conical models coated with elastomeric ablative materials were tested in supersonic arc-heated wind tunnels to evaluate performance of the ablators over a range of conditions typical of lifting entry. Four test conditions were combinations of stagnation point-heat transfer rates of 2.3 and 4.5 MW/m2 and stagnation pressures of 20 and 2kN/m2. Afterbody values of heat transfer rate and pressure were 0.05 to 0.20 of stagnation point values. Stagnation enthalpy varied from 4.4 to 25 MJ/kg (1900 to 11000 Btu/lbm) and free-stream Mach number was in a range from 3.5 to 4. Ablative materials retained the spherical nose shape throughout tests at the lower heat transfer level, but receded, assuming a flattened nose shape, during tests at the high heat transfer level. The residue layer that formed on the conical after-body was weak, friable, and extensively cracked. The reference ablative material, which contained phenolic microspheres, generally retained the conical shape on the model afterbody. However, a modified ablator, in which phenolic microspheres were replaced with silica microspheres, deformed and separated from the undegraded material, and thereby produced a very uneven surface. Substrate temperatures and ablator recession were in good agreement with values computed by a numerical analysis.

Champman, A. J.↗
NASA NTRS1972

Development of seal ring carbon-graphite materials (tasks 5, 6, and 7)

Carbon-graphite seal ring bodies for operation at air temperatures to 1300 F(704 C) were manufactured from three select formulations. Mechanical and thermal properties, porosities, and oxidation rates were measured. The results have shown that: (1) Major property improvements anticipated from the screening studies were not realized because of processing problems associated with the scale-up in material size and probable deterioration of a phenolic resin binder; (2) the mechanical properties of a phenolic resin-bonded, carbon-graphite material can be improved by applying high pressure during carbonization; and (3) the textile form of graphite fiber used as the minor filler component in a carbon-graphite material can beneficially affect mechanical properties.

Fechter, N. J.↗
NASA NTRS1973

Effects of material composition on the ablation performance of low density elastomeric ablators

The ablation performance of materials composed of various concentrations of nylon, hollow silica spheres, hollow phenolic spheres, and four elastomeric resins was determined. Both blunt-body and flat-panel specimens were used, the cold-wall heating-rate ranges being 0.11 to 0.8 MW/sq m, respectively. The corresponding surface pressure ranges for these tests were 0.017 to 0.037 atmosphere and 0.004 to 0.005 atmosphere. Some of the results show that (1) the addition of nylon significantly improved the ablation performance, but the nylon was not compatible with one resin system; (2) panel and blunt-body specimen data do not show the same effect of phenolic sphere content on ablation effectiveness; and (3) there appears to be an optimum concentration of hollow silica spheres for good ablation performance. The composition of an efficient, nonproprietary ablator for lifting body application is identified and the ablation performance of this ablator is compared with the performance of three commercially available materials.

Tompkins, S. S.↗
NASA NTRS1974

The effect of ablation injection on radiative and convective heating

A viscous shock-layer analysis is for calculating high energy equilibrium flow fields about blunt axisymmetric bodies is applied to the problem of massive ablation injection with radiation transport. A nongray radiation model is used that accounts for both line and continuum radiation. The solution method is direct and provides both stagnation and downstream solutions. Results for shock heated air show that phenolic-nylon injection is substantially more effective in reducing the wall radiant flux than air injection. Also, for large included body angles, the wall radiative flux and the coupled phenolic-nylon injection rate do not continue to decrease with increasing distance downstream.

Moss, J. N.↗
NASA NTRS1975

Improvement in oxidation resistance of the leading edge thermal protection for a space shuttle

To improve the oxidation resistance of a carbon-carbon composite, impregnations were performed using pitches, polyfurfuryl alcohols, and phenolic resins, including a silicon-doped phenolic resin. Oxidation resistance and strength increased for all of the composites as the impregnant-carbon residue increased. The properties of the composites impregnated with the nonsilicon-bearing resins were nearly identical and depended only on the amount of impregnant residue present. However, for equivalent residue concentrations, composites produced with the silicon-bearing resin gave higher strengths and at least 100% better oxidation resistance than was observed for the other composites or for a prototype control material.

Williams, J. M.↗
NASA NTRS1976

Polymeric foams stable at high temperatures

Crosslinked poly(N-arylenebenzimidazoles) are stable up to 370 C. Polymers are made by mixing appropriate stoichiometric amounts of tetramine and aromatic dicarboxylic acid anhydride with phenol or alkyl-substituted phenol.

Riccitiello, S. R.↗
NASA NTRS1976

Heat shield characterization: Outer planet atmospheric entry probe

A full scale carbon phenolic heat shield was fabricated for the Outer Planet Probe in order to demonstrate the feasibility of molding large carbon phenolic parts with a new fabrication processing method (multistep). The sphere-cone heat shield was molded as an integral unit with the nose cap plies configured into a double inverse chevron shape to achieve the desired ply orientation. The fabrication activity was successful and the feasibility of the multistep processing technology was established. Delaminations or unbonded plies were visible on the heat shield and resulted from excessive loss of resin and lack of sufficient pressure applied on the part during the curing cycle. A comprehensive heat shield characterization test program was conducted, including: nondestructive tests with the full scale heat shield and thermal and mechanical property tests with small test specimen.

Mezines, S. A.↗