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At least 1,027 records · Page 57
All sourcesNASA NTRSDOE OSTI
DOE OSTI2014

Addition of gaseous olefin to produce boiler fuel and stability studies

As a renewable liquid fuel, bio‐oil produced from fast pyrolysis of biomass is receiving increasing attention. However, bio‐oil has some negative properties, such as polymerization over time, high water content, high viscosity, and low energy value. It must be upgraded to be used as a fuel. The objective of this study was to develop an upgrading method by esterification and olefination reactions to produce bio‐oil with lower water content and higher energy value for combustion as a boiler fuel. Loblolly pine wood was pyrolyzed at a feed rate of ∼7 kg/h in a Mississippi State University proprietary auger reactor to produce bio‐oil with 65% yield. Upgrading reactions were performed in a high‐pressure batch autoclave. Bio‐oil was reacted with alcohols and gaseous olefins in the presence of a heterogeneous catalyst to produce upgraded bio‐oil. The influence of reaction conditions such as reaction time, reaction temperature, and catalyst content were evaluated. Physical and chemical properties such as acid value, higher heating value, water content, and optimal conditions were identified. The result of olefination shows improved bio‐oil quality and increased energy density. Accelerated aging tests were also performed. © 2014 American Institute of Chemical Engineers Environ Prog, 2014 34: 933–941, 2015

Tao, Jingming↗
DOE OSTI2017

TC2015: Life cycle analysis of co-formed coal fines and hydrochar produced in twin-screw extruder (TSE)

Life cycle analysis (LCA) is a quantitative tool that evaluates the environmental performance of a process or system. The main objective of this LCA study is to assess the greenhouse gas (GHG) emissions and life cycle energy use associated with solid fuels produced by co-forming coal fines and hydrochar. The hydrochar is derived from loblolly pine wood via hydrothermal carbonization (HTC) conducted in a reactive twin-screw extruder (TSE). The final product is a drop-in replacement for coal. The life cycle impacts of the co-formed end products are quantified from ‘cradle-to-grave’. Model input parameters are collected from life cycle databases, literature, experimental measurements and simulations by engineering software. Results show that electricity generated from the co-formed products has significantly lower GHG intensity and slightly higher life cycle energy use than coal-generated electricity. The most carbon-intensive component in the overall hydrochar system is the HTC plant. However, this could be improved in the future by plant re-design to recover and recycle thermal energy for more efficient operation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Adsorption of methylene blue by bismuth impregnated biochar of different biomass materials: pore structure and surface chemistry characteristics

Abstract In this study, three different types of biochar (biomass materials were beech wood, corncob, and bamboo) were loaded with bismuth to form bismuth impregnated biochars (named respectively as Bi@WBC, Bi@CBC, and Bi@BBC) to investigate their properties (pore structure and surface chemistry characteristics) on methylene blue (MB) removal capacities. Three bismuth impregnated biochars made from different biomass materials were ranked for their adsorption capacity of MB as follows: Bi@WBC > Bi@CBC > Bi@BBC, in which Bi@WBC showed the largest Langmuir adsorption capacity of 178.59 mg g −1 . While the specific surface area (SSA) and pore volume of Bi@WBC were the largest (accounting for 477.74 m 2 g −1 and 0.15 cm 3 g −1 , respectively), according to the FTIR and XPS results, Bi@WBC (72.3%) exhibited a higher proportion of BiO bonds than the Bi@CBC (52.3%) and Bi@BBC (48.4%) did. Conclusively, the rich porous structure and surface functional groups of Bi@WBC affected the adsorption capacity of MB, and the chemical adsorption provided the main contribution. © 2022 Society of Chemical Industry (SCI).

Li, Peiyi↗
DOE OSTI2018

Incubation temperature influences the behavioral traits of a young precocial bird

Abstract The environment in which animals develop can have important consequences for their phenotype. In reptiles, incubation temperature is a critical aspect of the early developmental environment. Incubation temperature influences morphology, physiology, and behavior of non‐avian reptiles, however, little is known about how incubation temperature influences offspring phenotype and behaviors important to avian survival. To investigate whether incubation temperature influences avian behaviors, we collected wood duck ( Aix sponsa ) eggs from the field and incubated them at three naturally occurring incubation temperatures (35.0, 35.8, and 37.0°C). We conducted multiple repeated behavioral trials on individual ducklings between 5 and 15 days post‐hatch to assess activity, exploratory, and boldness behaviors, classified along a proactive‐reactive continuum. We measured growth rates and circulating levels of baseline and stress‐induced corticosterone levels to investigate possible physiological correlates of behavior. Ducklings incubated at the lowest temperature displayed more proactive behaviors than those incubated at the two higher temperatures. We also found that younger ducklings exhibited more proactive behavior than older ducklings and males exhibited more proactive behavior than females. Further, duckling behaviors were repeatable across time and contexts, indicative of a proactive–reactive continuum of behavioral tendencies. However, neither corticosterone levels nor growth rates were related to behavior. This provides some of the first evidence that incubation temperature, a critical parental effect, influences avian offspring behaviors that may be important for survival. Our results identify incubation temperature as a mechanism that contributes to the development of behavioral traits and, in part, explains how multiple behavioral types may be maintained within populations.

Hope, Sydney F.↗
DOE OSTI2024

Getting allometry right at the Oak Ridge free‐air CO 2 enrichment experiment: Old problems and new opportunities for global change experiments

Societal Impact Statement Free‐air CO 2 enrichment (FACE) experiments provide essential data on forest responses to increasing atmospheric CO 2 for evaluations of climate change impacts on humanity. Understanding and reducing the uncertainty in the experimental results is critical to ensure scientific and public confidence in the models and policy initiatives that derive therefrom. One source of uncertainty is the estimation of tree biomass using mathematical relationships between biomass and easily obtained and non‐destructive measurements (allometry). We evaluated the robustness of the allometric relationships established at the beginning of a FACE experiment and discuss the challenges and opportunities for the new generation of FACE experiments. Summary Long‐term field experiments to elucidate forest responses to rising atmospheric CO 2 concentration require allometric equations to estimate tree biomass from non‐destructive measurements of tree size. We analyzed whether the allometric equations established at the beginning of a free‐air CO 2 enrichment (FACE) experiment in a Liquidambar styraciflua plantation were still valid at the end of the 12 year experiment. Aboveground woody biomass was initially predicted by an equation that included bole diameter, taper, and height, assuming that including taper and height as predictors would accommodate changes in tree structure that might occur over time and in response to elevated CO 2 . At the conclusion of the FACE experiment, we harvested 23 trees, measured dimensions and dry mass of boles and branches, and extracted and measured the woody root mass of 10 trees. Although 10 of the harvested trees were larger than the trees used to establish the allometric relationship, measured aboveground woody biomass was well predicted by the original allometry. The initial linear equation between bole basal area and woody root biomass underestimated final root biomass by 28%, but root biomass was just 21% of total wood mass, and errors in aboveground and belowground estimates were offsetting. The allometry established at the beginning of the experiment provided valid predictions of tree biomass throughout the experiment. New allometric approaches using terrestrial laser scanning should reduce an important source of uncertainty in decade‐long forest experiments and in assessments of centuries‐long forest biomass accretion used in evaluating carbon offsets and climate mitigation.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Bxy‐fuca encoding α‐L‐fucosidase plays crucial roles in development and reproduction of the pathogenic pinewood nematode, Bursaphelenchus xylophilus

Abstract BACKGROUND The pine wood nematode (PWN) Bursaphelenchus xylophilus is the causal agent of pine wilt disease (PWD). This disease is a serious threat to pine forests globally. The fuca gene encodes α‐L‐fucosidase, which plays crucial roles in numerous biological and pathological processes in bacteria, fungi, plants and animals. To find promising control strategies against PWD, we investigated the expression and functions of Bxy‐fuca in B. xylophilus . RESULTS Bxy‐fuca encoding α‐L‐fucosidase is highly conserved within the deduced functional domains and key residues. It is expressed continuously across all developmental stages of B. xylophilus . mRNA in situ hybridization demonstrated that Bxy‐fuca was mainly localized in the body wall muscles and intestine. RNA interference indicated that the zygotic expression of Bxy‐fuca was indispensable for embryogenesis. The rate of B. xylophilus egg hatch was significantly decreased after Bxy‐fuca was interfered. Postembryonic silence of Bxy‐fuca resulted in a dramatic decrease in the longevity of and the total number of eggs produced by B. xylophilus . In addition, the motility of the nematode was greatly hampered with a significant drop in head thrashing frequency. CONCLUSION Bxy‐fuca plays crucial roles in development, lifespan and reproduction of B. xylophilus . Our results provide promising hints for control of PWD by blocking embryogenesis and ontogenesis, decreasing nematode fecundity, and disrupting the connection between B. xylophilus and its vector beetle by preventing nematode movement into the tracheal system. © 2019 Society of Chemical Industry

Tang, Jia↗
DOE OSTI2022

Trichoderma species isolated from grapevine with tolerance towards common copper fungicides used in viticulture for plant protection

Abstract BACKGROUND Copper‐containing fungicides are applied broadly in organic viticulture against downy mildew caused by Plasmopara viticola . Although long‐term application of copper‐based fungicides is associated with ecotoxic effects on the environment, their use in viticulture is required until sustainable alternatives are available. Trichoderma spp. might be a promising approach to fungicide reduction while promoting plant growth and development and displaying biocontrol activity. This study aims to examine the tolerance and compatibility of Trichoderma spp. to copper fungicides. This work contributes to the development of a spray application consisting of a copper‐tolerant Trichoderma sp. combined with a downscaled copper fungicide rate against P. viticola . RESULTS Trichoderma spp. isolated from grapevine wood in vineyards were identified and used for tolerance screening in various concentrations of copper fungicides. Copper hydroxide was identified as being highly compatible with Trichoderma . Two Trichoderma candidates, T. koningiopsis and T. harzianum , showed high copper tolerance in mycelial growth and germination tests, and were adapted to 2.85 g Cu L −1 of the selected fungicide. Microscopic investigations showed the attachment of copper compounds to fungal cell walls and copper uptake within the cytoplasm. In the case of high tolerance, large‐scale copper uptake was prevented. CONCLUSION Our findings identified two highly copper‐tolerant Trichoderma isolates with natural adaptation to the vineyard ecosystem, which could be further tested as biostimulants and biocontrol agents, combined with a reduced fungicide rate for sustainable plant protection. © 2022 Society of Chemical Industry.

Küpper, Verena↗
DOE OSTI2018

Tungsten isotopic constraints on the origin and evolution of the Moon

Here we report the Moon most likely formed as the result of a collision between the proto-Earth and a differentiated body possibly the size of Mars (Cameron and Benz, 1991; Hartmann and Davis, 1975). The enormous amount of energy released by this giant impact caused widespread melting on the proto-Earth and the ejection of material into Earth’s orbit from which the Moon subsequently accreted. Upon accretion of the Moon, the lunar mantle underwent global silicate differentiation most likely facilitated by a lunar magma ocean (e.g. Wood et al., 1970). Magma ocean crystallization likely produced the wide diversity of lunar source rocks and involved the successive crystallization of mafic cumulates consisting of olivine and pyroxene, followed by crystallization of plagioclase which floated to the lunar surface to form the lunar crust consisting of ferroan anorthosites (FAN). Lastly, the residual liquid of the lunar magma ocean represents a separate component within the Moon termed KREEP (enriched in Potassium K, Rare Earth Elements, and Phosphorous). Re-melting of these magma ocean crystallization products of the low-Ti and high-Ti mare basalt source regions as well as the formation of Mg-suite lunar highland rocks.

58 GEOSCIENCES↗
DOE OSTI2019

Mercury Complexation with Dissolved Organic Matter Released from Thirty-Six Types of Biochar

Previous studies show mercury (Hg) can be effectively removed from solution by biochar, but limited attention was paid on the complexation between Hg and components released from biochars, e.g. dissolved organic matter (DOM). Here, aqueous data from batch-style experiments were modeled using PHREEQC, incorporating thermodynamic constants between Hg and DOM, which was assumed to be composed of thiol, carboxylic, and phenolic functional groups. Modelling results suggest that > 99% Hg complexed with thiol groups in DOM. The modelled concentrations of Hg–DOM complexes from low-T (low-temperature, 300°C) biochars were greater than from high-T (600°C) biochars. The concentrations of Hg–DOM complexes were lower in wood-based than in agricultural residue- and manure-based biochars. Hg–DOM complexes may affect Hg speciation, bioavailability, transport, and methylation processes. This research describes a method to evaluate Hg–DOM interactions, and the results indicate extra caution regarding Hg–DOM complex formation is required in the selection of biochar for Hg remediation.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Unraveling the Hsp70-ROS-autophagy axis in pentachlorophenol-challenged lung and liver epithelial cells

Pentachlorophenol (PCP) was extensively utilized as an organochlorine pesticide and wood preservative in the United States from the 1930s until the Environmental Protection Agency (EPA) imposed restrictions due to concerns about its toxicity and potential carcinogenic properties. Although it is no longer widely used, PCP remains a concern due to its environmental persistence and potential for long-term health effects. Significant occupational and environmental exposures have likely occurred, with the health and economic costs of PCP exposure potentially being substantial given its known toxicity. Notably, PCP exhibits rapid absorption through both the skin and respiratory system and has been shown to cause hepatotoxicity, developmental toxicity, immunotoxicity, irritation, and carcinogenicity in laboratory animal studies. PCP exposure induces oxidative stress, a key mechanism underlying its inflammatory and toxic effects, which can activate cellular stress responses including upregulation of heat shock protein 70 (Hsp70). Previous studies in lung and liver epithelial cells have shown that Hsp70 and oxidative stress play pivotal roles in triggering autophagy. This study establishes the critical role of the Hsp70-reactive oxygen species (ROS)-autophagy axis in regulating cellular responses to PCP exposure in human alveolar (A549) and liver carcinoma (HepG2) epithelial cells. Our research elucidated the molecular mechanisms underlying PCP's cellular effects, demonstrating that its exposure resulted in increased expression of autophagy-related proteins (Beclin-1, LC3B, ATG12, and ATG16), subunits of NADPH oxidase (NCF-1, NCF-2, NOX2, and Rac), and antioxidant proteins (SOD and GPx) in both lung and liver cell types. Notably, PCP augmented the interaction between Hsp70 and the autophagy regulator Beclin-1. Pretreatment with the ROS inhibitor N-acetylcysteine or Hsp70 knockdown markedly reversed PCP-induced responses. Our in-silico protein–protein docking analysis and molecular dynamics simulation studies revealed enhanced interactions and/or stable confirmations maintained throughout the simulations for TLR4-Hsp70 and Hsp70-Beclin-1 complexes in the presence of PCP. These findings provide a strong foundation for future studies, employing in vivo experimental models and human populations to identify promising targets for PCP-induced toxicity and cellular injury. As a result, these findings may have far-reaching implications for public health and environmental policy, ultimately leading to the identification of biomarkers and the development of more effective interventions for environmentally induced toxicity and diseases.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Stem respiration and growth in a central Amazon rainforest

Tropical forests cycle a large amount of CO 2 between the land and atmosphere, with a substantial portion of the return flux due tree respiratory processes. However, in situ estimates of woody tissue respiratory fluxes and carbon use efficiencies (CUEW) and their dependencies on physiological processes including stem wood production (Pw) and transpiration in tropical forests remain scarce. In this work, we synthesize monthly Pw and daytime stem CO 2 efflux (ES) measurements over one year from 80 trees with variable biomass accumulation rates in the central Amazon. On average, carbon flux to woody tissues, expressed in the same stem area normalized units as ES, averaged 0.90 ± 1.2 µmol m -2 s -1 for Pw, and 0.55 ± 0.33 µmol m -2 s -1 for daytime ES. A positive linear correlation was found between stem growth rates and stem CO 2 efflux, with respiratory carbon loss equivalent to 15 ± 3% of stem carbon accrual. CUEW of stems was non-linearly correlated with growth and was as high as 77-87% for a fast-growing tree. Diurnal measurements of stem CO 2 efflux for three individuals showed a daytime reduction of ES by 15-50% during periods of high sap flow and transpiration. The results demonstrate that high daytime ES fluxes are associated with high CUE W during fast tree growth, reaching higher values than previously observed in the Amazon Basin (e.g. maximum CUEW up to 77-87%, versus 30-56%). The observations are consistent with the emerging view that diurnal dynamics of stem water status influences growth processes and associated respiratory metabolism.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

The second most disastrous windstorm of the nineteenth century in the Czech Lands, 26-27 October 1870

One of the most disastrous windstorms to take place over the Czech Lands occurred on the night of 26/27 October 1870. It is here analysed through the use of documentary data (narrative sources, newspapers, forestry journals, printed documents) and systematic meteorological observations (wind force and direction). Combining this evidence with information derived from an atmospheric reanalysis dataset allows the severity of the windstorm to be attributed to the passage of a cold front, a frontal system associated with a secondary low in a typically storm-prone synoptic environment. Its social impacts were characterised by great material damage, particularly to buildings and other structures, trees and forests. These are recorded not only for 174 places around the countryside and lesser settlements of the Czech Lands, but also for 28 city quarters in Prague, the capital city. The windstorm occurred in the night hours, so only a few people were killed or injured. However, the 1870 windstorm totally devastated many forested areas of the Šumava Mts. in south-west Bohemia. Damage to forests in other parts of the Czech Lands was also severe, but difficult to quantify exactly for lack of high-resolution spatial data. Because this windstorm followed only shortly upon a previous similarly disastrous wind event on 7 December 1868, the enormous quantity of windthrown wood in forests, which simply could not be fast-processed, contributed significantly to a subsequent bark-beetle infestation calamity in the 1870s. In certain forest stands, imprints of these aggregate effects appear to this day. The central-European scale of 1870 windstorm is also well documented by meteorological and documentary data from Germany, Austria and Slovakia.

Meteorology & Atmospheric Sciences↗
DOE OSTI2018

Removal of Woody Riparian Vegetation Substantially Altered a Stream Ecosystem in an Otherwise Undisturbed Grassland Watershed

Riparian zones are key interfaces between stream and terrestrial ecosystems. Yet, we know of no whole-watershed experiments that cut only woody vegetation in the riparian zone in an otherwise intact watershed to isolate the role of riparian zones on stream ecology. We removed all of the woody riparian vegetation (from 10- and 30-m-wide buffers in headwaters and main channels, respectively) for 5 km of stream in a single watershed while leaving the remainder of the grassland watershed un-impacted. We assessed water chemistry changes 3 years before and 3 years after riparian wood removal and in two neighboring control watersheds with a before–after, control-impact design and analysis. Riparian woody removal caused 10–100-fold increases in mean stream water nitrate concentrations and pulses of high nitrate for 3 years thereafter. Other nutrients and total suspended solids increased 2–25 times for the 3 years of post-removal. In-stream rates of gross primary production, ecosystem respiration, and net ecosystem production had large treatment effect sizes but also high variance among samples. Past studies of whole-watershed deforestations showed similar water quality responses to our riparian deforestation. Riparian zones of grassland streams are sensitive to disturbance and likely impart relatively greater influence on stream structure and function than the upslope of the watershed. Finally, our results further emphasize the role of riparian zones in biogeochemically linking aquatic and terrestrial habitats.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Forest Structural Complexity and Biomass Predict First-Year Carbon Cycling Responses to Disturbance

The pre-disturbance vegetation characteristics that predict carbon (C) cycling responses to disturbance are not well known. To address this gap, we initiated the Forest Resilience Threshold Experiment, a manipulative study in which more than 3600 trees were stem girdled to achieve replicated factorial combinations of four levels (control, 45, 65, and 85% gross defoliation) of disturbance severity and two disturbance types (targeting upper or lower canopy strata). Applying a standardized stability framework in which initial C cycling resistance to disturbance was calculated as the first-year natural log response ratio of disturbance and control treatments, we investigated to what extent pre-disturbance levels of species diversity, aboveground woody biomass, leaf area index, and canopy rugosity—a measure of structural complexity—predict the initial responses of subcanopy light-saturated leaf CO 2 assimilation (A sat ), aboveground wood NPP (ANPP w ), and soil respiration (R s ) to phloem-disrupting disturbance. In the year following stem girdling, we found that above-ground C cycling processes, A sat and ANPP w , were highly resistant to increases in disturbance severity, while Rs resistance declined as severity increased. Disturbance type had no effect on first-year resistance. Pre-disturbance aboveground woody biomass, and canopy rugosity were positive predictors of ANPP w resistance and, conversely, negatively related to R s resistance. Subcanopy A sat resistance was not related to pre-disturbance vegetation characteristics. Stability of C uptake processes along with R s declines suggest the net C sink was sustained in the initial months following disturbance. Therefore, we conclude that biomass and complexity are significant, but not universal, predictors of initial C cycling resistance to disturbance. Moreover, our findings highlight the utility of standardized stability measures when comparing functional responses to disturbance.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Exploring the Role of Cryptic Nitrogen Fixers in Terrestrial Ecosystems: A Frontier in Nitrogen Cycling Research

Biological nitrogen fixation represents the largest natural flux of new nitrogen (N) into terrestrial ecosystems, providing a critical N source to support net primary productivity of both natural and agricultural systems. When they are common, symbiotic associations between plants and bacteria can add more than 100 kg N ha –1 y –1 to ecosystems. Yet, these associations are uncommon in many terrestrial ecosystems. In most cases, N inputs derive from more cryptic sources, including mutualistic and/or free-living microorganisms in soil, plant litter, decomposing roots and wood, lichens, insects, and mosses, among others. Unfortunately, large gaps remain in the understanding of cryptic N fixation. Here, we conducted a literature review to explore rates, patterns, and controls of cryptic N fixation in both unmanaged and agricultural ecosystems. Our analysis indicates that, as is common with N fixation, rates are highly variable across most cryptic niches, with N inputs in any particular cryptic niche ranging from near zero to more than 20 kg ha –1 y –1 . Such large variation underscores the need for more comprehensive measurements of N fixation by organisms not in symbiotic relationships with vascular plants in terrestrial ecosystems, as well as identifying the factors that govern cryptic N fixation rates. We highlight several challenges, opportunities, and priorities in this important research area, and we propose a conceptual model that posits an interacting hierarchy of biophysical and biogeochemical controls over N fixation that should generate valuable new hypotheses and research.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Relaxation dynamics of water in the vicinity of cellulose nanocrystals

Water molecules near cellulose nanocrystals (CNCs; produced via the sulfuric acid-catalyzed hydrolysis of wood pulp) are believed to relax slower than those in the bulk liquid, which may result in unique properties of CNC aqueous dispersions. Herein this study analyzed the polarization behavior of water molecules in CNC aqueous dispersions and other reference samples using a dielectric relaxation spectroscopy (DRS) technique in the microwave frequency range (0.2–20 GHz). As the CNC concentration increases, two slow relaxation components become prominent. The comparison with DRS data of aqueous dispersions of nanoporous silica, polyvinyl alcohol (PVA), and hairy CNC (HCNC) with amorphous chains protruding from both ends suggested that these slow relaxation modes of water near CNC surfaces cannot be attributed to direct hydrogen bonding interactions with the hydroxyl (OH) groups exposed and immobilized at the solid surface. Instead, they are similar to the water molecules interacting with OH groups attached to flexible polymer chains. Molecular dynamics (MD) simulations of the polarization behavior of water near the (110) facet of cellulose Iβ crystals confirmed that the interactions of water molecules with the cellulose crystal surface do not cause slower relaxations in the frequency range studied via the DRS. These results indicated that the CNC surface cannot be depicted with the crystallographic facets of cellulose Iβ; instead, it resembles a polymer-brush surface on which the short glucan residues or fragments of the strong acid-catalyzed hydrolysis process are swollen and extended into the aqueous phase.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2018

Isolation and Characterization of Cellulose Micro/Nanofibrils from Douglas Fir

Cellulose micro/nanofibrils were successfully extracted from softwood Douglas fir in three distinct stages. Initially raw Douglas fir wood chips were subjected to a hot water extraction (HWE) treatment. Then HWE treated cellulosic fibers underwent a bleaching process followed by a mild ultrasonication. Chemical composition analysis according to ASTM standards confirmed that most of hemicelluloses and nearly all lignin were removed during the first two stages, respectively. Microscopy studies showed formation of nanofibrils during the ultrasonication process, and increasing ultrasonication time led to generation of greater percentage of nanofibrils. With the removal of the matrix materials, the crystallinity of the cellulosic fibers was increased, whereas thermal stability was maintained. HWE opened up the cell wall structure, thereby facilitating the subsequent fractionation into micro/nanofibrils. The obtained cellulose micro/nanofibrils could serve as reinforcing material in composite products or raw material for other applications, such as filtration membrane.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Surface-Modified Cellulose Nanofibers-graft-poly(lactic acid)s Made by Ring-Opening Polymerization of L-Lactide

Highly crystalline cellulose nanofibers with a high density of carboxylate groups only on the surfaces were prepared from both softwood and non-wood cellulose pulp. The preparation method used 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of native cellulose fibrils in an aqueous TEMPO/NaBr/NaClO system and subsequent postoxidation with NaClO{sub 2} in acetate buffer (pH 4.8). The TEMPO-oxidized cellulose nanofibers (TOCNs) possessed a carboxylate content of 1.7 mmol g{sup −1} and a crystallinity of 67–69% with a crystallite size of ∼3 nm. The TOCNs were used to produce highly crystalline TOCN-graft-poly(lactic acid) (PLA) nanocomposites via ring-opening polymerization of L-lactide in a polar aprotic solvent. Effects of the reaction temperature and the molar ratio of L-lactide to carboxylate surface groups, on the efficiency of surface grafting were investigated to potentially improve the crystallinity and thermal properties of the nanocomposites. The crystallinity of TOCN-g-PLA products was 59–66% greater than the crystallinity of neat PLA.

36 MATERIALS SCIENCE↗