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At least 199 records · Page 11

Physico-chemical properties of lignin fractions from acid pretreated corn stover and their effects on enzymatic hydrolysis of microcrystalline cellulose

Lignin has been shown to be a recalcitrance factor in many biomass conversion studies. To better understand the effects of lignin on cellulose conversion, different lignin fractions were extracted from the same dilute acid pretreated corn stover by three sequential isolation methods, namely ethanol extraction, dioxane extraction, and enzyme purification. The physicochemical properties of each lignin fraction including molecular weight distribution, surface area, surface charge, and other structural features varied, depending on the isolation methods. All three lignin fractions had negative surface charges, and ethanol-extracted lignin carried the highest surface charges, followed by dioxane-extracted lignin and cellulase-purified residual lignin. These physicochemical properties of lignin fractions also resulted in different extent of inhibitory effects on enzymatic hydrolysis of microcrystalline cellulose (MCC). Dioxane-extracted lignin exhibited the highest inhibitory effect on glucose release from MCC, followed by the cellulase-purified residual lignin fraction and ethanol-extracted lignin. Furthermore, lignin fractions with higher contents of syringyl (S) substructure and β-O-4 aryl ether interunit linkages showed a stronger negative effect on cellulase hydrolysis of MCC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nanomechanical mapping and strain rate sensitivity of microcrystalline cellulose

Nanoindentation provides a convenient and high-throughput means for mapping mechanical properties and for measuring the strain rate sensitivity of a material. Here, nanoindentation was applied to the study of microcrystalline cellulose. Here, constant strain rate nanoindentation revealed a depth dependence of nanohardness and modulus, mostly attributed to material densification. Nanomechanical maps of storage modulus and hardness resolved the shape and size of voids present in larger particles. In smaller, denser particles, however, where storage modulus varied little spatially, there was still some spatial dependence of hardness, which can be explained by cellulose’s structural anisotropy. Additionally, hardness changed with the indentation strain rate in strain rate jump tests. The resulting strain rate sensitivity values were found to be in agreement with those obtained by other techniques in the literature.

36 MATERIALS SCIENCE↗

Using Incremental Changes to Convert Lignocellulosic Feedstocks to Cellulosic Ethanol

One billion tons of biomass feedstocks have been identified for the production of renewable biofuels and biochemicals. This is one of the key carbon feedstocks to supply energy to the transportation sector for light duty, heavy duty and aviation fuels. Utilization of lignocellulosic feedstocks supports an improved energy security by reducing demand of petroleum imports, agricultural development, job creation, and reducing greenhouse gas emissions. To date, however, operational challenges have stymied the industrial production of large volumes of lignocellulosic-based fuels and chemicals. As a result, significant research investment has been led by the United States Department of Energy to understand and improve operational reliability at pioneer cellulosic biorefineries. In this perspective article lignocellulosic conversion technologies are described that have been adopted from the starch ethanol process. The developed process culminated in successful demonstration of 1,000-h integrated runs using several feedstocks, including switchgrass, energy sorghum, and two types of corn kernel fiber. This report highlights process development that solved several of the issues that plagued—and continue to plague—many in the cellulosic sugars space such as biomass feeding into equipment, high ash content, diversified co-product value, and others.

09 BIOMASS FUELS↗

Cellulose Nanofibers as Rheological Modifiers to Improve Biomass Slurry Processing and Fermentation

This study investigates the enhancement of biomass slurry processability through the addition of rheological modifiers, focusing on carboxymethyl cellulose (CMC) and TEMPO-mediated oxidized cellulose nanofibrils (TCNF). Three sets of experiments were conducted to assess the effects of these additives on slurry processing and fermentation. Initial experiments evaluated the slurry extrudability, concluding that TCNF aids extrusion similarly to CMC. Subsequent experiments explored slurry viscosity reduction mechanisms, revealing that while CMC significantly reduced the viscosity, TCNF’s impact is negligible. Additionally, TCNF performed comparably to CMC in water retention tests across different conditions, which suggests that TCNF have potential as an effective additive for maintaining slurry fluidity at high solid concentrations through enhanced water retention. Lastly, both additives were investigated to ensure that they did not impact hydrolyzed biomass fermentation. The findings suggest that TCNF’s mechanisms differ from those of traditional water-soluble polymers like CMC, offering insights into novel approaches to improve the biomass processing efficiency and subsequent fermentation.

Jamieson, Zachary↗

Analysis of carbon capture at cellulosic biorefineries

The large-scale production of cellulosic biofuels would involve spatially distributed systems including biomass fields, logistics networks and biorefineries. Better understanding of the interactions between landscape-related decisions and the design of biorefineries with carbon capture and storage (CCS) in a supply chain context is needed to enable efficient systems. Here we analyse the cost and greenhouse gas mitigation potential for cellulosic biofuel supply chains in the US Midwest using realistic spatially explicit land availability and crop productivity data and consider fuel conversion technologies with detailed CCS design for their associated CO2 streams.

carbon capture and storage (CCS)↗

Mechanisms and kinetics of cellulose fermentation for protein production

The development of a process (and ancillary processing and analytical techniques) to produce bacterial single-cell protein of good nutritional quality from waste cellulose is discussed. A fermentation pilot plant and laboratory were developed and have been in operation for about two years. Single-cell protein (SCP) can be produced from sugarcane bagasse--a typical agricultural cellulosic waste. The optimization and understanding of this process and its controlling variables are examined. Both batch and continuous fermentation runs have been made under controlled conditions in the 535 liter pilot plant vessel and in the laboratory 14-liter fermenters.

Dunlap, C. A.↗

The effect of fire retardants on the fire response characteristics of cellulosic materials

The resistance to ignition of fire retardant-treated wood, cotton, and cellulose insulation was studied. The proprietary composition used to treat wood was found to increase resistance to ignition and to reduce smoke toxicity. Cotton treated with boric acid (added by padding on or by vapor phase process) was found to have increased resistance to ignition and decreased smoke toxicity. Boric acid increased the resistance of cellulose insulation to ignition but also slightly increased the smoke toxicity.

Hilado, C. J.↗

Heat and Mass Transport from Thermally Degrading Thin Cellulosic Materials in a Microgravity Environment

Attention is given to a theoretical model describing the behavior of a thermally thin cellulosic sheet heated by external thermal radiation in a quiescent microgravity environment. This model describes thermal and oxidative degradation of the sheet and the heat and mass transfer of evolved degradation products from the heated cellulosic surface into the gas phase. Two calculations are carried out: heating without thermal degradation, and heating with thermal degradation of the sheet with endothermic pyrolysis, exothermic thermal oxidative degradation, and highly exothermic char oxidation. It is shown that pyrolysis is the main degradation reaction. Self-sustained smoldering is controlled and severely limited by the reduced oxygen supply.

Kushida, G.↗

Cellulose Triacetate Dielectric Films For Capacitors

Cellulose triacetate investigated for use as dielectric material in high-energy-density capacitors for pulsed-electrical-power systems. Films of cellulose triacetate metalized on one or both sides for use as substrates for electrodes and/or as dielectrics between electrodes in capacitors. Used without metalization as simple dielectric films. Advantages include high breakdown strength and self-healing capability.

Yen, Shiao-Ping S.↗

Application of a two-stream radiative transfer model for leaf lignin and cellulose concentrations from spectral reflectance measurements, part 1

Lignin and nitrogen contents of leaves constitute the primary rate-limiting parameters for the decomposition of forest litter, and are determinants of nutrient- and carbon-cyclic rates in forest ecosystems (Melillo et al., 1982). Wessman et al. (1988a) developed empirical multivariate relationships between forest canopy lignin amount and the (first-difference) AIS spectral response in three bands spread over the wavelength interval 1256-1555 nm. Wessman et al. (1988b) and McLellan et al. (1991) developed similar regression relationships from laboratory reflectance measurements on dried samples prepared in a standard fashion. They used four to six infrared bands for analysis of nitrogen, lignin and cellulose content of foliage in forest and prairie species. In the present article (Parts 1 and 2) the feasibility of compositional determinations is explored using positions of composite absorption bands that originate from mixtures of lignin, cellulose, and possibly other chemical constituents in the spectral reflectance of green leaves. To carry out this program, we employ full-spectral-resolution single-leaf diffuse reflectance measurements made with a laboratory spectrometer and integrating sphere. The leaf and other chemical reflectance data compiled by Elvidge (1990) have also been utilized extensively.

Conel, James E.↗

Application of a two-stream radiative transfer model for leaf lignin and cellulose concentrations from spectral reflectance measurements, part 2

We used the Kubelka-Munk theory of diffuse spectral reflectance in layers to analyze influences of multiple chemical components in leaves. As opposed to empirical approaches to estimation of plant chemistry, the full spectral resolution of laboratory reflectance data was retained in an attempt to estimate lignin or other constituent concentrations from spectral band positions. A leaf water reflectance spectrum was derived from theoretical mixing rules, reflectance observations, and calculations from theory of intrinsic k- and s-functions. Residual reflectance bands were then isolated from spectra of fresh green leaves. These proved hard to interpret for composition in terms of simple two component mixtures such as lignin and cellulose. We next investigated spectral and dilution influences of other possible components (starch, protein). These components, among others, added to cellulose in hypothetical mixtures, produce band displacements similar to lignin, but will disguise by dilution the actual abundance of lignin present in a multicomponent system. This renders interpretation of band positions problematical. Knowledge of end-members and their spectra, and a more elaborate mixture analysis procedure may be called for. Good observational atmospheric and instrumental conditions and knowledge thereof are required for retrieval of expected subtle reflectance variations present in spectra of green vegetation.

Conel, James E.↗

Optimization of moisture content for wheat seedling germination in a cellulose acetate medium for a space flight experiment

The Porous Tube Plant Nutrient Delivery System (PTPNDS), a hydrophilic, microporous ceramic tube hydroponic system designed for microgravity, will be tested in a middeck locker of the Space Shuttle. The flight experiment will focus on hardware operation and assess its ability to support seed germination and early seedling growth in microgravity. The water controlling system of the PTPNDS hardware has been successfully tested during the parabolic flight of the KC-135. One challenge to the development of the spaceflight experiment was to devise a method of holding seeds to the cylindrical porous tube. The seed holder must provide water and air to the seed, absorb water from the porous tube, withstand sterilization, provide a clear path for shoots and roots to emerge, and be composed of flight qualified materials. In preparation for the flight experiment, a wheat seed-holder has been designed that utilizes a cellulose acetate plug to facilitate imbibition and to hold the wheat seeds in contact with the porous tube in the correct orientation during the vibration of launch and the microgravity environment of orbit. Germination and growth studies with wheat at a range of temperatures showed that optimal moisture was 78% (by weight) in the cellulose acetate seed holders. These and other design considerations are discussed.

Johnson, Corinne F.↗

Ignition of Cellulosic Paper at Low Radiant Fluxes

The ignition of cellulosic paper by low level thermal radiation is investigated. Past work on radiative ignition of paper is briefly reviewed. No experimental study has been reported for radiative ignition of paper at irradiances below 10 Watts/sq.cm. An experimental study of radiative ignition of paper at these low irradiances is reported. Experimental parameters investigated and discussed include radiant power levels incident on the sample, the method of applying the radiation (focussed vs. diffuse Gaussian source), the presence and relative position of a separate pilot ignition source, and the effects of natural convection (buoyancy) on the ignition process in a normal gravity environment. It is observed that the incident radiative flux (in W/sq.cm) has the greatest influence on ignition time. For a given flux level, a focussed Gaussian source is found to be advantageous to a more diffuse, lower amplitude, thermal source. The precise positioning of a pilot igniter relative to gravity and to the fuel sample affects the ignition process, but the precise effects are not fully understood. Ignition was more readily achieved and sustained with a horizontal fuel sample, indicating the buoyancy plays a role in the ignition process of cellulosic paper. Smoldering combustion of doped paper samples was briefly investigated, and results are discussed.

White, K. Alan↗

Optimization of moisture content for wheat seedling germination in a cellulose acetate medium for a space flight experiment

The Porous Tube Plant Nutrient Delivery System (PTPNDS), a hydrophilic, microporous ceramic tube hydroponic system designed for microgravity, will be tested in a middeck locker of the Space Shuttle. The flight experiment will focus on hardware operation and assess its ability to support seed germination and early seedling growth in microgravity. The water controlling system of the PTPNDS hardware has been successfully tested during the parabolic flight of the KC-135. One challenge to the development of the space flight experiment was to devise a method of holding seeds to the cylindrical porous tube. The seed-holder must provide water and air to the seed, absorb water from the porous tube, withstand sterilization, provide a clear path for shoots and roots to emerge, and be composed of flight qualified materials. In preparation for the flight experiment, a wheat seed-holder has been designed that utilizes a cellulose acetate plug to facilitate imbibition and to hold the wheat seeds in contact with the porous tube in the correct orientation during the vibration of launch and the microgravity environment of orbit. Germination and growth studies with wheat at a range of temperatures showed that optimal moisture was 78% (by weight) in the cellulose acetate seed holders. These and other design considerations are discussed.

NASA Discipline Number 61-20↗

Quantitative Infrared Image Analysis Of Thermally-Thin Cellulose Surface Temperatures During Upstream and Downstream Microgravity Flame Spread from A Central Ignition Line

Surface view calibrated infrared images of ignition and flame spread over a thin cellulose fuel were obtained at 30 Hz during microgravity flame spread tests in the 10 second Japan Microgravity Center (JAMIC). The tests also used a color video of the surface view and color images of the edge view using 35 millimeter 1600 Kodak Ektapress film at 2 Hz. The cellulose fuel samples (50% long fibers from lumi pine and 50% short fibers from birch) were made with an area density of 60 grams per square meters. The samples were mounted in the center of a 12 centimeter wide by 16 centimeter tall flow duct that uses a downstream fan to draw the air through the flow duct. Samples were ignited after the experiment package was released using a straight hot wire across the center of the 7.5 centimeter wide by 14 centimeter long samples. One case, at 1 atmosphere 35%O2 in N2, at a forced flow of 10 centimeters per second, is presented here. In this case, as the test progresses, the single flame begins to separate into simultaneous upstream and downstream flames. Surface temperature profiles are evaluated as a function of time, and temperature gradients for upstream and downstream flame spread are measured. Flame spread rates from IR image data are compared to visible image spread rate data. IR blackbody temperatures are compared to surface thermocouple readings to evaluate the effective emissivity of the pyrolyzing surface. Preheat lengths are evaluated both upstream and downstream of the central ignition point. A surface energy balance estimates the net heat flux from the flame to the fuel surface along the length of the fuel.

Olson, Sandra L.↗

Quantitative Infrared Image Analysis Of Simultaneous Upstream and Downstream Microgravity Flame Spread over Thermally-Thin Cellulose in Low Speed Forced Flow

The effect of low velocity forced flow on microgravity flame spread is examined using quantitative analysis of infrared video imaging. The objective of the quantitative analysis is to provide insight into the mechanisms of flame spread in microgravity where the flame is able to spread from a central location on the fuel surface, rather than from an edge. Surface view calibrated infrared images of ignition and flame spread over a thin cellulose fuel were obtained along with a color video of the surface view and color images of the edge view using 35 mm color film at 2 Hz. The cellulose fuel samples were mounted in the center of a 12 cm wide by 16 cm tall flow duct and were ignited in microgravity using a straight hot wire across the center of the 7.5 cm wide by 14 cm long samples. Four cases, at 1 atm. 35%O2 in N2, at forced flows from 2 cm/s to 20 cm/s are presented here. This flow range captures flame spread from strictly upstream spread at low flows, to predominantly downstream spread at high flow. Surface temperature profiles are evaluated as a function of time, and temperature gradients for upstream and downstream flame spread are measured. Flame spread rates from IR image data are compared to visible image spread rate data. IR blackbody temperatures are compared to surface thermocouple readings to evaluate the effective emissivity of the pyrolyzing surface. Preheat lengths and pyrolysis lengths are evaluated both upstream and downstream of the central ignition point. A surface energy balance estimates the net heat flux from the flame to the fuel surface along the length of the fuel. Surface radiative loss and gas-phase radiation from soot are measured relative to the net heat feedback from the flame. At high surface heat loss relative to heat feedback, the downstream flame spread does not occur.

Olson, S. L.↗

Self-Assembly Interactions in Magnetite-Coated Cellulose Nanocrystals: Implications for Magnetic Hyperthermia Applications

Magnetic cellulose nanocrystal (MCNC) nanocomposites are promising sustainable and biocompatible platforms for magnetic hyperthermia; however, the molecular mechanisms governing Fe 3 O 4 adsorption and deposition onto CNCs remain poorly understood. Here, sulfated (S-CNC) and TEMPO-oxidized CNCs (T-CNC) were used to prepare nanocomposites at 1:2 and 1:4 CNC:Fe 3 O 4 mass ratios, enabling a systematic evaluation of how surface chemistry and nanoparticle loading dictate interfacial interactions and magneto-colloidal behavior. Bare magnetite nanoparticles were 21 ± 5 nm by TEM but grew to 144 ± 18 in the DLS measurement at pH 7. The S-CNC nanocomposites had hydrodynamic sizes between 144 and 210 nm, not much larger than the 140 nm long CNC rods, suggesting an enhanced dispersion stability compared to Fe3O4 alone. X-ray photoelectron spectroscopy combined with density functional theory revealed that −OH and −COOH groups drive electrostatic adsorption with charge transfer from Fe 3 O 4 to the CNC surface, while T-CNCs showed more favorable adsorption energies and evidence of covalent Fe−O bonding. Vibrating sample magnetometry demonstrated superparamagnetic behavior for all samples, with S-CNC/Fe 3 O 4 1:4 and 1:2 displaying saturation magnetizations of 78 and 77 emu/g-Fe 3 O 4 , close to the 83 emu/g of bare magnetite. The T-CNC composites showed lower (60 and 66 emu/g-Fe3O4) saturation magnetizations. Zero-field-cooled/field-cooled measurements resulted in a blocking temperature of 112 K for all samples, except T-CNC/Fe 3 O 4 1:2 (100 K). Magnetic hyperthermia studies revealed that specific absorption rate (SAR) increased with field strength and Fe 3 O 4 content; however, S-CNC/Fe 3 O 4 (1:2) achieved the highest intrinsic SAR per gram of Fe 3 O 4 (649 W/g-Fe 3 O 4 ) likely due to its anisotropy and fast magnetic relaxation. Cytotoxicity assays confirmed that all nanocomposites were nontoxic toward mammalian cells. These results establish quantitative structure−property relationships between CNC surface chemistry, interfacial bonding mechanisms, and magnetic heating performance, providing a foundation for rational design of biocompatible magnetic nanocomposites for hyperthermia and related applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pretreatment of lignocellulosic feedstocks for cellulose nanofibril production

Cellulose nanofibrils (CNFs) have attracted a great deal of research interest in recent years attributable to the low cost and abundance of lignocellulosic biomass from which they can be extracted. These materials have potential applications in a wide array of areas because of their unique properties such as ultra-high aspect ratios and specific strengths. However, the high energy required to extract CNFs from biomass through fibrillation often makes them prohibitively expensive or negates their inherent sustainability. As such, a variety of biomass treatments prior to fibrillation have been investigated by researchers to reduce the energy requirements of CNF extraction, improve the efficacy of biomass fibrillation and subsequent processes, and/or impart functionality in resulting nanofibrils. In this work, both widely used and emerging mechanical, chemical, and enzymatic pretreatments used prior to fibrillation of lignocellulosic biomass for CNF extraction are reviewed. Attention is given to the effect of these various pretreatments on the properties of the resulting CNFs. Finally, the energy consumption in fibrillation processes with and without the use of pretreatments is compared, and future perspectives on challenges and opportunities in lignocellulosic feedstock pretreatments are discussed.

59 BASIC BIOLOGICAL SCIENCES↗