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Ciesielski, Peter N.

Publications and source records attributed to Ciesielski, Peter N..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Dataset_for_Conserved_macromolecular_architecture_of_Poplar_secondary_cell_walls_revealed_by_ssNMR_and_atomistic_modeling

This dataset contains solid-state 13C NMR data and atomistic molecular dynamics simulation files supporting the study of nanoscale secondary cell wall architecture across 13 genetically diverse Populus trichocarpa genotypes grown under uniform greenhouse conditions in 13C-enriched CO2 atmospheres (~89% 13C enrichment).The dataset contains two collections of solid-state 13C NMR data. (1) 200 MHz data (Bruker Avance III HD, 4 mm HX probe, 10 kHz MAS): raw Bruker TopSpin experiment folders and DMFIT-exported ascii spectra for selective and non-selective 1D 13C-13C spin diffusion experiments (3000 ms mixing) used to quantify inter-polymer spatial proximities, and short-mixing (1 ms) reference spectra used for polymeric abundance quantification by spectral deconvolution. (2) 600 MHz data (Bruker Avance III, 1.6 mm PhoenixNMR HXY probe, 30 kHz MAS): raw Bruker TopSpin experiment folders containing 2D CORD, 2D CP-INADEQUATE, and 13C/1H relaxation (T1, T1rho) experiments for all 13 genotypes, with processed Excel workbooks per experiment type. Molecular dynamics simulation code, coordinate files, and analysis scripts (NAMD/CHARMM/Python) for six atomistic cell wall models are included. Summarized ssNMR data are compiled into a single excel file and subjected to statistical analysis. Multivariate analysis code (PCA, Pearson correlation) and summary data are provided as excel worksheets and Jupyter notebooks (Python 3).

09 BIOMASS FUELS↗
DOE OSTI2024

Structural and chemical changes in hardwood cell walls during early stages of flash pyrolysis

Volatile products from thermal decomposition of lignocellulosic biomass have been well characterized, but the solid- and liquid-phase reactions during the early stages of decomposition are largely unknown. Here the initial solid-phase biomass thermal deconstruction reactions were analyzed in situ and with high particle heating rates, delineating how these processes occur. A variety of instrumentation was used to quantify the extent and relative rates of deconstruction, demonstrating that biopolymers resist the thermally energetic conditions to differing degrees, even when ensconced in biomass cell walls. Hemicellulose and the more frangible lignin components decompose and volatilize more readily than cellulose, which temporarily enriches biomass with cellulose. These chemical changes manifest in larger cell wall structural and mechanical property transformations. In all, this investigation concludes that these solid-phase reactions strongly influence the production rates of volatile species and will require additional study before these processes can be modeled precisely to improve yields of desired product.

09 BIOMASS FUELS↗
DOE OSTI2024

Atomistic, macromolecular model of the Populus secondary cell wall informed by solid-state NMR

Plant secondary cell walls (SCWs) are composed of a heterogeneous interplay of three major biopolymers: cellulose, hemicelluloses, and lignin. Details regarding specific intermolecular interactions and higher-order architecture of the SCW superstructure remain ambiguous. Here, we use solid-state nuclear magnetic resonance (ssNMR) measurements to infer refined details about the structural configuration, intermolecular interactions, and relative proximity of all three major biopolymers within air-dried Populus wood. To enhance the utility of these findings and enable evaluation of hypotheses in a physics-based environment in silico, the NMR observables are articulated into an atomistic, macromolecular model for biopolymer assemblies within the plant SCW. Through molecular dynamics simulation, we quantitatively evaluate several variations of atomistic models to determine structural details that are corroborated by ssNMR measurements.

09 BIOMASS FUELS↗
DOE OSTI2023

Diffusion in intact secondary cell wall models of plants at different equilibrium moisture content

Secondary plant cell walls are composed of carbohydrate and lignin polymers, and collectively represent a significant renewable resource. Leveraging these resources depends in part on a mechanistic understanding for diffusive processes within plant cell walls. Common wood protection treatments and biomass conversion processes to create biorefinery feedstocks feature ion or solvent diffusion within the cell wall. X-ray fluorescence microscopy experiments have determined that ionic diffusion rates are dependent on cell wall hydration as well as the ionic species through non-linear relationships. In this work, we use classical molecular dynamics simulations to map the diffusion behavior of different plant cell wall components (cellulose, hemicellulose, lignin), ions (Na + , K + , Cu2 + , Cl - ) and water within a model for an intact plant cell wall at various hydration states (3-30 wt% water). From these simulations, we analyze the contacts between different plant cell wall components with each other and their interaction with the ions. Generally, diffusion increases with increasing hydration, with lignin and hemicellulose components increasing diffusion by an order of magnitude over the tested hydration range. Ion diffusion depends on charge. Positively charged cations preferentially interact with hemicellulose components, which include negatively charged carboxylates. As a result, positive ions diffuse more slowly than negatively charged ions. Measured diffusion coefficients are largely observed to best fit piecewise linear trends, with an inflection point between 10 and 15% hydration. These observations shed light onto the molecular mechanisms for diffusive processes within secondary plant cell walls at atomic resolution.

09 BIOMASS FUELS↗
DOE OSTI2022

Fast estimation of reaction rates in spherical and non-spherical porous catalysts

Here we present a methodology for modeling multi-step reaction rates in porous catalyst particles for use in CFD-DEM and two fluid models. Single-step effectiveness factors based on a Thiele modulus, while useful, cannot accurately capture the cascading reaction systems common in high temperature vapor-phase chemical reactors like fluidized catalytic cracking units and catalytic biomass fast pyrolysis systems. Instead, multi-step effectiveness vectors derived from steady-state solutions to the governing reaction-diffusion equations are needed. Solutions for various catalyst shapes are presented, including spheres, cylinders, and prisms. Computational challenges inherent in repeated evaluation of reaction rates with diffusion limitations are discussed, and an efficient implementation based on pre-computed lookup tables is proposed and demonstrated on a simulation of a fluidized bed reactor. Open-source code is provided for the compilation of reaction rate tables for use in ODE, DEM, and two-fluid models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Roll-to-Roll, Dual-Layer Slot Die Coating of Chitin and Cellulose Oxygen Barrier Films for Renewable Packaging

Cellulose and chitin are the two most abundant naturally produced biopolymers and are being extensively studied as candidates for renewable oxygen barrier films used in packaging. It has been shown that bilayers formed from cellulose nanocrystals (CNCs) and chitin nanofibers (ChNFs) exhibit oxygen barrier properties similar to polyethylene terephthalate (PET). However, this prior work explored only coating each layer individually in sequence through techniques such as spray coating. Here, we demonstrate the viability of dual-layer slot die coating of CNC/ChNF bilayers onto cellulose acetate (CA) substrates. The dual-layer slot die method enables significantly lower oxygen permeability versus spray coating while using a roll-to-roll system that applies the bilayer in a single pass. This work discusses suspension properties, wetting, and drying conditions required to achieve well-controlled ChNF/CNC bilayers. Spray-coated bilayer films were on average 25% thinner than the dual-layer bilayer film; however, the thickness-normalized oxygen permeability (OP) of the dual-layer-coated ChNF/CNC bilayer film on CA was 20 times better than that of the spray-coated bilayers. Additionally, it has been shown that ChNF contributes to the wetting and barrier properties. Values of OP for the slot die-coated bilayers under optimized drying conditions were as low as 1.2 cm 3 ∙μm∙m -2 ∙d -1 ∙kPa -1 , corresponding to a normalized oxygen transmission rate of 0.32 cm 3 ∙m -2 ∙d -1 at 23 °C and 50% relative humidity. It is also noted that the adhesive properties of the dual-layer coating are also improved when films are air-dried and that ChNF contributes to the wetting and barrier properties.

09 BIOMASS FUELS↗
DOE OSTI2022

CFD-DEM Modeling of Autothermal Pyrolysis of Corn Stover with a Coupled Particle- and Reactor-Scale Framework

Autothermal operation of fast pyrolysis is an efficient process-intensification technique wherein exothermic oxidation reactions are used to overcome the heat-transfer bottleneck of conventional pyrolysis. The development of accurate, reliable modeling toolsets is imperative to generating a deeper understanding of biomass autothermal pyrolysis systems to support scale-up and industrial deployment. This modeling effort describes the development of single-particle and reactor models which incorporate detailed reaction schemes and simultaneous exothermic oxidation reactions. The particle-scale model was parameterized for corn stover feedstock with particle morphology, density, ash content, and biopolymer composition, all of which impact the emergent conversion characteristics during pyrolysis. Results were then used to parameterize a reactor-scale autothermal pyrolysis model, which was developed using a coarse-grained computational fluid dynamic-discrete element method. The simulation results compared well with experimental results, with the predicted bio-oil, light gas, and biochar yield within 3.0 wt% of the experimental yields. Further analyses were performed to test the influence of equivalence ratio, biomass injection position, and particle size distribution on autothermal pyrolysis. The analysis of the physio-chemical properties of the fluid and solid phase inside the reactor and at the reactor outlet help reveal important process interactions of autothermal pyrolysis.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗
DOE OSTI2022

Measurement of Transport Properties of Woody Biomass Feedstock Particles Before and After Pyrolysis by Numerical Analysis of X-Ray Tomographic Reconstructions

Lignocellulosic biomass has a complex, species-specific microstructure that governs heat and mass transport during conversion processes. A quantitative understanding of the evolution of pore size and structure is critical to optimize conversion processes for biofuel and bio-based chemical production. Further, improving our understanding of the microstructure of biochar coproduct will accelerate development of its myriad applications. This work quantitatively compares the microstructural features and the anisotropic permeabilities of two woody feedstocks, red oak and Douglas fir, using X-ray computed tomography (XCT) before and after the feedstocks are subjected to pyrolysis. Quantitative analysis of the three-dimensional (3D) reconstructions allows for direct calculations of void fractions, pore size distributions and tortuosity factors. Next, 3D images are imported into an immersed boundary based finite volume solver to simulate gas flow through the porous structure and to directly calculate the principal permeabilities along longitudinal, radial, and tangential directions. The permeabilities of native biomass are seen to differ by three to four orders of magnitude in the different principal directions, but we find that this anisotropy is substantially reduced in the biochar formed during pyrolysis. The quantitative transport properties reported here enhance the ability of pyrolysis simulations to account for feedstock-specific effects and thereby provide a useful touchstone for the biorefining community.

09 BIOMASS FUELS↗
DOE OSTI2022

Mass Transport Limitations and Kinetic Consequences of Corn Stover Deacetylation

Alkaline pretreatment of herbaceous feedstocks such as corn stover prior to mechanical refining and enzymatic saccharification improves downstream sugar yields by removing acetyl moieties from hemicellulose. However, the relationship between transport phenomena and deacetylation kinetics is virtually unknown for such feedstocks and this pretreatment process. Here, we report the development of an experimentally validated reaction–diffusion model for the deacetylation of corn stover. A tissue-specific transport model is used to estimate transport-independent kinetic rate constants for the reactive extraction of acetate, hemicellulose and lignin from corn stover under representative alkaline conditions (5–7 g L -1 NaOH, 10 wt% solids loadings) and at low to mild temperatures (4–70°C) selected to attenuate individual component extraction rates under differential kinetic regimes. The underlying transport model is based on microstructural characteristics of corn stover derived from statistically meaningful geometric particle and pore measurements. These physical descriptors are incorporated into distinct particle models of the three major anatomical fractions (cobs, husks and stalks) alongside an unsorted, aggregate corn stover particle, capturing average Feret lengths of 917–1239 μm and length-to-width aspect ratios of 1.8–2.9 for this highly heterogeneous feedstock. Individual reaction–diffusion models and their resulting particle model ensembles are used to validate and predict anatomically-specific and bulk feedstock performance under kinetic-controlled vs. diffusion-controlled regimes. In general, deacetylation kinetics and mass transfer processes are predicted to compete on similar time and length scales, emphasizing the significance of intraparticle transport phenomena. Critically, we predict that typical corn stover particles as small as ~2.3 mm in length are entirely diffusion-limited for acetate extraction, with experimental effectiveness factors calculated to be 0.50 for such processes. Debilitatingly low effectiveness factors of 0.021–0.054 are uncovered for cobs—implying that intraparticle mass transfer resistances may impair observable kinetic measurements of this anatomical fraction by up to 98%. These first-reported quantitative maps of reaction vs. diffusion control link fundamental insights into corn stover anatomy, biopolymer composition, practical size reduction thresholds and their kinetic consequences. These results offer a guidepost for industrial deacetylation reactor design, scale-up and feedstock selection, further establishing deacetylation as a viable biorefinery pretreatment for the conversion of lignocellulosics into value-added fuels and chemicals.

09 BIOMASS FUELS↗
DOE OSTI2021

Minimizing Oxygen Permeability in Chitin/Cellulose Nanomaterial Coatings by Tuning Chitin Deacetylation

The demand for packaging materials with low gas permeabilities is increasing, but commonly used petroleum-derived single-use plastics are not renewable, biodegradable, or easy to recycle. Nanomaterials composed of chitin and cellulose, which are abundant in nature, have high crystallinities and low oxygen permeabilities (OP), providing a viable alternative. In this work, we explore how deacetylation conditions of crab shell chitin can be used to tune the charge and size of resulting chitin nanowhiskers (ChNWs) and the resulting OP of layered film structures. Three deacetylation factors, the concentration of sodium hydroxide (%NaOH), temperature (T), and reaction time, were explored using a three-factor three-level Taguchi design with an orthogonal array. Furthermore, the resulting ChNW suspensions were sequentially spray-coated with suspensions of cellulose nanocrystals (CNCs) onto cellulose acetate (CA) films to form a multilayer structure. We show that ChNWs prepared under more aggressive deacetylation conditions inside the original orthogonal array (higher %NaOH, T, and time) had shorter lengths but the surface charge was significantly influenced only by more aggressive deacetylation outside of the original design conditions. With only ~10% decrease in the ultimate tensile strength and no significant loss in failure strain, the ChNW-CNC coating resulted in ~20% decrease in WVTR in comparison to uncoated CA films. The optimization of process conditions resulted in CA-ChNW-CNC films with a 91-99% decrease in OP (132-16.7 cm 3 ∙μm/m 2 /day/kPa versus 1553 cm3∙μm/m2/day/kPa for uncoated CA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Impacts of Anisotropic Porosity on Heat Transfer and Off-Gassing during Biomass Pyrolysis

The pore structure of biogenic materials imbues the ability to deliver water and nutrients through a plant from root to leaf. This anisotropic pore granularity can also play a significant role in processes such as biomass pyrolysis that are used to convert these materials into useful products like heat, fuel, and chemicals. Evolutions in modeling of biomass pyrolysis as well as imaging of pore structures allow for further insights into the concerted physics of phase change-induced off-gassing, heat transfer, and chemical reactions. In this work, we report a biomass single particle model which incorporates these physics to explore the impact of implementing anisotropic permeability and diffusivity on the conversion time and yields predicted for pyrolysis of oak and pine particles. Simulation results showed that anisotropic permeability impacts predicted conversion time more than 2 times when the Biot number is above 0.1 and pyrolysis numbers (Py 1 , Py 2 ) are less than 20. Pore structure significantly impacts predicted pyrolytic conversion time (>8 times) when the Biot number is above 1 and the pyrolysis number is below 1, i.e., the “conduction controlled” regime. Therefore, these nondimensional numbers reflect that when internal heat conduction limits pyrolysis performance, internal pyrolysis off-gassing further retards effective heat transfer rates as a closely coupled phenomenon. Overall, this study highlights physically meaningful opportunities to improve particle-scale pyrolysis modeling and experimental validation relevant to a variety of feedstock identities and preparations, guiding the future design of pyrolyzers for efficient biomass conversion.

09 BIOMASS FUELS↗
DOE OSTI2021

A simplified integrated framework for predicting the economic impacts of feedstock variations in a catalytic fast pyrolysis conversion process

Feedstock attributes of lignocellulosic biomass, such as particle size, compositional makeup, and moisture content, can vary substantially even within pre-processed materials and have a significant effect on conversion in fast pyrolysis-based processes. However, the economic impacts of these attributes are not well understood. To address this, biomass deconstruction phenomena captured with a versatile particle-scale simulation were linked to techno-economic impacts via reduced-order models. Parametric analysis of the particle-scale model, which was validated using literature data, was used in combination with multiple linear regression models to develop correlations between feedstock attributes and yields of pyrolysis oil, gas, and char. Yields were then correlated with the minimum fuel selling price (MFSP) using a techno-economic model, bridging the gap between physics-based biomass conversion simulations and predictions of MFSP for a catalytic fast-pyrolysis process. Empirical correlations derived from the literature regarding the impact of mineral matter (ash) on oil yield were also considered. The model correlations deployed in the integrated framework capture the impacts of variation in feedstock attributes on the MFSP. Variations in ash were shown to have the biggest impact, varying MFSP by -13%/+22% due to catalytic effects and lower relative amounts of convertible lignocellulosic material. It was also found that, if ash can be controlled to low levels, the increased extractives in forest residues can help compensate for some yield losses associated with increased ash. As a result, other inputs considered (particle size, moisture content, and reactor temperature) had relatively negligible effects on process economics within the ranges analyzed considering particle-scale effects alone.

BIOMASS FUELS↗
DOE OSTI2021

Bridging Scales in Bioenergy and Catalysis: A Review of Mesoscale Modeling Applications, Methods, and Future Directions

Between the molecular and reactor scales, which are familiar to the chemical engineering community, lies an intermediate regime, here termed the “mesoscale,” where transport phenomena and reaction kinetics compete on similar time scales. Bioenergy and catalytic processes offer particularly important examples of mesoscale phenomena owing to their multiphase nature and the complex, highly variable porosity characteristic of biomass and many structured catalysts. In this review, we overview applications and methods central to mesoscale modeling as they apply to reaction engineering of biomass conversion and catalytic processing. A brief historical perspective is offered to put recent advances in context. Applications of mesoscale modeling are described, and several specific examples from biomass pyrolysis and catalytic upgrading of bioderived intermediates are highlighted. Methods including reduced order modeling, finite element and finite volume approaches, geometry construction and import, and visualization of simulation results are described; in each category, recent advances, current limitations, and areas for future development are presented. Owing to improved access to high-performance computational resources, advances in algorithm development, and sustained interest in reaction engineering to sustainably meet societal needs, we conclude that a significant upsurge in mesoscale modeling capabilities is on the horizon that will accelerate design, deployment, and optimization of new bioenergy and catalytic technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Filtration Performance of Layering Masks and Face Coverings and the Reusability of Cotton Masks after Repeated Washing and Drying

In this study, filtration efficiency of different respirators, face masks, and a 2-ply cotton handkerchief bandana was compared for particles in the size range of 60 nm-4 um under a "perfect fit" condition. The filtration efficiency at the most penetrating particle size of 0.3 um on average ranged from 83-99% for N95 and KN95 respirators, 42-88% for surgical masks, 16-23% for cloth masks, and 9% for bandana. We also investigated the effects of using double surgical masks or layering a cloth mask over various surgical masks in terms of their filtration characteristics. In most of these combinations, the filtration efficiency improved by ~25% for particles 0.3-1 um in diameter without any substantial change in the filter quality factor when compared to the highest of the individual mask results. To investigate the reusability of cotton cloth masks, 2-layer cotton fabric sample coupons were machine washed and dried for 52 cycles leading to an increase in inhalation resistance (~20 Pa) without affecting size-resolved filtration efficiency. Scanning electron microscopy revealed that washing and drying led to the gradual deconstruction of cotton fibers at the scale of several micrometers to hundreds of nanometers in the form of delamination of the fiber wall and fibrillation of the nanofiber constituents. Results indicate that cloth masks may be layered over surgical masks for additional benefits, and that cloth masks made out of cotton fabric can be washed and reused numerous times without a significant loss in filtration efficiency.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2021

Towards sustainable production and utilization of plant-biomass-based nanomaterials: a review and analysis of recent developments

Abstract Plant-biomass-based nanomaterials have attracted great interest recently for their potential to replace petroleum-sourced polymeric materials for sustained economic development. However, challenges associated with sustainable production of lignocellulosic nanoscale polymeric materials (NPMs) need to be addressed. Producing materials from lignocellulosic biomass is a value-added proposition compared with fuel-centric approach. This report focuses on recent progress made in understanding NPMs—specifically lignin nanoparticles (LNPs) and cellulosic nanomaterials (CNMs)—and their sustainable production. Special attention is focused on understanding key issues in nano-level deconstruction of cell walls and utilization of key properties of the resultant NPMs to allow flexibility in production to promote sustainability. Specifically, suitable processes for producing LNPs and their potential for scaled-up production, along with the resultant LNP properties and prospective applications, are discussed. In the case of CNMs, terminologies such as cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) used in the literature are examined. The term cellulose nano-whiskers (CNWs) is used here to describe a class of CNMs that has a morphology similar to CNCs but without specifying its crystallinity, because most applications of CNCs do not need its crystalline characteristic. Additionally, progress in enzymatic processing and drying of NPMs is also summarized. Finally, the report provides some perspective of future research that is likely to result in commercialization of plant-based NPMs.

09 BIOMASS FUELS↗
DOE OSTI2020

Investigating biomass composition and size effects on fast pyrolysis using global sensitivity analysis and CFD simulations

It is notoriously difficult to build an accurate universal model for biomass pyrolysis due to its sensitivity to a wide number of critical material attributes such as chemical species and physical sizes. In this work, a biomass pyrolysis kinetics with 32 heterogeneous reactions and 59 species was implemented in an open-source multiphase computational fluid dynamics (CFD) software MFiX and validated against two different experimental pyrolysis data sets that provided detailed data describing chemical component yields. The reaction scheme was then used to build a surrogate model and assess the sensitivity of pyrolysis yields to feedstock compositions. The sensitivity analysis determined that the yield of bio-char showed a strong positive sensitivity to the carbon-rich lignin and tannin pseudo-species in the reaction scheme while the bio-oil and bio-gas were correlated to oxygen-rich lignin pseudo-species. The reaction scheme was then integrated into a coarse-grained discrete element model to simulate fast pyrolysis in a bubbling fluidized bed over a range of feedstock particle sizes. The reactor simulations showed further sensitivity to particle size and hydrodynamics. Notably, particles under 0.5 mm have small heat transfer limitations but left the reactor before completely converting and thus reduced the bio-oil yield. Results from this study can be used to guide future development of highly accurate models for fast pyrolysis reactors with a variety of feedstock properties and operating conditions.

09 BIOMASS FUELS↗