Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Elemental analysis”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Parallel projection—An improved return mapping algorithm for finite element modeling of shape memory alloys

Here, we present a novel finite element analysis of inelastic structures containing Shape Memory Alloys (SMAs). Phenomenological constitutive models for SMAs lead to material nonlinearities, that require substantial computational effort to resolve. Finite element analysis methods, which rely on Gauss quadrature integration schemes, must solve two sets of coupled differential equations: one at the global level and the other at the local, i.e. Gauss point level. In contrast to the conventional return mapping algorithm, which solves these two sets of coupled differential equations separately using a nested Newton procedure, we propose a scheme to solve the local and global differential equations simultaneously. In the process we also derive closed-form expressions used to update the internal/constitutive state variables, and unify the popular closest-point and cutting plane methods with our formulas. Numerical testing indicates that our method allows for larger thermomechanical loading steps and provides increased computational efficiency, over the standard return mapping algorithm.

42 ENGINEERING↗
DOE OSTI2023

Exploration of LIBS as a novel and rapid elemental mapping technique of nuclear fuels in the form of surrogate TRISO particles

Laser-induced breakdown spectroscopy (LIBS) was employed to characterize coatings on surrogate fuel particles. Tri-structural isotropic (TRISO) particles are a proposed nuclear fuel alternative for high temperature reactors. These particles are constructed of a ZrO 2 kernel (as a surrogate to uranium), surrounded by an inner pyrolytic carbon layer and are surrounded by an outer carbide layer (ZrC, presented here) to act as a barrier to fission products generated during nuclear reactions. These particles are embedded within a graphite compact and housed within the reactor core. Simply put, due to their robust nature, performing elemental analysis of these particles poses a challenge. Presented here, LIBS is explored as a method for characterizing elemental constituents of these particles, with the focus being on rapid elemental mapping and depth profiling. Different from traditional elemental analysis techniques (e.g., inductively coupled plasma – based methods), LIBS is advantageous because it can directly analyze the sample surface and can detect light elements such as C and O, making it a viable technique for the analysis of small, multilayered particles as spatial elemental information is warranted in the production of these particles. In the work presented here, LIBS was successfully used for discerning small layers (30–50 μm), detecting the location of carbon and oxygen layers, providing fast 2-D mapping (<5 min per particle) and rapid depth profiling (10 s per particle).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Synthesis, Structure, and Photophysical Properties of Platinum Compounds with Thiophene-Derived Cyclohexyl Diimine Ligands

Platinum(II) and platinum(IV) compounds were prepared by the stereoselective and regioselective reactions of thiophene-derived cyclohexyl diimine C^N^N-ligands with [Pt 2 Me 4 (μ-SMe 2 ) 2 ]. Newly synthesized ligands were characterized by NMR spectroscopy and elemental analysis, and Pt(II)/Pt(IV) compounds were characterized by NMR spectroscopy, elemental analysis, high-resolution mass spectrometry, and single-crystal X-ray diffraction. UV–vis absorbance and photoluminescence measurements were performed on newly synthesized complexes, as well as structurally related Pt(II)/Pt(IV) compounds with benzene-derived cyclohexyl diimine ligands, in dichloromethane solution, as solids, and as 5% by weight PMMA-doped films. DFT and TD-DFT calculations were performed, and the results were compared with the observed spectroscopic properties of the newly synthesized complexes. X-ray total scattering measurements and real space pair distribution function analysis were performed on the synthesized complexes to examine the local- and intermediate-range atomic structures of the emissive solid states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

The importance of ester cleavage in the butylamine pretreatment of hybrid poplar

Butylamine is an effective in-and-out pretreatment solvent for hybrid poplar. It penetrates the cell walls and breaks ester cross-linkages, facilitating lignin release and improving enzymatic digestion. This work explores the “in-and-out” pretreatment of hybrid poplar with butylamine as a distillable protic solvent and reagent. The butylamine solvent can be removed by vacuum distillation with >95% solvent removal in all cases, providing a valuable scheme for efficient solvent recovery and recycling. Running the reaction with neat butylamine at 140 °C for 3 hours results in high yields of monosaccharides (90% glucose and 71% xylose) after enzymatic digestion, and a good tolerance to water content with no significant reduction in glucose yield up to an 8 : 1 water : butylamine ratio. We investigate the mechanisms of this pretreatment using powder X-ray diffraction, thermogravimetric analysis, fluorescence microscopy, elemental analysis, solid state and solution state nuclear magnetic spectroscopy to observe chemical and material markers of the pretreatment chemistry. The results suggest that the butylamine leaves the macro and microstructural properties of the lignocellulose relatively unaltered, but conducts targeted ester cleavage chemistry to remove cross-links between the various biopolymers and partially solubilize the lignin component of the biomass. These findings should act to guide future development of pretreatment chemistry for the development of biorefinery processes, and assist in the utilization of biomass as a starting point for chemical syntheses.

Palasz, Joseph M↗
DOE OSTI2026

A meshing framework for digital twins for extrusion based additive manufacturing

Additive manufacturing (AM) allows for manufacturing of complex three-dimensional geometries not typically realizable with standard manufacturing practices. The internal microstructure of AM components has a significant impact on mechanical, vibrational, and shock properties and permits richer design space when this is controllable. Due to complex interactions of internal geometry of an extrusion-based AM component, it is common practice to assume homogeneous behavior or to perform characterization testing on specific toolpath configurations. To avoid testing or material waste, it is necessary to develop a consistently accurate numerical simulation framework with relevant boundary value problems that can handle the complicated geometry of internal material microstructure present in AM components. Herein, a framework is proposed to directly create computational meshes suitable for finite element analysis (FEA) of the fine-scale features generated from extrusion-based AM tool paths to maintain a strong process–structure–property-performance linkage. This mesh can be manually or automatically analyzed using standard FEA simulations such as quasi-static preloading or modal analysis. The framework allows an in-silico assessment of a target AM geometry where fine-scale features greatly impact quantities of design interest such as in soft elastomeric lattices where toolpath infill can greatly influence the self-contact of a structure in compression, which we use as a motivating exemplar. This approach greatly reduces both time and resource waste present in traditional build and test design cycles for non-intuitive design spaces, and acts as a tool for use in the production of a key component of a digital twin, a mesh suitable for finite element analysis. In conclusion, it also further allows for the exploration of toolpath infill to optimize component properties beyond simple linear properties such as density and stiffness.

Additive manufacturing↗
DOE OSTI2020

Experimentally Validated Computational Modeling of Creep and Creep-Cracking for Nuclear Concrete Structures

In a Nuclear Power Plant, one of the most important components is the concrete nuclear reactor cavity, which serves both a structural and protective function as the biological radiation shield. Given that creep has been identified as a major knowledge gap in the assessment of nuclear structures (NUREG/CR-7153), this work helps to further the understanding of creep behavior of massive concrete containment structures for decades to enable safe and long-term operation of these facilities. This project has developed a robust, experimentally validated model to predict creep in nuclear concrete structures for up 60 years using short-term creep data thereby enabling a longer service life of critical facilities and early detection of structural failure. The work presented in this report is a pairing of computational and experimental methods. For the first time, the time temperature superposition (TTS) principle was successfully used to generate a uniaxial creep compliance master curve to predict mortar creep response for up to 22,500 days (nearly 60 years) at a reference temperature of 20°C. These data were used as input into finite element analysis (FEA) codes that use highly realistic random, 3D concrete microstructures from reconstructed coarse limestone aggregates. Finite element analysis performed provides the ability to quickly upscale mortar viscoelastic behavior to long-term concrete creep/relaxation data. A master creep compliance curve, constructed from the TTS principle, spanning 27 years, was used to validate two and a half decades of simulated concrete creep. Concurrently, three different simulated wall specimens were designed to mimic the behavior of post-tensioned concrete nuclear containment facility vessel walls over time as a result of concrete creep. The specimens were designed with different thicknesses, transverse and longitudinal reinforcement ratios, and level of post-tensioning stress. Each specimen contained various instrumentation to measure internal concrete temperature, concrete strain, and post-tensioning strain hourly for over 3 years. The concrete creep model developed in this project, based on the FEA concrete simulations, was applied to simulate the structural-scale experiments of prestressed concrete walls conducted in this project using the Grizzly code. These models can represent the effects of reinforcing and prestressing. Although there are some discrepancies with the experimental data, the model can predict the overall trends of the creep response in these experiments. One of these experimental models was also applied to an extended time to demonstrate how the findings from this study can be used to predict the behavior of actual structures of interest that have been in service for extended periods of time.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2024

Feasibility Study for Cathodic Protection of Waste Tanks at Hanford

The Hanford Nuclear Reservation site contains approximately 211 million liters of radioactive and chemically hazardous waste arising from nuclear weapons production, beginning with World War II, and continuing through the Cold War. The waste is stored in 177 carbon-steel underground storage tanks, of which 149 are single-shell tanks (SSTs) and the remaining are double-shell tanks (DSTs). The mission of an ongoing River Protection Project is to retrieve the waste from the underground storage tanks and then treat and immobilize (i.e., vitrify) it for disposal. Waste from the older SSTs is being progressively retrieved into the newer DSTs for storage pending treatment, immobilization, and disposal. Waste chemistry controls are in place to mitigate general corrosion, pitting corrosion, and stress corrosion cracking (SCC) and minimize corrosion risks to the carbon steel tank liners of DST at the Hanford Site. The chemistry control program focuses on preserving liner integrity while balancing the need for caustic/nitrite additions that have large downstream impacts on vitrification. Some of the DSTs store salt cake or sludge waste layers contain out-of-specification interstitial liquids that contact the primary tank bottom or sidewall. Remediation of such layers through chemical additions is not practical. At the present time, the most significant leak integrity concern at Hanford is for corrosion of the tank bottoms of DSTs where the solids layer is out of specification because of hydroxide ion depletion and consequently, pH values that are less than 12. Cathodic protection (CP) has been proposed as a possible way to protect the liners of such tanks against corrosion. The objective of this project was to investigate the feasibility of applying CP to Hanford DSTs to mitigate internal corrosion of the carbon steel tank primary liners. The scope of the project included (1) a literature review on the application of CP to storage tank systems, in general, and to waste tanks at the Savannah River Site (SRS) and Hanford, (2) a review of the finite element analysis (FEA) model recently developed to evaluate potentials for a DST, and (3) the development of a boundary element analysis (BEA) model for CP for a DST. Tank AN-107, one of the Hanford DSTs, was selected for this work because (1) the bottommost waste layer in the tank is out-of-specification, and (2) electrochemical and resistivity data, based on recent waste sampling and testing, are available for this tank. The overarching conclusion of this study is that, based on the available information, it is feasible to apply CP to mitigate internal corrosion of the primary liners of the Hanford DSTs. However, significant additional information and work are required before a CP system can be designed. Recommendations for next steps in the design of the CP system will be presented.

WIERSMA, BRUCE↗
DOE OSTI2020

Thermo-mechanical modeling and experimental validation for multilayered metallic microstructures

This paper presents thermo-mechanical modeling on multilayered metallic microstructures consisting of two bilayers that enable 3D deployment once being Joule heated. Additionally, a representative design of such microstructures, as well as their working principle is introduced. Furthermore, a mathematical model is derived using Euler–Bernoulli beam theory, and analytical solutions describing out-of-plane displacement of the multilayered microstructures when uniformly heated, which is validated by finite element analysis. Parametric analysis on thermal load and dimensional change of beam shows a good agreement between the analytical solutions and results given by finite element analysis. The phases of the near-equiatomic NiTi layer are analyzed by EDS and XRD, which prove to be austenite during the Joule heating process. The mechanical properties of austenite NiTi are incorporated into the analytical solutions that provides a good estimation of 3D deployment of microstructures made of NiTi and aluminum. The experimental results provide an approximately 7 µm out-of-plane deployment by applying a uniform temperature increase of 132 K, and parametric analysis on the dimension of top aluminum beam offers another promising approach to larger 3D deployment. The proposed mathematical model provides an efficient tool for predicting the out-of-plane deployment of such multilayered microstructures.

36 MATERIALS SCIENCE↗
DOE OSTI2025

A TOpographic Mapping (ATOM) Method to Design Magnetic Cores

Wireless power transfer offers safe, convenient, and efficient way of charging electric vehicles. Ongoing research is targeting wireless charging pad design optimization; designing the magnetic component is the most important part of the coupler design because the magnetic part determines the coupling factor and efficiency. Optimizing the coil layout and geometry as well as ferrite design requires finite elements analysis based modeling and simulation for minimized core losses, maximized magnetic coupling, and minimized material use for cost-effectiveness. Although parametric finite element analysis or emerging artificial intelligence methods can generate very accurate results, simulation times are extremely long. To address this issue, this study proposes a simple, effective core design called A TOpographic Mapping (ATOM). The proposed design is based on the design of magnetic core by using the magnetic flux distribution. The thickness of the core increases with increasing magnetic flux density, forming a variable thickness core design with less material and minimized core losses compared to conventional designs. A superimposing method is used to create an optimal design for a rotational magnetic field-based system. According to simulation results, the ATOM design reduces the required material volume by 13.19% and yields the lowest core loss and highest mutual inductance compared to other designs. In addition, misalignment, electromagnetic interference, and thermal performance were evaluated for the proposed design.

Aydin, Emrullah [Oak Ridge National Laboratory (OR↗
DOE OSTI2024

Full-field quantitative visualization of shock-driven pore collapse and failure modes in PMMA

The dynamic collapse of pores under shock loading is thought to be directly related to hot spot generation and material failure, which is critical to the performance of porous energetic and structural materials. However, the shock compression response of porous materials at the local, individual pore scale is not well understood. This study examines, quantitatively, the collapse phenomenon of a single spherical void in PMMA at shock stresses ranging from 0.4 to 1.0 GPa. Using a newly developed internal digital image correlation technique in conjunction with plate impact experiments, full-field quantitative deformation measurements are conducted in the material surrounding the collapsing pore for the first time. The experimental results reveal two failure mode transitions as shock stress is increased: (i) the first in situ evidence of shear localization via adiabatic shear banding and (ii) dynamic fracture initiation at the pore surface. Numerical simulations using thermo-viscoplastic dynamic finite element analysis provide insights into the formation of adiabatic shear bands (ASBs) and stresses at which failure mode transitions occur. Further numerical and theoretical modeling indicates the dynamic fracture to occur along the weakened material inside an adiabatic shear band. Finally, analysis of the evolution of pore asymmetry and models for ASB spacing elucidate the mechanisms for the shear band initiation sites, and elastostatic theory explains the experimentally observed ASB and fracture paths based on the directions of maximum shear.

42 ENGINEERING↗
DOE OSTI2023

Radiative transition probabilities of neutral and singly ionized rare earth elements (La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) estimated by laser-induced breakdown spectroscopy

Rare earth elements (REEs) are essential to society given their prevalence in many modern technologies. Quantitative elemental analysis of REEs is therefore a critical capability. Calibration free–laser-induced breakdown spectroscopy (CF-LIBS) is a rapidly maturing and promising approach to quantitative elemental analysis with many attractive qualities. The application of CF-LIBS to analyzing samples containing the REEs is hindered by a lack of fundamental data, specifically transition probabilities (TPs). As such, this study seeks to help address this knowledge deficiency by reporting 967 previously unreported TPs for 13 REEs (lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium). The method developed in this study to estimate the TPs requires small amounts of material (a few nanograms) compared with other approaches (~ milligrams), uses non-specialized equipment, and does not involve complicated sample preparations.

(LIBS)↗
DOE OSTI2023

Guidelines for predicting stress in cemented doublets undergoing temperature change

This work explores quick predictive methods for calculating potentially risky stresses and deflections in cemented doublets experiencing temperature change that agree well with finite element analysis. There are three failure modes of interest: cohesive failure of the adhesive, delamination (surface bond failure or debonding), and glass fracture. Adhesive theory, confirmed by finite element analysis, predicts stress singularities that complicate interpretation of the stress calculations. The presence of a stress singularity indicates the breakdown of linear elastic assumptions, but damage initiation and stress singularities are related. The authors find that geometry details near a bond edge can exacerbate or minimize damage initiation and stress concentrations. Because the interpretation of the stress results is complicated, the authors investigated predicted stresses in doublets that have been successfully tested between -40 and 85 °C. This study found that the product (ΔT ∙ Δα) should be less than 189 ppm, where ΔT is the temperature excursion and Δα is the difference in glass coefficient of thermal expansion. If the product (ΔT ∙ Δα) is equal to or greater than 189 ppm, further analysis and testing is warranted. But the authors also show that the fabrication process can significantly influence stress failure, particularly with large diameter doublets.

47 OTHER INSTRUMENTATION↗
DOE OSTI2023

Guidelines for predicting stress in cemented doublets undergoing temperature change

This work explores quick predictive methods for calculating potentially risky stresses and deflections in cemented doublets experiencing temperature change that agree well with finite element analysis. There are three failure modes of interest: cohesive failure of the adhesive, delamination (surface bond failure or debonding), and glass fracture. Adhesive theory, confirmed by finite element analysis, predicts stress singularities that complicate interpretation of the stress calculations. The presence of a stress singularity indicates the breakdown of linear elastic assumptions, but damage initiation and stress singularities are related. The authors find that geometry details near a bond edge can exacerbate or minimize damage initiation and stress concentrations. Because the interpretation of the stress results is complicated, the authors investigated predicted stresses in doublets that have been successfully tested between -40 and 85 °C. This study found that the product (∆T ∙ ∆α) should be less than 189 ppm, where ∆T is the temperature excursion and ∆α is the difference in glass coefficient of thermal expansion. If the product (∆T ∙ ∆α) is equal to or greater than 189 ppm, further analysis and testing is warranted. But the authors also show that the fabrication process can significantly influence stress failure, particularly with large diameter doublets

42 ENGINEERING↗
DOE OSTI2021

A Practical Analysis Framework for Assessment of Printed Circuit Heat Exchangers in High-Temperature Nuclear Service

Abstract Printed circuit heat exchangers (PCHEs) have high thermal efficiency because of the numerous minuscule channels. These minuscule channels result in a high thermal exchange area per unit volume, making PCHE a top contender for an intermediate heat exchanger (IHX) in high-temperature reactors. Thousands of minuscule channels make finite element analysis of the PCHE computationally infeasible. A two-dimensional analysis is usually performed for the PCHE core, which cannot simulate the local channel level responses reasonably because of the absence of global constraint influence. At present, there is no analysis technique available in the ASME Code or literature that is computationally efficient and suitable for engineers to estimate PCHE local responses. A novel but practical two-step analysis framework is proposed for performing PCHE analysis. In the first step, the channeled core is replaced by orthotropic solids with similar stiffness to simulate the global thermomechanical elastic responses of the PCHE. In the second step, local submodel analysis with detailed channel geometry and loading is performed using the elastic-perfectly plastic (EPP) material model. The proposed two-step analysis technique provides a unique capability to estimate the channel corner responses to be used for PCHE performance assessment. This study first developed a methodology for calculating the elastic orthotropic properties of the PCHE core. Next, the two-step analysis is performed for a realistic size PCHE core, and different issues observed in the results are scrutinized and resolved. Finally, a practical finite element analysis framework for PCHEs in high-temperature nuclear service is recommended.

Engineering↗
DOE OSTI2024

Aliphatic Amines from Waste Polyolefins by Tandem Pyrolysis, Hydroformylation, and Reductive Amination

Pyrolysis of waste plastics can produce a product mixture with a high concentration of olefins (>50 wt%). The olefins, as building blocks in the petroleum industry, are potential precursors for valuable commodity chemicals with higher values (>$2000 per ton). In this work, we produce aldehydes by hydroformylation of the olefins present in pyrolysis oil from colored post-consumer recycled high-density polyethylene (PCR-HDPE). The obtained aldehydes in the oil are then converted into aliphatic amines via reductive amination with a Ru/C catalyst. The aminated oil was characterized by multiple analytical chemistry techniques including elemental analysis, nuclear magnetic resonance spectroscopy, high-resolution liquid chromatography-mass spectrometry, and gas chromatography-mass spectrometry with a Polyarc flame ionization detector. The concentration of metals in the PCR-HDPE and oil changes during the tandem processes, showing limited effects of these elements (e.g., Al, Ca, Fe, Mg, Ti, Zn) on hydroformylation and reductive amination. Additionally, we demonstrated that reductive amination of aldehydes with varied carbon numbers and branching properties can be achieved in the presence of a complex mixture, including paraffins and aromatics. The results indicate that waste plastics have the potential to serve as a renewable source for mono and di aliphatic amines, thereby diminishing reliance on fossil feedstocks as the current primary amine source.

aliphatic amines↗
DOE OSTI2024

Poromechanical cohesive interface element with combined Mode I-II cohesive zone elastoplasticity for simulating fracture in fluid-saturated porous media

A combined Mode I-II cohesive zone (CZ) elasto-plastic constitutive model, and a two-dimensional (2D) cohesive interface element (CIE) are formulated and implemented at small strain within an ABAQUS User Element (UEL) for simulating 2D crack nucleation and propagation in fluid-saturated porous media. Here, the CZ model mitigates problems of convergence for the global Newton-Raphson solver within ABAQUS, which when combined with a viscous stabilization procedure allows for simulation of post-peak response under load control for coupled poromechanical finite element analysis, such as concrete gravity dam stability analysis. Verification examples are presented, along with a more complex ambient limestone-concrete wedge fracture experiment, water-pressurized concrete wedge experiment, and concrete gravity dam stability analyses. A calibration procedure for estimating the CZ parameters is demonstrated with the limestone-concrete wedge fracture process. For the water-pressurized concrete wedge fracture experiment it is shown that the inherent time-dependence of the poromechanical CIE analysis provides a good match with experimental force versus displacement results at various crack mouth opening rates, yet misses the pore water pressure evolution ahead of the crack tip propagation. This is likely a result of the concrete being partially-saturated in the experiment, whereas the finite element analysis assumes fully water saturated concrete. For the concrete gravity dam analysis, it is shown that base crack opening and associated water uplift pressure leads to a reduced Factor of Safety, which is confirmed by separate analytical calculations.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

Minimizing thickness variation in monolithic U-10Mo fuel foil and Zr interlayer during hot rolling: A microstructure-based finite element method analysis

Low-enriched uranium alloyed with 10 wt. % molybdenum (U-10Mo) has been identified as a promising alternative to highly enriched uranium fuel for the United States’ high performance research reactors. The monolithic U-10Mo fuel plate consists of a metallic U-10Mo fuel foil with a 25 µm Zr interlayer and a relatively thick cladding of aluminum alloy 6061. The Zr interlayer is typically applied during the hot co-rolling process, and this process dictates the uniformity of the Zr interlayer. Thickness variation observed in the U-10Mo and Zr interlayer has been attributed to several sources: the initial grain size of the U-10Mo castings, can materials, rolling temperature, inhomogeneous molybdenum content, and porosity in the cast U-10Mo. This thickness variation limits the ability to meet the dimensional specification; thus, a better understanding of the factors causing the nonuniform thickness is needed. In this work, we used a novel, microstructure-based finite element method to model the hot rolling process to address these concerns. Grain microstructures in U-10Mo were tessellated and explicitly considered in the finite element model. Each grain was assigned a random material property to mimic the grain strength variations induced by different grain orientations. Simulations were performed using six steel can thicknesses, four grain sizes, and with or without a Zr interlayer to investigate the influences of those variables on the thickness nonuniformity. The simulation results showed that a thinner steel can and finer U-10Mo grain size reduce thickness variations in both the U-10Mo fuel foil and Zr interlayer. The direct findings from the simulations and analysis can be used to optimize the hot rolling schedule, reduce fabrication defects, and meet the dimensional specifications. The proposed microstructure-based finite element model can be also coupled with experimental microstructure characterization data, images, and models to simulate multi-pass hot rolling.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Structural characterization of sugarcane lignins extracted from different protic ionic liquid pretreatments

Previous studies based on protic ionic liquids have shown them to be effective for extracting lignins from biomass. Moreover, ILs synthesized with amine cations can promote the insertion of nitrogen into lignin, favoring its valorization for industrial applications. Here, lignins extracted from sugarcane bagasse by eight different PILs were analyzed. Several techniques of characterization were employed (2D HSQC NMR, 31P NMR, GPC, Py-GC/MS, TGA, FTIR, and elemental analysis), seeking a deeper understanding of lignin structure post-PILS treatment. In particular, lignin obtained with acetate and lactate anions with monoethanolamonium cations showed similar structural compositions. Lignins obtained from ethylenediamonium cation combined anions acetate and lactate exhibited relatively higher molecular weights compared to the other lignins studied. The elemental analysis of these lignins further revealed the presence of nitrogen in their structures, suggesting that amination occurred. In this work we used PILs not yet reported in the literature for this purpose, and consequently obtained lignins with specific structures. Overall, our results demonstrated that depending on the PILs used, lignins with distinct properties could be obtained which might be used for value-added applications. This work covered new advances in elucidation of lignin chemical structure and opened a new path for lignin valorization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗