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At least 253 records · Page 14

Opening twisted polymer chains for simultaneously high printability and battery fast-charge

Fast-charging is key to the widespread adoption of battery-based electric vehicles. However, improving fast-charging through architecture optimization is expensive. To reduce costs and expand to commercialization, we applied roll-to-roll screen printing technology to create channels and decrease the tortuosity of electrodes. For the first time, this work successfully opened twisted polymer chains within high-solid-content inks to improve their screen printability and battery performance of as-printed electrodes. With LiNi 0.6 Mn 0.2 Co 0.2 O 2 as active materials, the 60% solid content ink presents superior screen printability after opening the twisted binder chains. As-printed electrode exhibits 33% higher charge capacity at 6 C than printed electrode with chains twisted ink at mass loading of 6.5 mg/cm 2 . Furthermore, coarse-grained molecular dynamics simulations are performed to study the underlying mechanism systematically. In conclusion, the new ink preparation procedure provides a scalable, effective strategy for manufacturing screen-printable battery ink and promotes screen-printed electrode technology.

25 ENERGY STORAGE↗

Solid State Transformer Controls for Mitigation of E3a High-Altitude Electromagnetic Pulse Insults

This paper explores the use of a solid state transformer (SST) to mitigate the 𝐸 3𝐴 component of a high-altitude electromagnetic pulse (HEMP) insult using external energy storage optimal control techniques. In lieu of conventional passive blocking devices or feedback-controlled energy storage devices, a novel implementation of Hamiltonian error tracking is utilized to develop a feedback control law for the variable converter ratio in an SST. The findings of the simulations performed in this paper suggest that additional energy storage is not necessary to protect an individual load from a HEMP insult. The simulations performed examine the response of a single-phase SST connected to a single voltage source on a long transmission line on the one side and a single linear resistor on the other. The control law is specifically developed for the late-time, low-frequency portion of a HEMP insult, namely the 𝐸 3𝐴 components. The Hamiltonian error-based converter ratio control law is compared with nonlinear optimal feedforward controls to show that the HSSPFC is an external energy storage optimal controller.

HEMP mitigation↗

Design, fabrication, and testing of a water-cooled tungsten-foam high-heat flux plasma-facing module

Here, we present a comprehensive study detailing the design, fabrication and testing a new modular “finger” component, featuring a hexagonal tungsten foam armor tile bonded to the top surface of the water-cooled finger unit. The mechanical, thermal, and particle transport properties of the tungsten foam armor were determined for a wide range of porosity and cell size, and then combined in an equivalent solid material with “effective” properties suitable for large-scale simulations. A series of 3-D multiphysics simulations for coupled thermal and mechanical behavior of the “finger” module are used to optimize the design before fabrication. The simulation results show that, for the expected experimental conditions, a safe range of heat flux and foam porosity is possible for both water-cooling and helium-cooling. Based on these multiphysics simulations, an optimum finger cooling module has been fabricated at Ultramet, Inc. A series of experiments were designed to study the thermomechanical performance of the “finger” unit under steady-state and transient thermal loading at surface heat flux up to 16 MW/m 2 in the High Energy Flux Test facility (HEFTY) at UCLA. Testing conditions included low-power, steady-state plasma exposure at 6 MW/m 2 , followed by severe high heat flux cycles at 16 MW/m 2 . Results of these tests are explained through comparisons with multiphysics simulations. To eliminate the effects of thermomechanical damage carried out on a module on its thermo-mechanical response on a subsequent test, three different yet identically designed and fabricated finger modules were tested. The results show that the current design is capable of cooling the walls of fusion devices at surface heat flux up to 6 MW/m 2 without failure, and that the failure heat flux limit is below 16 MW/m 2 .

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The Impact of Catalyst Layer Composition and Structure on Performance and Durability of PEMWE Anodes

A study of various compositions of anodes for proton exchange membrane water electrolysis aimed at reducing precious metal content and system costs without compromising performance and durability is presented. A key challenge in current water electrolysis technologies is the reliance on high iridium loadings to ensure sufficient catalytic activity, electronic conductivity, and durability for the oxygen evolution reaction. To address this, catalyst layers based on the stable but kinetically limited rutile phase of iridium oxide are combined with platinum nanoparticles and carbon-based additives to improve structural properties and ink processability. By systematically varying the volume ratios of carbon to precious metals and ionomer to solids, compositional trends have been identified, and significant performance improvements have been achieved. Structural and elemental analysis confirms improved dispersion of platinum and iridium can be achieved, as well as electronic conductivity improvements within the catalyst layer. Polarization curve analysis has shown the ability of added Pt and C to significantly increase catalytic activity. These results highlight the potential positive impact of Pt and C on anode structure, composition, and cell performance.

36 MATERIALS SCIENCE↗

Crustal Deformation and Gravitational Effects From Dynamic Ocean Mass Redistribution Impact Projected Sea‐Level Change

As the climate warms, associated changes in ocean dynamics will redistribute sea‐water mass within the ocean, contributing to relative sea‐level change. This mass redistribution will cause additional sea‐level changes due to gravitational self‐attraction, deformation of the solid Earth, and shifts in the Earth's rotation axis (GRD), which are not incorporated in sea‐level projections. Using CMIP6 climate model output, we quantify relative sea‐level changes induced by GRD from ocean‐dynamic mass loading through 2100. These effects act to amplify projected ocean‐dynamic sea‐level patterns, causing sea‐level rise in coastal regions, particularly along wide continental shelves and at high latitudes. On average, the magnitude of such GRD‐induced sea‐level change is equivalent to ∼15% of the signal due to dynamic ocean mass redistribution. Although our results show substantial inter‐model spread, they reveal that GRD‐induced relative sea‐level changes from ocean mass redistribution represent a non‐negligible component of regional sea‐level change and should be considered in projections.

58 GEOSCIENCES↗

Universal Approach to Fabricating Graphene-Supported Single-Atom Catalysts from Doped ZnO Solid Solutions

Single-atom catalysts (SACs) have attracted widespread interest for many catalytic applications because of their distinguishing properties. However, general and scalable synthesis of efficient SACs remains significantly challenging, which limits their applications. Here we report an efficient and universal approach to fabricating a series of high-content metal atoms anchored into hollow nitrogen-doped graphene frameworks (M-N-Grs; M represents Fe, Co, Ni, Cu, etc.) at gram-scale. The highly compatible doped ZnO templates, acting as the dispersants of targeted metal heteroatoms, can react with the incoming gaseous organic ligands to form doped metal-organic framework thin shells, whose composition determines the heteroatom species and contents in M-N-Grs. We achieved over 1.2 atom % (5.85 wt %) metal loading content, superior oxygen reduction activity over commercial Pt/C catalyst, and a very high diffusion-limiting current (6.82 mA cm -2 ). Both experimental analyses and theoretical calculations reveal the oxygen reduction activity sequence of M-N-Grs. Additionally, the superior performance in Fe-N-Gr is mainly attributed to its unique electron structure, rich exposed active sites, and robust hollow framework: This synthesis strategy will stimulate the rapid development of SACs for diverse energy-related fields.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hydrodynamics of countercurrent flows in a structured packed column: effects of initial wetting and dynamic contact angle

The structured packed column has gained considerable attention as a prospective technology to mitigate carbon dioxide emissions from thermal power plants. The computational flow investigation of such systems is a multiscale problem, and local hydrodynamics plays a key role in overall column efficiency. Accordingly, multiphase flow studies in the representative elementary unit (REU) of a packed column can offer insights into the local flow behavior such as flow pattern, interfacial area, etc. The interfacial area plays a key role in the overall interphase mass transfer and thereby in separation efficiency. The predicted effective area matches well with corresponding ones in experiments for Mellapak 250.Y packings. The contact angle (i.e., solid substrate behavior) is one of the critical factors that dictates wettings, and thereby the interfacial area. The dynamic contact angle (DCA) was considered in order to explore the effects of contact angle hysteresis on the interfacial area. DCA has more pronounced impact on the interfacial area for a solvent possessing a higher value of surface tension and equilibrium contact angle. The interfacial area shows temporal undulation and does not achieve a pseudo steady state due to the capillary force. In contrary, the interfacial area gets a net value for a solvent having low surface tension value. Further, specification of the static contact angle at the solid substrate shows the least value of the interfacial area. We also extensively studied the effect of the initial sheet condition (dry vs wet) on the interfacial area. The initially wetted sheets show slightly higher value of the interfacial area as compared to the initially dry sheets at a fixed flow rate for a solvent having high surface tension value. Wetting hysteresis decreases with increasing liquid loads. On the other hand, wetting hysteresis does not occur for a solvent having value of low surface tension and equilibrium contact angle.

structured packings, dynamic contact angle, interf↗

Polyimide as a durable cathode for all-solid-state Li(Na)–organic batteries with boosted cell-level energy density

The integration of organic electrode materials (OEMs) with solid-state electrolytes (SSEs) is expected to build an all-solid-state battery (ASSB) with long-term sustainability, high safety, and high energy density. Despite this great promise, the cell-level energy density is still far from practically applicable, which stems from the ultrathick SSE layer and thin cathode layer used in a pellet-type ASSB design. Here, a cost-effective polyimide (PI) material was first exploited as an organic cathode for sulfide-based ASSBs. A capacity of ~190 mAh g -1 was delivered with almost no capacity decay over 300 cycles. Moreover, for the first time, a dry-film approach was introduced to manufacture a sheet-type Li–organic ASSB with an ultrathin SSE layer and a high-areal-loading PI cathode. Notably, PI is a perfect candidate for dry-film technology due to its high thermal stability and extraordinary chemical inertness toward sulfide SSEs. Remarkably, the free-standing SSE membrane was merely 46 μm thick, and an ultralow areal resistance of 3.3 Ω cm 2 was achieved, more than tenfold lower than that of reported SSE pellets. One order of magnitude boost in the cell-level energy density was achieved. This work presents a significant leap in transferring organic ASSB technology from laboratory research to factory manufacturing.

25 ENERGY STORAGE↗

Unveiling enhanced oxidation resistance and mechanical integrity of multicomponent ultra–high temperature carbides

The development of a new class of multicomponent ultra-high temperature ceramics (MC-UHTCs), often referred to as high-entropy UHTCs, has gained increased interest due to the possibility of improved thermomechanical and oxidation properties. In this study, a systematic approach by gradual addition in the UHTC components ranging from a binary to a dense quaternary (Ta,Nb,Hf,Ti)C is synthesized using spark plasma sintering (SPS). The solid solutioning was the critical factor in homogenizing the composition in the multicomponent system. The segregation of NbC and HfC was seen in binary and ternary UHTC systems, while a single-phase homogeneity was observed in the quaternary UHTC improving its hardness up to 34.8 GPa. The presence of closely spaced slip lines in the MC-UHTCs enhances resistance to indentation damage up to 72% at an applied load of 200 N. The formation of complex mixed oxide phase of Hf6Ta2O17 ensued in the lower to negligible oxidation even up to 3 min of plasma exposure with temperature exceeding 2800°C. In sum, though the entropy remains medium (0.96R) for the selected system, the quaternary UHTC system undoubtedly has significantly better thermomechanical performance when compared to established baseline UHTCs. Furthermore, this raises the debate on the justification for calling a multicomponent system a “high entropy” to be seen in a new light. The developed MC-UHTCs elicits the paradigm of this new class of UHTCs expanding their potential in thermal protection systems for hypersonic applications.

36 MATERIALS SCIENCE↗

A Fast‐Charging and High‐Temperature All‐Organic Rechargeable Potassium Battery

Abstract Developing fast‐charging, high‐temperature, and sustainable batteries is critical for the large‐scale deployment of energy storage devices in electric vehicles, grid‐scale electrical energy storage, and high temperature regions. Here, a transition metal‐free all‐organic rechargeable potassium battery (RPB) based on abundant and sustainable organic electrode materials (OEMs) and potassium resources for fast‐charging and high‐temperature applications is demonstrated. N‐doped graphene and a 2.8 m potassium hexafluorophosphate (KPF 6 ) in diethylene glycol dimethyl ether (DEGDME) electrolyte are employed to mitigate the dissolution of OEMs, enhance the electrode conductivity, accommodate large volume change, and form stable solid electrolyte interphase in the all‐organic RPB. At room temperature, the RPB delivers a high specific capacity of 188.1 mAh g −1 at 50 mA g −1 and superior cycle life of 6000 and 50000 cycles at 1 and 5 A g −1 , respectively, demonstrating an ultra‐stable and fast‐charging all‐organic battery. The impressive performance at room temperature is extended to high temperatures, where the high‐mass‐loading (6.5 mg cm −2 ) all‐organic RPB exhibits high‐rate capability up to 2 A g −1 and a long lifetime of 500 cycles at 70–100 °C, demonstrating a superb fast‐charging and high‐temperature battery. The cell configuration demonstrated in this work shows great promise for practical applications of sustainable batteries at extreme conditions.

25 ENERGY STORAGE↗

Polyethylene Furanoate ( PEF ) Production Using Nanowire Based Super Acid Catalysts

ABSTRACT In this article, bioplastic polyethylene furanoate (PEF) is synthesized using polycondensation of 2,5‐furandicarboxylic acid and ethylene glycol at a temperature of 220°C using a solid nanowire based super‐acid catalyst. The super acid catalyst is made by phosphating titania nanowires. Specifically, the reactions resulted in over 90% FDCA conversion and 85% PEF yield in a short period of 3 h using superacid catalysts at a loading of < 1% by wt. The mechanical properties of PEF, including glass transition temperature (84°C), melting point (210°C), and crystallinity (1.48 g/cm 3 ), demonstrate the high quality of the PEF produced. Barocaloric properties of resulting PEF polymers are also studied which show promise.

Kannapu, Hari Prasad Reddy [Advanced Energy Materi↗

Study on the Carbon Nanostructures for Nanosized Si Electrodes

Silicon (Si) has been considered as a next-generation anode material due to natural abundance, low operating potential (<0.5 V vs. Li/Li+), and high theoretical specific capacity of 4200 mAh g-1.[1] However, the electrochemical alloying reaction of Si involves large volume changes of 400% during lithiation and delithiation, causing cracking and pulverization of Si.[1] In addition, solid electrolyte interface (SEI) of Si anode experiences constant changes due to unstable SEI reactivity.[2] Considerable efforts have been made to design nanostructured Si materials to address the issues because nanostructuring can relieve the mechanical strain.[3] However, when compared to micrometer-sized active materials having sufficient electrolyte pathway through interparticle space, the nanoparticle (NP)-based electrodes tend to be densely packed. As mass loading is higher and electrode is thicker, ion transport issue can become more severe in the densely packed electrodes.[4] In this work, we will present studies on engineered porosity impacts performance in Si NP electrodes by altering carbon nanostructures. We explore the extreme limit of effectively non-porous electrodes using quasi-spherical, Si NPs, which result in densely packed electrodes when slurry is prepared with conventional carbon black. We engineer porosity using carbon nanostructures including multi-walled carbon nanotubes and carbon nanorods in place of conventional carbon black to create pore structure in Si NP-based electrodes. These experiments provide a correlation between mass loading, porosity and silicon utilization in Si NP-based electrodes. References: [1] C. K. Chan, H. Peng, G. Liu, K. Mcllwrath, X. F. Zhang, R. A. Huggins, Y. Cui, "High-performance lithium battery anodes using silicon nanowires", Nat. Nanotechnol., 2008, 3, 31, [2] J. D. McBrayer, M.-T. F. Rodrigues, M. C. Schulze, D. P. Abraham, C. A. Apblett, I. Bloom, G. M. Carroll, A. M. Coclasure, C. Fang, K. L. Harrison, G. Liu, S. D. Minteer, N. R. Neale, G. M. Veith, C. S. Johnson, J. T. Vaughey, A. K. Burrel, B. Cunningham, "Calendar aging of silicon-containing batteries", Nat. Energy, 2021, 6, 1164, [3] H. Wu, G. Zheng, N. Liu, T. J. Carney, Y. Yang, Y. Cui, "Engineering Empty space between Si Nanoparticles for Lithium-Ion Battery Anodes", Nano Lett., 2012, 12, 904, [4] X. Zhang, Z. Ju, Y. Zhu, K. J. Takeuchi, E. S. Takeuchi, A. C. Marschilok, G. Yu, "Multiscale Understanding and Architecture Design of High Energy/Power Lithium-Ion Battery Electrodes", Adv. Energy Mater., 2021, 11, 2000808

carbon nanostructure↗

Data for Conversion of High-Solids Hydrothermally Pretreated Bioenergy Sorghum to Lipids and Ethanol Using Yeast Cultures

Glucose and xylose are the major sugars present in cellulosic hydrolysates. The cellulosic sugars can be used for the production of platform chemicals. In this study, productions of lipid and ethanol by yeasts were compared for concentrated bioenergy sorghum syrup. Bioenergy sorghum was hydrothermally pretreated at 50% w/w solids in a continuous industrial reactor and sequentially mechanically refined using a burr mill to improve biomass accessibility for hydrolysis. Fed-batch enzymatic hydrolysis was conducted with 50% w/v solids loading and cellulase cocktail (50 FPU/g biomass) to achieve 230 g/L sugar concentration. Various strains of Rhodosporidium toruloides were evaluated for converting sugars into lipids, and strain Y-6987 had the highest lipid titer (9.2 g/L). The lipid titer was improved to 19.0 g/L by implementing a two-stage culture scheme, where the first stage was optimized for yeast growth and the second for lipid production. For ethanol production, the engineered Saccharomyces cerevisiae SR8ΔADH6 was used to coferment glucose and xylose. Ethanol fermentation was optimized for media nutrients (YP, YNB/urea, and urea), cellulosic sugar concentration, and sulfite conditioning to maximize the ethanol concentration from sorghum syrups. Fermentation of 70% v/v concentrated hydrolysate conditioned with sulfite produces 50.1 g/L ethanol from 141 g/L of sugars.

Conversion↗

Impact of particle loading and phase coupling on gas–solid flow dynamics: A case study of a two-phase, gas–solid flow in an annular pipe

The present study is devoted to a two-phase, gas–solid flow in an annular pipe (hollow cylinder) at an elevated pressure of 15 bars and moderate Reynolds number of circa 6000. The influence of the particle loading, the interaction between the phases, and turbulence dispersion on the flow dynamics is systematically studied by means of computational fluid dynamics simulations, employing the Ansys FLUENT commercial package. The cases with a particle volumetric fraction of 1.2% are referred to as “high particle loading,” and those with 0.13% are denoted as “low particle loading.” The following cases are investigated: (1) pure gas flow; (2) low particle loading two-phase flow with one-way coupling and with turbulence dispersion; (3) low particle loading two-phase flow with two-way coupling but without turbulence dispersion; (4) low particle loading two-phase flow with two-way coupling and with turbulence dispersion; (5) high particle loading two-phase flow with one-way coupling and with turbulence dispersion; (6) high particle loading two-phase flow with two-way coupling but without turbulence dispersion; and (7) high particle loading two-phase flow with two-way coupling and with turbulence dispersion. Additionally, the boundary layer is found to grow without fluctuations of the turbulent kinetic energy (TKE) for cases 1, 2, and 5. For case 4, the TKE fluctuations have been identified, although they appear to be less substantial than those in cases 6 and 7. The authors attribute the semi-chaotic nature of the TKE fluctuations to the particle loading and two-way coupling. In addition, the onset and development of the flow instability have been observed at a random axial distance in cases 4, 6, and 7. Such instability is also attributed to the two-way coupling with turbulence dispersion in the flow. It is concluded that the particle loading, one-way, or two-way coupling between the phases, and the turbulence dispersion models significantly influence the development of the flow dynamics with the same inlet and boundary conditions. Consequently, it is not a trivial question, which result a user should trust. The present computational results inspire to perform verification as well as experimental validation of the simulations, so the simulation results can subsequently be used with confidence for design analysis.

42 ENGINEERING↗

Using Best Basis Inventory Data to Direct Strategies for Real-Time Monitoring of Hanford High Level Waste

The proposed Direct Feed High Level Waste (DFHLW) approach for processing high-level tank waste at Hanford is intended to reduce processing time by bypassing the Pretreatment Facility and transferring waste directly from the tank farm to the WTP HLW vitrification facility. This processing strategy could reduce or eliminate the washing and leaching steps that would have occurred in the Pretreatment facility. Operation of the vitrification facility is subject to chemical and radiological limits protecting safety (e.g. Waste Acceptance Criteria, or WACs) and process quality (e.g. Process Control Limits, or PCLs). Without washing and leaching, there is a greater risk of exceeding the WACs and PCLs. Hanford process engineers have devised blending strategies based on known chemical and radiological composition, volumes, and solids loadings of individual layers within each waste tank. These blending campaigns succeed in predicting a processing strategy that does not exceed the WACs and PCLs. However, the calculations do not ascribe uncertainties to the tank analysis data, quantities of material taken from the tanks to make the blend, or potential for mixing of layers within tanks. In order to confirm that a process strategy is working, it would be advantageous to have inline or at-line analytical instrumentation installed in the processing facilities that deliver measurement results in real time.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Combining solution-, precipitation- and load-transfer strengthening in a cast Al-Ce-Mn- Sc -Zr alloy

Here, a cast Al-9Ce-0.75Mn-0.18Sc-0.12Zr (wt%) alloy is designed to combine three strengthening phases: (i) micron-scale Al 11 Ce 3 platelets formed during eutectic solidification, (ii) nano-scale L1 2 -Al 3 (Sc,Zr) precipitates formed during aging, and (iii) Mn in solid solution in the α-Al matrix. Microstructural analyses by SEM, TEM, and atom-probe tomography reveal that Mn remains in solid solution in the as-cast alloy, providing solution strengthening with no influence on the eutectic Al-Al 11 Ce 3 microstructure, which provides precipitation- and load-transfer strengthening. During long-term over-aging at 400 °C, Mn-rich precipitates grow at the Al-Al 11 Ce 3 interface, with no effect on the microhardness. However, after short aging at 350 °C, a high number density of fine L1 2 -Al 3 (Sc,Zr) nanoprecipitates form in the Al matrix (with a coarser size at the Al-Al 11 Ce 3 interface), providing precipitation strengthening. The synergistic combination of the three strengthening mechanisms (solution, precipitation, and load transfer) in our Al-Ce-Mn-Sc-Zr alloy results in higher microhardness after aging at 350 and 400 °C, and higher creep resistance at 300 °C, as compared to alloys with two strengthening mechanisms: an Al-10Ce-0.93Mn control alloy (without precipitation strengthening from Sc and Zr), Al-Ce-Sc-Zr (without solution strengthening from Mn), and Al-Mn-Zr-Er (without load-transfer strengthening from Ce). Furthermore, these dual-strengthened alloys are more creep resistant than alloys with a single strengthening mechanism (Al-Ce, Al-Mn, and Al-Sc-Zr), confirming that the three mechanisms can be combined in pairs or all together.

36 MATERIALS SCIENCE↗

Sr 1-x Ca x Fe 1-y Co y O 3-δ as facile and tunable oxygen sorbents for chemical looping air separation

Abstract Chemical looping air separation (CLAS) is a promising technology for oxygen generation with high efficiency. The key challenge for CLAS is to design robust oxygen sorbents with suitable redox properties and fast redox kinetics. In this work, perovskite-structured Sr 1-x Ca x Fe 1-y Co y O 3 oxygen sorbents were investigated and demonstrated for oxygen production with tunable redox properties, high redox rate, and excellent thermal/steam stability. Cobalt doping at B site was found to be highly effective, 33% improvement in oxygen productivity was observed at 500 °C. Moreover, it stabilizes the perovskite structure and prevents phase segregation under pressure swing conditions in the presence of steam. Scalable synthesis of Sr 0.8 Ca 0.2 Fe 0.4 Co 0.6 O 3 oxygen sorbents was carried out through solid state reaction, co-precipitation, and sol-gel methods. Both co-precipitation and sol-gel methods are capable of producing Sr 0.8 Ca 0.2 Fe 0.4 Co 0.6 O 3 sorbents with satisfactory phase purity, high oxygen capacity, and fast redox kinetics. Large scale evaluation of Sr 0.8 Ca 0.2 Fe 0.4 Co 0.6 O 3 , using an automated CLAS testbed with over 300 g sorbent loading, further demonstrated the effectiveness of the oxygen sorbent to produce 95% pure O 2 with a satisfactory productivity of 0.04 g O2 g sorbent −1 h −1 at 600 °C.

25 ENERGY STORAGE↗

A New Method to Overcome Carboxyamide Formation During AFEX Pretreatment of Lignocellulosic Biomass

Lignin-carbohydrate complexes (LCCs) in the plant cell wall are responsible for providing resistance against biomass-degrading enzymes produced by microorganisms. Four major types of lignin-carbohydrate bonds are reported in the literature, namely, benzyl ethers, benzyl esters, phenyl glycosides, and acetyl ester linkages. Ester’s linkages in the plant cell wall are labile to alkaline pretreatments, such as ammonia fiber expansion (AFEX), which uses liquid or gaseous ammonia to cleave those linkages in the plant cell wall and reduce biomass recalcitrance. Two competing reactions, notably hydrolysis and ammonolysis, take place during AFEX pretreatment process, producing different aliphatic and aromatic acids, as well as their amide counterparts. AFEX pretreated grasses and agricultural residues are known to increase conversion of biomass to sugars by four- to five-fold when subjected to commercial enzyme hydrolysis, yielding a sustainable feedstock for producing biofuels, biomaterials, and animal feed. Animal feed trials on dairy cows have demonstrated a 27% increase in milk production when compared to a control feedstock. However, the presence of carboxamides in feedstocks could promote neurotoxicity in animals if consumed beyond a certain concentration. Thus, there is the need to overcome regulatory hurdles associated with commercializing AFEX pretreated biomass as animal feed in the United States. This manuscript demonstrates a modified pretreatment for increasing the digestibility of industrial byproducts such as Brewer’s spent grains (BSG) and high-fiber meal (HFM) produced from BSG and dry distillers grains with soluble (DDGS), while avoiding the production of carboxamides. The three industrial byproducts were first treated with calculated amounts of alkali such as NaOH, Ca(OH) 2 , or KOH followed by AFEX pretreatment. We found that 4% alkali was able to de-esterify BSG and DDGS more efficiently than using 2% alkali at both 10 and 20% solids loading. AFEX pretreatment of de-esterified BSG, HFM, and DDGS produced twofold higher glucan conversion than respective untreated biomass. This new discovery can help overcome potential regulatory issues associated with the presence of carboxamides in ammonia-pretreated animal feeds and is expected to benefit several farmers around the world.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗