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At least 793 records · Page 44

The influence of mechanical constraints introduced by β annealed microstructures on the yield strength and ductility of Ti-6Al-4V

Discussed is a computational study of the influence of the microstructure’s geometric morphology on the yield strength and ductility of Ti-6Al-4V. Uniaxial tension tests were conducted on physical specimens to determine the macroscopic yield strength and ductility of two microstructural variations (mill annealed and β annealed) to establish comparisons of macroscopic properties. A multi-experimental approach was utilized to gather two dimensional and three dimensional data, which were used to inform the construction of representative β annealed polycrystals. A highly parallelized crystal plasticity finite element framework was employed to model the deformation response of the generated polycrystals subjected to uniaxial tension. To gauge the macroscopic response’s sensitivity to the morphology of the geometry, the key geometrical features - namely the number of high temperature β phase grains, α phase colonies, and size of remnant secondary β phase lamellae - were altered systematically in a suite of simulations. Both single phase and dual phase aggregates were studied. Presented are the calculated yield strengths and ductilities, and the resulting trends as functions of geometric parameters are examined in light of the heterogeneity in deformation at the crystal scale.

36 MATERIALS SCIENCE↗

In situ measurement of three-dimensional intergranular stress localizations and grain yielding under elastoplastic axial-torsional loading

The three-dimensional grain-averaged response of solid bar samples under non-proportional (NP) elastoplastic axial-torsional loading was investigated using in situ high energy diffraction microscopy (HEDM) and companion crystal plasticity finite element (CPFE) modeling. Important stress metrics including applied shear (σ θZ ) and axial (σ ZZ ) stress tensor components, stress and stress deviator tensor invariants (I 1 , J 2 , and J 3 ), von Mises equivalent stress (σ$^{grain}_{VM}$), maximum resolved shear stress (mRSS), stress triaxiality (η), and lode angle parameter ($\barθ$) values were tracked for ~300 grains under two different loading conditions: (1) Torsion-dominated loading (low NP) and (2) Tension-torsion loading (high NP) in equiatomic NiCoCr, a representative multicomponent face-centered cubic (FCC) superalloy. Overall, significant stress localizations existed within both samples as evidenced by the radial dependence of grain-resolved σ θZ , σ$^{grain}_{VM}$, and J 2 ; by comparison, I 1 , J 3 , η, and $\barθ$ metrics did not show discernible trends within the volume. These stress localizations reveal a complex interplay between axial and shear stress components (e.g., stress coupling) resulting in grain yielding near the sample surface largely driven by shear stress, whereas internal grain yielding was largely accommodated by axial stress. Grain-resolved stress localization trends were described well by the CPFE model, although some discrepancies in magnitude occurred, particularly for volumetric stress metrics (I 1 and η) due to initial type II residual stress distributions. The superposition of initial residual stress states onto CPFE grain-resolved data significantly improved model accuracy for η. This suggests that residual stresses more strongly influence the simulation of volumetric rather than deviatoric (yield) stress metrics.

36 MATERIALS SCIENCE↗

Fabrication and characterization of a novel β metastable Ti-Mo-Zr alloy with large ductility and improved yield strength

Highlights: • Ti-12Mo-5Zr alloy exhibits excellent combination of improved yielding strength (>650 MPa), high ductility (uniform elongation ≈30%) and work-hardening behaviour. • The superior performances arise from the synergic effects between phase transformation induced plasticity and twinning induced plasticity. • The ‘d-electron’ alloy design approach in Ti-12Mo-5Zr alloy, i.e. Zr substitution to Ti, validates the feasibility of yielding stress improvement of TWIP/TRIP titanium alloys. - Abstract: In this paper, a novel ternary β-metastable titanium alloy, Ti-12Mo-5Zr (wt%), was designed based on the “d-electron” alloy design theory. The Ti-12Mo-5Zr alloy displays excellent combination of improved yielding stress (>650 MPa), high ductility (uniform elongation ≈30%) and work-hardening behaviour. The detailed microstructural analysis indicates that the superior performances arise from the synergic effects between phase transformation induced plasticity (TRIP) and twinning induced plasticity (TWIP). Conforming to the design strategy, the improvement of mechanical performance results from the addition of Zr alloying element in substituting Ti, attributing to solution hardening effect and the increasing of critical resolved shear stress (CRSS) of stress induced martensitic transformation (SIM α″).

36 MATERIALS SCIENCE↗

Gas-phase surface modification to control catalyst structure and yields in methane dehydroaromatization

Methane dehydroaromatization (MDA) is a promising approach for direct methane transformation to aromatics and hydrogen. The benchmark catalyst Mo/H-ZSM-5 struggles to find commercial adoption because of thermodynamically-limited yields and rapid coking on Brønsted acid and molybdenum carbide species, especially on zeolite external surfaces. Here, gas-phase atomic layer deposition (ALD) overcoats H-ZSM-5 external surfaces with SiO 2 or Al 2 O 3 . NH 3 -TPD, HRTEM, and textural properties show that these overcoats exclusively passivate zeolite external surfaces. Under MDA conditions, SiO 2 gives softer coke and increases cumulative benzene yields by 25%, while Al 2 O 3 strongly decreases yields. H 2 -TPR and UV-visible and Raman spectroscopy show how the overcoats redisperse the MoO x precatalysts, especially over multiple deactivation and isothermal oxidative regeneration cycles. Combined with 27 Al-MAS NMR, MoO x redistribution and dealumination are seen as the causes of long-term deactivation over multiple regeneration cycles, and this process continues to occur regardless of the overcoat. Altogether, the deposition of a small amount of silica on the outer surface of Mo/H-ZSM-5 reduces the formation of hard coke, which could be regenerated by milder methods such as hydrogen treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Creation of a High-Yield AAV Vector Production Platform in Suspension Cells Using a Design-of-Experiment Approach

Recombinant adeno-associated virus (rAAV) vectors are a leading gene delivery platform, but vector manufacturing remains a challenge. New methods are needed to increase rAAV yields and reduce costs. Past efforts to improve rAAV production have focused on optimizing a single variable at a time, but this approach does not account for the interactions of multiple factors that contribute to vector generation. Here, we utilized a design-of-experiment (DOE) methodology to optimize rAAV production in a HEK293T suspension cell system. We simultaneously varied the transgene, packaging, and helper plasmid ratios, the total DNA concentration, and the cell density to systematically evaluate the impact of each variable across 52 conditions. The results revealed a unique set of parameters with a lower concentration of transgene plasmid, a higher concentration of packaging plasmid, and a higher cell density than previously described protocols. Using this DOE-optimized protocol, we achieved unpurified yields approaching 3 × 10 14 viral genomes (VGs)/L of cell culture. Additionally, we incorporated polyethylene glycol (PEG)-based virus precipitation, pH-mediated protein removal, and affinity chromatography to our downstream processing, enabling average purified yields of >1 × 10 14 VGs/L for rAAV-EGFPs across 13 serotypes and capsid variants.

59 BASIC BIOLOGICAL SCIENCES↗

Beam energy dependence of net-hyperon yield and its implication on baryon transport mechanism

In the constituent quark model, each quark inside a baryon carries 1/3 unit of the baryon number. An alternative picture exists where the center of a Y-shaped topology of gluon fields, called the baryon junction, carries a unit baryon number. Studying baryon transport over a large rapidity gap (δy) in nuclear collisions provides a possible tool to distinguish these two pictures. A recent analysis of global data on net-proton yield at mid-rapidity in Au+Au collisions showed an exponential dependence on δy and the exponential slope does not vary with event centrality, favoring the baryon junction picture. Since junctions are flavor blind, hyperons – baryons containing valence strange quarks – are expected to exhibit a similar behavior as the proton. This study aims to test this prediction by analyzing hyperon yields in Au+Au collisions at various energies. We observe that net-hyperon yields, after correcting for the strangeness production suppression, adhere to the expected exponential form. The extracted slope parameters for net-Λ, net-$Ξ$ and net-Ω are consistent with each other and with those of net-proton within uncertainties, and exhibit no centrality dependence. Various implementations of the PYTHIA event generator, primarily based on valence quarks for baryon transport, are unable to simultaneously describe the slope parameters for all baryons.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Steam gasification of waste tyre: Influence of process temperature on yield and product composition

Highlights: ► Steam gasification of waste tyre as matter and energy recovery treatment. ► Process temperature affects products yield and gas composition. ► High temperature promotes hydrogen production. ► Char exploitation as activated carbon or carbon source. - Abstract: An experimental survey of waste tyre gasification with steam as oxidizing agent has been conducted in a continuous bench scale reactor, with the aim of studying the influence of the process temperature on the yield and the composition of the products; the tests have been performed at three different temperatures, in the range of 850–1000 °C, holding all the other operational parameters (pressure, carrier gas flow, solid residence time). The experimental results show that the process seems promising in view of obtaining a good quality syngas, indicating that a higher temperature results in a higher syngas production (86 wt%) and a lower char yield, due to an enhancement of the solid–gas phase reactions with the temperature. Higher temperatures clearly result in higher hydrogen concentrations: the hydrogen content rapidly increases, attaining values higher than 65% v/v, while methane and ethylene gradually decrease over the range of the temperatures; carbon monoxide and dioxide instead, after an initial increase, show a nearly constant concentration at 1000 °C. Furthermore, in regards to the elemental composition of the synthesis gas, as the temperature increases, the carbon content continuously decreases, while the oxygen content increases; the hydrogen, being the main component of the gas fraction and having a small atomic weight, is responsible for the progressive reduction of the gas density at higher temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phosphoketolase overexpression increases biomass and lipid yield from methane in an obligate methanotrophic biocatalyst

Microbial conversion of methane to high-value bio-based chemicals and materials offers a path to mitigate GHG emissions and valorize this abundant-yet -underutilized carbon source. In addition to fermentation optimization strategies, rational methanotrophic bacterial strain engineering offers a means to reach industrially relevant titers, carbon yields, and productivities of target products. The phosphoketolase pathway functions in heterofermentative bacteria where carbon flux through two sugar catabolic pathways to mixed acids (lactic acid and acetic acid) increases cellular ATP production. Importantly, this pathway also serves as an alternative route to produce acetyl-CoA that bypasses the CO 2 lost through pyruvate decarboxylation in the Embden-Meyerhof-Parnas pathway. Thus, the phosphoketolase pathway can be leveraged for carbon efficient biocatalysis to acetyl-CoA-derived intermediates and products. Here, we show that the industrially promising methane biocatalyst, Methylomicrobium buryatense , encodes two phosphoketolase isoforms that are expressed in methanol- and methane-grown cells. Overexpression of the PktB isoform led to a 2-fold increase in intracellular acetyl-CoA concentration, and a 2.6-fold yield enhancement from methane to microbial biomass and lipids compared to wild-type, increasing the potential for methanotroph lipid-based fuel production. Off-gas analysis and metabolite profiling indicated that global metabolic rearrangements, including significant increases in post-translational protein acetylation and gene expression of the tetrahydromethanopterin-linked pathway, along with decreases in several excreted products, coincided with the superior biomass and lipid yield observed in the engineered strain. Further, these data suggest that phosphoketolase may play a key regulatory role in methanotrophic bacterial metabolism. As a result, given that acetyl-CoA is a key intermediate in several biosynthetic pathways, phosphoketolase overexpression offers a viable strategy to enhance the economics of an array of biological methane conversion processes.

09 BIOMASS FUELS↗

The reaction between CH 3 O 2 and OH radicals: Product yields and atmospheric implications

The reaction between CH 3 O 2 and OH radicals has been shown to be fast and to play an appreciable role for the removal of CH 3 O 2 radials in remote environments such as the marine boundary layer. Two different experimental techniques have been used here to determine the products of this reaction. The HO 2 yield has been obtained from simultaneous time-resolved measurements of the absolute concentration of CH 3 O 2 , OH, and HO 2 radicals by cw-CRDS. The possible formation of a Criegee intermediate has been measured by broadband cavity enhanced UV absorption. A yield of Φ HO 2 = (0.8 ± 0.2) and an upper limit for Φ Criegee = 0.05 has been determined for this reaction, suggesting a minor yield of methanol or stabilized trioxide as a product. The impact of this reaction on the composition of the remote marine boundary layer has been determined by implementing these findings into a box model utilizing the Master Chemical Mechanism v3.2, and constraining the model for conditions found at the Cape Verde Atmospheric Observatory in the remote tropical Atlantic Ocean. Inclusion of the CH 3 O 2 +OH reaction into the model results in up to 30% decrease in the CH 3 O 2 radical concentration while the HO 2 concentration increased by up to 20%. Finally, production and destruction of O 3 are also influenced by these changes, and the model indicates that taking into account the reaction between CH 3 O 2 and OH leads to a 6% decrease of O 3 .

54 ENVIRONMENTAL SCIENCES↗

Parameterized yields of semivolatile products from isoprene oxidation under different NOx levels: impacts of chemical aging and wall-loss of reactive gases

We developed a new parameterization for the yields of semi-volatile/intermediate volatility products from isoprene oxidation that took into account the chemical aging under different NOx levels, including functionalization and fragmentation reactions within the gas phase, oligomerization and photolysis within the condensed phase, as well as the loss of particles and gases to chamber walls. We used a box model to fit the dynamic evolution of measured secondary organic aerosol (SOA) concentrations from chamber experiments. The explicit inclusion of multigenerational gas phase chemistry and SOA oligomerization/photolysis during fitting itself had large impacts on the fitted yields that relate to the initial volatility distribution of isoprene oxidation products. During further multigenerational aging of these initial organics, we varied the branching ratio between functionalization and fragmentation. The best fits suggested increasing amounts of fragmentation with increasing initial NOx levels for mixed experiments. Using a box model to simulate evolution of SOA in the atmosphere at constant dilution rate (in absence of wall losses), we found that the yields determined by including different chemical scenarios during fitting changed predicted SOA mass concentrations substantially over aging timescale of 1-2 days. Our results demonstrated the need for better constraining smog-chamber-derived volatility distributions of both gas- and particle-phase SOA constituents with measurements.

Xing, Li↗

Solvated Electron in Acetonitrile: Radiation Yield, Absorption Spectrum, and Equilibrium between Cavity- and Solvent-Localized States

The equilibrium between a solvent cavity-localized electron, ecav-, and a dimeric solvent anion, (CH 3 CN)$_{2}^{•-}$, which are the two lowest energy states of the solvated electron in acetonitrile, has been investigated by pulse radiolysis at 233-353 K. The enthalpy and entropy for the e$_{cav}^{-}$ to (CH 3 CN)$_{2}^{•-}$ conversion amount to -11.2 ± 0.3 kcal/mol and -39.3 ± 1.2 cal/(mol K), corresponding to a 0.44 ± 0.35 equilibrium constant at 25 °C. The radiation yield of the solvated electron has been quantified using a Co(II) macrocycle that scavenges electrons with a 1.55 × 10 11 M -1 s -1 rate constant. The apparent yield increases without saturation over the attainable scavenger concentration range, reaching 2.8 per 100 eV; this value represents the lower limit for the acetonitrile ionization yield in pulse radiolysis. The apparent molar absorption coefficient of (20.8 ± 1.5) × 10 3 M -1 cm -1 at 1450 nm and 20 °C for the solvated electron and individual vis-near-infrared (NIR) absorption spectra of e$_{cav}^{-}$ and (CH 3 CN)$_{2}^{•-}$ are derived from the data. Variances with previous reports are thoroughly discussed. All together, these results resolve several controversies concerning the solvated electron properties in acetonitrile and furnish requisite data for quantitative pulse radiolysis investigations in this commonly used solvent.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Femtosecond Nonadiabatic Confinement of Molecular Dication Yield

Doubly charged molecular cations often carry signatures of electronic correlation and electron–nuclear entanglement present in the parent cation. Here, we produce ethylene dications using a combination of an extreme ultraviolet pump and near-infrared probe pulses, observing a peak in the dication yield at a pump–probe delay of approximately 15 fs. Ab-initio calculations, which explicitly take into account coupled electron–nuclear dynamics induced by the pump and the multiphoton nature of the probe-induced ionization step, reproduced the observed delay in the yield. It originates from resonant enhancement of the multiphoton ionization of the electronically excited ethylene cation as the carbon–carbon double bond expands. However, this effect is tempered by rapid nonadiabatic relaxation of the excited ionic states. Our results suggest a general mechanism whereby ultrafast nonadiabatic relaxation of a molecular ion can compete with its strong-field ionization rate, confining the dication yield to a narrow temporal window of a few femtoseconds.

74 ATOMIC AND MOLECULAR PHYSICS↗

High Photoluminescence Quantum Yield in Band Gap Tunable Bromide Containing Mixed Halide Perovskites

Hybrid organic-inorganic halide perovskite based semiconductor materials are attractive for use in a wide range of optoelectronic devices because they combine the advantages of suitable optoelectronic attributes and simultaneously low-cost solution processability. Here, we present a two-step low-pressure vapor-assisted solution process to grow high quality homogeneous CH 3 NH 3 PbI 3-x Br x perovskite films over the full band gap range of 1.6-2.3 eV. Photoluminescence light-in versus light-out characterization techniques are used to provide new insights into the optoelectronic properties of Br-containing hybrid organic-inorganic perovskites as a function of optical carrier injection by employing pump-powers over a 6 orders of magnitude dynamic range. The internal luminescence quantum yield of wide band gap perovskites reaches impressive values up to 30%. This high quantum yield translates into substantial quasi-Fermi level splitting and high "luminescence or optically implied" open-circuit voltage. Most importantly, both attributes, high internal quantum yield and high optically implied open-circuit voltage, are demonstrated over the entire band gap range (1.6 eV ≤ E g ≤ 2.3 eV). These results establish the versatility of Br-containing perovskite semiconductors for a variety of applications and especially for the use as high-quality top cell in tandem photovoltaic devices in combination with industry dominant Si bottom cells. (Figure Presented).

36 MATERIALS SCIENCE↗

Pretreatment with Sodium Methyl Mercaptide Increases Carbohydrate Yield during Kraft Pulping

Kraft pulping is the predominant technology in the pulp and paper industry for removing lignin from wood carbohydrates to produce paper, board, packaging, tissue, and specialty cellulose. However, the kraft process is energy intensive and expensive, and its yield is limited by the degradation of carbohydrates. Pretreatment can increase carbohydrate yield by limiting degradation via primary peeling of reducing end groups. However, protection of galactoglucomannan (GGM), the primary hemicellulose component of softwood, is minimal when conventional pretreatments are used. Here, we investigated the effectiveness of sodium methyl mercaptide pretreatment on southern pine wood chips under a range of experimental conditions. We found that pretreatment of biomass with 4.38% sodium methyl mercaptide at pH 12 and 105 °C for 60 min provided small but significant increases in xylan and cellulose yields relative to control conditions, but preservation of GGM was minimal. Furthermore, to provide insight into molecular-scale details of primary peeling, pretreatment, and alkaline hydrolysis, we performed classical molecular dynamics (MD) simulations under selected process conditions and quantum mechanical (QM) calculations of selected reactions. MD simulations showed that C1 of the GGM reducing end is more readily accessible by HO – and CH 3 S – ions than in cellulose. The free energy barrier for peeling calculated with QM is lower for GGM than for cellulose, indicating increased susceptibility to peeling. In addition, we found that GGM may be more susceptible to internal chain cleavage than cellulose. Thus, even though reducing end groups may be protected initially through pretreatment, new unprotected reducing end groups may be generated through alkaline hydrolysis. Taken together, these findings show the promise of methyl mercaptide as a pretreatment technology for cellulose retention and also provide molecular insight for improving its effectiveness toward GGM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing Coke and Increasing Bio-Oil Yield during Catalytic Fast Pyrolysis of Biomass Using Phosphorus-Modified Zeolite Catalysts

Catalytic fast pyrolysis (CFP) is a promising strategy for producing hydrocarbon transportation fuels from biomass feedstocks. However, catalyst development is needed to increase bio-oil yields and enhance process economics. In this work, we demonstrate how post synthetic modification of formed ZSM-5 with phosphorus shifts CFP selectivity from coke and light gases toward the desired bio-oil product. Microscale experiments demonstrated reduced coke production relative to unmodified ZSM-5 and identified an optimal P loading. Extensive catalyst characterization revealed that P interacted with Al sites to reduce the acid site density, with preferential binding to the strongest acid sites. Insights from the microscale experiments were leveraged to produce kilogram quantities of formed P-ZSM-5 for evaluation in a larger semi-integrated process. These experiments generated liters of bio-oil that was hydrotreated and fractionated into gasoline, diesel, and jet cuts. The phosphorus-modified ZSM-5 improved CFP bio-oil yield, resulting in an 11% relative increase in the carbon yield from biomass to aviation fuel and a 14% decrease in the minimum fuel selling price. These results highlight the impact targeted changes in catalyst acidity, achieved by adding 2.5 wt % P, can have on the carbon efficiency and feasibility of fuel production from biomass feedstocks.

09 BIOMASS FUELS↗

Preserving Aryl Ether Linkages and Higher Yields of Isolated Lignin through Biomass Fibrillation

Ball milling is used for size reduction of biomass for isolating lignin. However, it is known that it can lead to some structural alteration of lignin. Fibrillation using ultrafriction grinding is a newer size reduction technology which was applied to poplar for isolating cellulolytic enzyme lignin. Compositional analysis of poplar, enzymatic hydrolysis yield, water retention value, lignin yield, lignin structural characterization, and lignin molecular weight analysis were carried out to compare lignin isolated from fibrillated and ball milled poplar. By using fibrillation instead of planetary ball milling for size reduction of poplar, higher β-O-4' linkage content, lignin yield, and molecular weight were obtained. Replacing ball milling with fibrillation for size reduction allows recovery of lignin whose structure is closer to that of lignin in biomass.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Excitation-emission spectra and fluorescence quantum yields for fresh and aged biogenic secondary organic aerosols

Certain biogenic secondary organic aerosols (SOA) become absorbent and fluorescent when exposed to reduced nitrogen compounds such as ammonia, amines and their salts. Fluorescent SOA may potentially be mistaken for biological particles by detection methods relying on fluorescence. This work quantifies the spectral distribution and effective quantum yields of fluorescence of SOA generated from two monoterpenes, limonene and a-pinene, and two different oxidants, ozone (O3) and hydroxyl radical (OH). The SOA was generated in a smog chamber, collected on substrates, and aged by exposure to ~100 ppb ammonia vapor in air saturated with water vapor. Absorption and excitation-emission matrix (EEM) spectra of aqueous extracts of aged and control SOA samples were measured, and the effective absorption coefficients and fluorescence quantum yields (~0.005 for 349 nm excitation) were determined from the data. The strongest fluorescence for the limonene-derived SOA was observed for excitation = 420+- 50 nm and emission = 475 +- 38 nm. The window of the strongest fluorescence shifted to excitation = 320 +- 25 nm and emission = 425 +- 38 nm for the a-pinene-derived SOA. Both regions overlap with the excitation-emission matrix (EEM) spectra of some of the fluorophores found in primary biological aerosols. Our study suggests that, despite the low quantum yield, the aged SOA particles should have sufficient fluorescence intensities to interfere with the fluorescence detection of common bioaerosols.

Environmental Molecular Sciences Laboratory↗

Cropland expansion in the United States produces marginal yields at high costs to wildlife

Recent expansion of croplands in the United States has caused widespread conversion of grasslands and other ecosystems with largely unknown consequences for agricultural production and the environment. Here we assess annual land use change 2008–16 and its impacts on crop yields and wildlife habitat. We find that croplands have expanded at a rate of over one million acres per year, and that 69.5% of new cropland areas produced yields below the national average, with a mean yield deficit of 6.5%. Observed conversion infringed upon high-quality habitat that, relative to unconverted land, had provided over three times higher milkweed stem densities in the Monarch butterfly Midwest summer breeding range and 37% more nesting opportunities per acre for waterfowl in the Prairie Pothole Region of the Northern Great Plains. Our findings demonstrate a pervasive pattern of encroachment into areas that are increasingly marginal for production, but highly significant for wildlife, and suggest that such tradeoffs may be further amplified by future cropland expansion.

54 ENVIRONMENTAL SCIENCES↗