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At least 1,495 records · Page 83

Layer-by-layer modification of aliphatic polyamide anion-exchange membranes to increase Cl - /SO 4 2- selectivity

Development of anion-exchange membranes (AEMs) with selectivities among anions may expand the applications of these membranes in salt separations. This work shows that layer-by-layer coating of aliphatic polyamide AEMs with poly(4-styrenesulfonate) (PSS)/protonated poly(allylamine) (PAH) films enhances Cl - /SO 4 2- dialysis selectivities, and the extent of this enhancement depends on the source-phase salt concentrations. For a source phase containing 0.01 M NaCl and 0.01 M Na 2 SO 4 and a receiving phase of 0.01 M Na 2 CO 3 , a (PSS/PAH) 5 PSS coating (5 PSS/PAH “bilayers” capped with a layer of PSS) increases the Cl - /SO 4 2- selectivity from 1.7 to 5.3 in diffusion dialysis and from 1.3 to 7.4 in electrodialysis. Remarkably, the diffusion dialysis selectivity of a coated membrane increases to 140 when the salt concentrations in the source phase are 0.1 M. Even with bare membranes, selectivity increases to 13 with 0.1 M source-phase salt concentrations. Moreover, AEMs coated only on the receiving side show much higher selectivities but lower fluxes than those coated only on the source side. In conclusion, partitioning experiments and modelling suggest that the increased Cl - /SO 4 2- selectivities at high source-phase salt concentrations stem from enhanced Cl - partitioning and electromigration that disproportionately decreases SO 4 2- flux in the AEM.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a high efficiency integration system and promoter library for rapid modification of Pseudomonas putida KT2440

Pseudomonas putida strains are highly robust bacteria known for their ability to efficiently utilize a variety of carbon sources, including aliphatic and aromatic hydrocarbons. Recently, P. putida has been engineered to valorize the lignin stream of a lignocellulosic biomass pretreatment process. Nonetheless, when compared to platform organisms such as Escherichia coli, the toolkit for engineering P. putida is underdeveloped. Heterologous gene expression in particular is problematic. Plasmid instability and copy number variance provide challenges for replicative plasmids, while use of homologous recombination for insertion of DNA into the chromosome is slow and laborious. Furthermore, heterologous expression efforts to date typically rely on overexpression of exogenous pathways using a handful of poorly characterized promoters. In order to improve the P. putida toolkit, we developed a rapid genome integration system using the site-specific recombinase from bacteriophage Bxb1 to enable rapid, high efficiency integration of DNA into the P. putida chromosome. We also developed a library of synthetic promoters with various UP elements, -35 sequences, and -10 sequences, as well as different ribosomal binding sites. We tested these promoters using a fluorescent reporter gene, mNeonGreen, to characterize the strength of each promoter, and identified UP-element-promoter-ribosomal binding sites combinations capable of driving a ~150-fold range of protein expression levels. One additional integrating vector was developed that confers more robust kanamycin resistance when integrated at single copy into the chromosome. This genome integration and reporter systems are extensible for testing other genetic parts, such as examining terminator strength, and will allow rapid integration of heterologous pathways for metabolic engineering.

59 BASIC BIOLOGICAL SCIENCES↗

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↗

Effects of Alloying and Processing Modifications on Precipitation Behavior and Elevated Temperature Strength in 9% Cr Ferritic/Martensitic Steels

Two low-carbon 9-Cr ferritic-martensitic steels were designed here with the aim of decreasing M 23 C 6 and maintaining or increasing MX phase fraction. A low-carbon (LC) alloy and a low-carbon, zero-niobium (0 Nb) alloy were fabricated, their designs based upon the P92 alloy system. Solutionizing temperatures to maximize V and Nb in solution while avoiding δ-ferrite were determined to be 1170 °C for the P92 alloy and 1050 °C for LC and 0 Nb, significantly lower than predicted using ThermoCalc ® modelling. As was intended, the M 23 C 6 phase fraction was reduced for LC and 0 Nb alloys after both heat treating and aging relative to the base P92 alloy, as determined by wide angle x-ray scattering (WAXS) analysis. Dislocation density measurements from x-ray line broadening in P92 and LC suggest these alloys had more stable dislocation substructures than 0 Nb at lower temperature and shorter time aging conditions. While LC exhibited lower microhardness than P92 at room temperature, the tensile properties were comparable at 650 °C, suggesting that elevated temperature strength can be achieved with lower carbon contents. Aging studies showed that P92 had a more stable microstructure for higher temperature and longer time aging conditions. The P92 alloy also had a longer stress rupture life, implying that the M 23 C 6 precipitate contribution to thermal stability is important. Evidence of Z-phase was discovered for the LC alloy aged 10,000 h at 650 °C, corresponding to decreased strength and increased ductility. Overall, the stress rupture lives of the modified heat-treatment variations of P92 and LC compare favorably to literature values for 9% Cr steels with conventional heat treatments.

36 MATERIALS SCIENCE↗

Grain subdivision and structural modifications by high-energy heavy ions in UO 2 with different initial grain size

Irradiation with 84 MeV Xe ions at peak fluence above 7 × 10 17 ions/cm 2 has been carried out on two UO 2 samples with different initial grain sizes at 300 °C and 500 °C. Characterization of both grain structure and bubble morphology has been performed using transmission electron microscopy, image analysis and precession electron diffraction. The bubble size in the large-grained sample was smaller than that in the standard-grain sample, confirming fission gas precipitation resistance in the former. The ion irradiation in the high electronic energy deposition range has caused formation of a large density of dislocations which resulted in grain polygonization for the sample with standard grain size, which was observed in multiple lamellas extracted next to each other at peak dose. The sample with large grains showed inconsistent behavior. In one case, dislocation pile-up occurred, but no sub-grain formation was observed. An adjacent location showed sub-grain formation, even if to less extent compared to the standard grain-size sample. Furthermore, these findings suggest a limited polygonization resistance in large-grained UO 2 compared to standard-grain UO 2 . Recrystallization of both sample surfaces was present, leaving unclear if this is a surface effect or a consequence of the highest energy deposition rate in this area.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Comparative study of surface modification and D retention between beryllium and beryllides under high flux plasma exposure

The microstructures and deuterium (D) retention properties were investigated for beryllium intermetallic compounds (beryllides), such as Be 12 Ti and Be 12 V, compared to pure beryllium (Be), exposed to high density pure D and helium (He) mixed plasmas. TEM cross-sectional observations revealed the formation of cone structures on the Be surface exposed to the plasmas at a moderate temperature of 573 K. The crystal structure of the cones and the mass loss caused by the plasma exposure implied that the cone structures were generated by sputtering. The Ti or V surface enrichment was observed on both beryllides with no cone structures developed. TDS measurements indicated that He seeding to D plasma caused a ~ 4 times reduction of the D retention for both beryllides, while no reduction was observed for Be. As a result, the beryllide samples exposed to D + He mixture plasmas showed a lower total D retention than in Be.

Hydrogen retention↗