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At least 127 records · Page 7

Kinetic processes of phase separation and aggregation behaviors in slot-die processed high efficiency Y6-based organic solar cells

Morphological optimization has proved to be one crucial factor contributing to the 19% efficiency of Y6-based organic solar cells (OSCs). Although the relationship between component miscibility and film morphology has been established, it has not been clarified how the film formation processes proceed, especially for methods compatible with large-area fabrication, i.e. slot-die coating, which restricts the further optimization of the morphology. Herein, we comprehensively investigate the effect of miscibility and the film-formation kinetic process on film morphology during processing with different solvents. A highest power conversion efficiency (PCE) of 17.38% can be obtained in a D18:Y6 device processed with slot-die coating in an open-air environment. However, due to their relatively poor miscibility, incorporating a trace amount of chlorobenzene (CB) into CF can sufficiently promote Y6 aggregation, leading to increased phase separation and thus the average PCE drops to 15.16%. In contrast, a PM6:Y6 blend shows insensitive changes in the kinetic process as well as the final morphology, and thus in the comparable PCEs when cast with different solvents, which is ascribed to their relatively good miscibility. As a result, this work provides scientific guidelines for device optimization by combining the intermediate gap from miscibility to kinetic process and their impact on final morphology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Regulating Gas Transport in Molecularly Engineered Polymer Membranes (Final Technical Report)

Energy-efficient separation processes are essential for a wide range of applications ranging from clean fuels (e.g., hydrogen purification) and petroleum refining (e.g., natural gas processing) to water purification and carbon capture. Membrane-mediated separations have shown tremendous promise in providing high productivity and high separation efficiency at significantly lower energy consumption, e.g., up to 90% less energy cost than traditional thermally driven processes such as distillation. Polymeric membranes–the dominant separation membrane materials–have yet to reach their full potential due to their limitations in long-term durability (e.g., productivity loss over the period of their lifetime due to physical aging) or insufficient stability under harsh conditions (e.g., high temperature, chemically complex feeds). This research seeks to establish a new paradigm in polymer membrane material design by harnessing crosslinked model networks with well-defined yet finely tailorable microstructure to facilitate fast and selective gas transport and simultaneously enhance membrane stability. Unlike traditional randomly crosslinked polymers, which suffer from structural inconsistencies and consequently suboptimal gas separation performance, crosslinked model network membranes prepared via a precisely controlled end-linking process enables the creation of previously unattainable microstructure tunability, which, in turn, results in versatile crosslinked membranes with high separation performance that meet the needs of various challenging gas separations. Using model network framework as a fundamental tool by applying this concept in diverse polymer categories, this work has led to the development of various innovative crosslinked membrane structures such as unimodal, bimodal and clustered model networks. These advanced crosslinked polymer membranes not only demonstrate exceptional gas separation performance that significantly outperform existing randomly crosslinked membranes, but also possess excellent long-term durability and robust stability under complex operating conditions. From a fundamental perspective, results from this research provide critical mechanistic insights into gas separation in crosslinked polymer membranes, addressing key knowledge gaps and opening new avenues for membrane design to meet various separation needs. The new membrane materials produced from this research enable the use of polymeric membranes for high temperature gas separations, offering substantial energy and cost savings by eliminating the need for repeated cooling-heating cycles in industrial processes.

02 PETROLEUM↗

Understanding the performance of membrane for direct air capture of CO 2

Abstract Direct air capture (DAC) of CO 2 is becoming increasingly important for reducing greenhouse gas concentrations in the atmosphere. However, the cost and energy requirements associated with DAC make it less economically feasible than carbon capture from flue gases. While various methods like solid sorbents and gas–liquid absorption have been explored for DAC, membrane processes have only recently been investigated. The objective of this study is to examine the separation performance of a membrane unit for capturing CO 2 from ambient air. The performance of a membrane depends on several factors, including the composition of the feed gas, pressure ratio, material selectivity, and membrane area. The single‐stage separation process with the co‐current flow and constant permeability flux model is evaluated using a commercial module integrated with a process simulator to separate a binary mixture of carbon dioxide and nitrogen to assess the sensitivity of selectivity on purity and recovery of CO 2 in permeate, and power requirement. Additionally, three levels of CO 2 reduction from the feed stream to the retentate stream (25%, 50%, and 75%) are studied. A trade‐off between purity and recovery factor is observed, and achieving high purity in permeate requires high concentration in the retentate.

Panja, Palash↗

Lithium isotopic analysis in depleted lithium salts

Lithium isotope separation processes require characterization of the isotopic compositions of the different output phases of the process. While considerable effort to develop isotope separation methods has been ongoing for decades, the analytical methods associated with these analyses are rarely provided. Here, in this work three types of mass spectrometers (Q-ICP-MS, MC-ICP-MS, TIMS) were tested for the ability to measure depleted lithium salts that are relevant materials for isotopic separations. Results indicate that, once stabilized, the Q-ICP-MS can provide equal precision for Li isotopic samples compared to TIMS or MC-ICP-MS. However, MC-ICP-MS consistently provides the highest precision for salts across both depleted and natural isotopic abundances. These data demonstrate that Q-ICP-MS is an appropriate choice for analysis of depleted lithium salts, especially when rapid analyses are desired for online process monitoring.

07 ISOTOPE AND RADIATION SOURCES↗

Graph-Based Representations and Applications to Process Simulation

Rapid and robust convergence of a process flowsheet is critical to enable large-scale simulations that address core scientific questions related to process design, optimization, and sustainability. However, due to the highly coupled and nonlinear nature of chemical processes, efficiently solving a flowsheet remains a challenge. In this work, we show that graph representations of the underlying physical phenomena in unit operations may help identify potential avenues to systematically reformulate the network of equations and enable more robust topology-based convergence of flowsheets. To this end, we developed graph abstractions of the governing equations of vapor-liquid and liquid-liquid equilibrium separation equipment. These graph abstractions consist of a mesh of interconnected variable nodes and equation nodes that are systematically generated through PhenomeNode, a new open-source library in Python developed in this study. We show that partitioning the graph into separate mass, energy, and equilibrium subgraphs can help decouple nonlinearities and guide decomposition algorithms. By employing the graph abstraction on an industrial separation process for separating glacial acetic acid from water, we implemented a new block decomposition scheme in BioSTEAM and demonstrated that this can accelerate convergence over a traditional sequential modular approach.

Distillation↗

Separation dynamics of the COMET FreeFlyer and an upper stage STAR-48V motor

In this report, the orbital separation between a STAR-48V upperstage motor and the COMET FreeFlyer is investigated. The time from nominal STAR-48 engine burnout is to be determined such that the STAR-48 will not collide with the FreeFlyer once the separation process has been initiated. To analyze this separation, the forces acting upon both the FreeFlyer and the STAR-48 are described in a body fixed coordinate system. These coordinates are then transformed into an Euler coordinate system and then further transformed into a relative inertial coordinate system. From this analysis and some basic assumptions about the Star-48/FreeFlyer vehicle, it can be concluded that the STAR-48 will not collide with the Free Flyer if the separation occurs at 120 seconds after nominal burnout of the STAR-48. In fact, the separation delay could be a shorter period of time, but it is recommended that this separation delay be as long as possible for risk mitigation. This delay is currently designed to be 120 seconds and the analysis presented in this report shows that this time is acceptable.

Fuller, Kevin M.↗

PING Gamma Ray and Neutron Measurements of a Meter-Sized Carbonaceous Asteroid Analog

Determining the elemental composition of carbonaceous (spectral type C) asteroids is still one of the basic problems when studying these objects. The only main source of elemental composition information for asteroids is from their optical, NIR and IR properties, which include their spectral reflectance characteristics, albedo, polarization, and the comparison of optical spectroscopy with meteorite groups corresponding to asteroids of every spectral type. Unfortunately, these sources reflect observations from widely contrasting spatial scales that presently yield a void in the continuum of microscopic and macroscopic evidence, a lack of in situ measurement confirmation, and require deeper sensing techniques to discern the nature of these asteroids. The Probing In situ with Neutrons and Gamma rays (PING) instrument is ideally suited to address this problem because it can be used to determine the bulk elemental composition, H and C content, the average atomic weight and density of the surface and subsurface layers of C-type asteroids, and can provide measurements used to determine the difference between and distinguish between different types of asteroids. We are currently developing the PING instrument that combines gamma ray and neutron detectors with a 14 Me V pulsed neutron generator to determine the in-situ bulk elemental abundances and geochemistry of C-type asteroids with a spatial resolution of 1 m down to depths of tens of cm to 1 m. One aspect of the current work includes experimentally testing and optimizing PING on a known meter-sized Columbia River basalt C-type asteroid analog sample that has a similar composition and the same neutron response as that of a C-type asteroid. An important part of this effort focuses on utilizing timing measurements to isolate gamma rays produced by neutron inelastic scattering, neutron capture and delayed activation processes. Separating the gamma ray spectra by nuclear processes results in higher precision and sensitivity elemental composition measurements. Using gated data acquisition techniques allows for the unambiguous identification of gamma ray lines from different isotopes and nuclear processes, especially in situations when limited detector resolution results in overlapping gamma ray lines that cannot be individually resolved. In this paper, we will present the PING basalt layering experimental data, taken at the test facility at NASA Goddard Space Flight Center using the time tagged event-by-event data analysis technique, compared to our MCNPX computer simulation results for the C-type asteroid and basalt layering simulant models. Comparison of these data will show the advantages, validity, and measurement sensitivity of PING's nuclear interrogation methods to obtain more precise and sensitive in situ bulk elemental composition and density measurements of the subsurface of asteroids.

Bodnarik, J.↗

Life Cycle Analysis of Greenhouse Gas Emissions for the Niagaran Reef Complex CO 2 -EOR Operations

The Midwest Regional Carbon Sequestration Partnership (MRCSP) was founded in 2003 as part of the U.S. Department of Energy’s (DOE’s) Regional Carbon Sequestration Partnership initiative. Since its founding, MRCSP has made significant strides toward making CCUS a viable option for states in the region. The public/private consortium, funded through the DOE Regional Carbon Sequestration Initiative, brings together nearly 40 industry partners and 10 states. Battelle, as the project lead, oversees research, development and operations and coordinates activities among the partners. The incremental, phased approach has built a valuable knowledge base for the industry and paved the way for commercial-scale adoption of CCUS technologies. From 2008 to 2020, MRCSP Phase III focused on the development of large-scale injection projects. This report is part of a series of reports prepared under the Midwestern Regional Carbon Sequestration Partnership (MRCSP) Phase III (Development Phase). These reports summarize and detail the findings of the work conducted under the Phase III project. A greenhouse gas emissions life cycle analysis (LCA) was completed for 22 years of carbon dioxide-enhanced oil recovery (CO 2 -EOR) operations at the Niagaran reef complex in the northern Michigan Basin based on research by the MRCSP. The objective of the greenhouse gas LCA was to account for the total greenhouse gas emissions generated through the CO 2 -EOR process. Methane produced from the 300 to 500 meter-deep Antrim shale has CO 2 content ranging from 5 percent to 30 percent. Therefore, the produced gas stream is gathered outside of Gaylord, Michigan, at the Chester 10 central gas processing plant, and run through an amine-based CO 2 separation process to remove the CO 2 so the methane can be sold to the market. The CO 2 is periodically dehydrated, compressed, and transported via pipeline for CO 2 -EOR in nearby 5,000- to 6,500-foot (1500-2000 m) deep carbonate Niagaran reefs. The produced mixture of oil, water, and CO 2 is separated at the Dover 36 oil processing facility. The processed CO 2 is recycled to the reefs for CO 2 -EOR in a closed loop system. During this process, a portion of the CO2 remains permanently stored in the reefs.

01 COAL, LIGNITE, AND PEAT↗

Assessment of critical-fluid extractions in the process industries

The potential for critical-fluid extraction as a separation process for improving the productive use of energy in the process industries is assessed. Critical-fluid extraction involves the use of fluids, normally gaseous at ambient conditions, as extraction solvents at temperatures and pressures around the critical point. Equilibrium and kinetic properties in this regime are very favorable for solvent applications, and generally allow major reductions in the energy requirements for separating and purifying chemical component of a mixture.

Source record↗

A fast computational framework for the design of solvent-based plastic recycling processes

Multicomponent plastics cannot be processed using mechanical recycling technologies, hindering efforts to deal with plastic waste. Multicomponent plastics include multilayer plastic films, which are widely used for food and healthcare packaging. Multilayer films combine several layers (potentially dozens) of different polymers to protect products from external factors (e.g., oxygen, water, temperature, shock, and light). Solvent-based separation processes have emerged as a promising alternative to recycle these complex materials. For instance, the Solvent-Targeted Recovery and Precipitation (STRAP TM ) process uses sequential solvent washes to selectively dissolve and separate constituent polymers from multicomponent plastic waste, including films. STRAP TM process design (separation sequence, type of solvents, and operating conditions) changes significantly depending on the design of the multilayer plastic film (e.g., number, types, and proportions of polymers). The ability to quickly quantify the economic and environmental benefits of diverse STRAP TM process designs is essential to accelerate the development of sustainable recycling processes and more recyclable multilayer film products. In this work, we present a fast computational framework that integrates molecular-scale models, process modeling, and techno-economic and life cycle analysis to quickly evaluate STRAP TM designs. The computational framework is general and can be used to study the processing of complex multilayer plastic waste streams that contain many layers. Furthermore, we highlight the different uses of the framework via targeted case studies.

Computational framework↗

Pervaporative Dehydration of 2,3-Butanediol by Dense Poly(vinylidene fluoride) Hollow Fiber Membranes: Parameter Estimation, Process Design, and Technoeconomic Evaluation under Uncertainty

Pervaporation, combined with other separation processes, can effectively remove water from fermentation product streams, making it highly suitable for purifying alcohols like 2,3-butanediol (BDO). In this study, a dense poly(vinylidene fluoride) (PVDF) hollow fiber membrane module prototype was fabricated for BDO dehydration, achieving >0.2 LMH total flux and >95% BDO rejection. With a Markov chain Monte Carlo (MCMC) approach, Bayesian inference was used to quantify the uncertainty of the permeance parameters. A membrane cascade model was developed to scale up a process that purifies a preconcentrated BDO feed (70 wt %) to high purity (90 wt %). Through propagation of the uncertainty of the parameters and sensitivity analyses of the process variables, a cascade design was recommended. Despite data and model limitations, the framework enabled a reliable system analysis and economic evaluation, validated through tight confidence intervals in key process metrics, establishing the foundation for future applications of Bayesian methods in membrane-based processes.

Animal feed↗

Development of Electrochemical Detectors for Elemental Characterization of Actinides - 20563

The characterization of the actinides contained in radioactive waste involves complex and expensive separation processes. Electrochemical methods allow identifying and quantifying quickly and accurately the elementary concentration of actinides such as Th, U, Pu, Am, and Cm in liquid waste. The objective of this research proposal is to build a low-cost portable miniaturized electrochemical detector, which can be an alternative for an initial characterization of actinides in liquid waste. Therefore, this work proposes the use of an electrochemical graphite detector modified with phthalocyanine, to detect and quantify actinides in aqueous media. The electrochemical response of the modified graphite electrodes was performed by cyclic voltammetry, and so the detection and quantification limits for U and Th were determined. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Linking the Salmonella enterica 1,2-Propanediol Utilization Bacterial Microcompartment Shell to the Enzymatic Core via the Shell Protein PduB

Bacterial microcompartments (MCPs) are protein-based organelles that house the enzymatic machinery for metabolism of niche carbon sources, allowing enteric pathogens to outcompete native microbiota during host colonization. While much progress has been made toward understanding MCP biogenesis, questions still remain regarding the mechanism by which core MCP enzymes are enveloped within the MCP protein shell. Here, we explore the hypothesis that the shell protein PduB is responsible for linking the shell of the 1,2-propanediol utilization (Pdu) MCP from Salmonella enterica serovar Typhimurium LT2 to its enzymatic core. Using fluorescent reporters, we demonstrate that all members of the Pdu enzymatic core are encapsulated in Pdu MCPs. We also demonstrate that PduB is critical for linking the entire Pdu enzyme core to the MCP shell. Using MCP purifications, transmission electron microscopy, and fluorescence microscopy, we find that shell assembly can be decoupled from the enzymatic core, as apparently empty MCPs are formed in Salmonella strains lacking PduB. Mutagenesis studies reveal that PduB is incorporated into the Pdu MCP shell via a conserved, lysine-mediated hydrogen bonding mechanism. Finally, growth assays and system-level pathway modeling reveal that unencapsulated pathway performance is strongly impacted by enzyme concentration, highlighting the importance of minimizing polar effects when conducting these functional assays. Together, these results provide insight into the mechanism of enzyme encapsulation within Pdu MCPs and demonstrate that the process of enzyme encapsulation and shell assembly are separate processes in this system, a finding that will aid future efforts to understand MCP biogenesis.

1, 2-propanediol utilization↗

Protein engineering for critical metal recovery beyond REEs

Achieving decarbonization and electrification goals will require expanded production of critical minerals (CM), including Li, Co, Cu, rare earths, Ni, and graphite, whose supply chains are geopolitically vulnerable. Problematically, current extraction and separation processes pose severe environmental burdens that impede the development of a diversified domestic supply chain and undercut the environmental benefits of energy technologies [1, 2]. The development of efficient, economical, and environmentally sustainable processing technologies is thus important for meeting the CM demand of the emerging energy technology market. To this end, we have recently developed an all-aqueous protein-based process for rare earth element (REE) extraction and separation. To extend our protein-based approach to critical metals beyond REEs, the goal of this project was to develop a protein discovery and engineering pipeline to generate a panel of proteins that selectively bind target critical metals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalizable Porous Aromatic Framework‐Included Polymer Membranes for Diffusion‐Enhanced Gas Separations

Industrial separation processes account for 10-15% of global energy consumption. Membrane-based processes are less energy-intensive than traditional gas separation technologies; however, enhanced material separation performance and stability for numerous gas mixtures are needed for widespread industrial adoption. This work presents a generalizable strategy for preparing mixed-matrix gas separation membranes exceeding the performance upper bounds of existing polymer membranes for a wide variety of industrial gases. By incorporating robust porous aromatic framework (PAF) particles into various dense commercial polymer matrices, gas diffusivity and solubility can be enhanced. For diverse gas mixtures (e.g., CO2/N2, O2/N2, He/CH4, H2/N2, and C2H4/C2H6), the resulting composite membranes exhibit enhanced gas permeabilities-by as much as 520%-and largely unchanged selectivities even after 6 years of aging under simulated flue gas conditions. These improvements arise from the ultrahigh porosity, excellent chemical compatibility, and unique physicochemical properties of the embedded PAF particles. Functionalizing the PAFs with polyamines also enables composite membranes that achieve among the highest reported performances against plasticization, a common obstacle in commercializing gas separation membranes. Significantly, the PAF-1 particles are readily dispersible in various common membrane casting solvents, suggesting their broader utility as a filler for designing high-performance membranes for many industrial gas separations.

Uliana, Adam A↗

Bioprocessing development: Immune/cellular applications: Anti-Ig autoantibody and complement-mediated destruction of neoplastic cells

This space bioprocessing contract effort was comprised of four general objectives. These were: (1) the evaluation of current separation processes, (2) the identification of problems relevant to the separation of important biologicals, (3) the identification of ground-based assay methods needed for pre- and postflight analysis of space bioprocessing separation technology; and (4) the establishment of methods to determine the efficiency of space bioprocessing separation procedures. Immunology was deemed advantageous to study the diversity of cells and cell products involved and the extensive interest being given to their separation. Upon recognition of a cellular or molecular agent as foreign to the body, the immune system becomes activated to produce cells whose function is to destroy that agent and cell products whose function is to inactivate the agent and assist in its destruction. Long after the agent is removed from the body, some cells remain in a state of readiness to continue these destructive actions specifically against that agent should further exposure to it occur. This is the basis of acquired immunity to disease.

Twomey, J. J.↗

DSN Beowulf Cluster-Based VLBI Correlator

The NASA Deep Space Network (DSN) requires a broadband VLBI (very long baseline interferometry) correlator to process data routinely taken as part of the VLBI source Catalogue Maintenance and Enhancement task (CAT M&E) and the Time and Earth Motion Precision Observations task (TEMPO). The data provided by these measurements are a crucial ingredient in the formation of precision deep-space navigation models. In addition, a VLBI correlator is needed to provide support for other VLBI related activities for both internal and external customers. The JPL VLBI Correlator (JVC) was designed, developed, and delivered to the DSN as a successor to the legacy Block II Correlator. The JVC is a full-capability VLBI correlator that uses software processes running on multiple computers to cross-correlate two-antenna broadband noise data. Components of this new system (see Figure 1) consist of Linux PCs integrated into a Beowulf Cluster, an existing Mark5 data storage system, a RAID array, an existing software correlator package (SoftC) originally developed for Delta DOR Navigation processing, and various custom- developed software processes and scripts. Parallel processing on the JVC is achieved by assigning slave nodes of the Beowulf cluster to process separate scans in parallel until all scans have been processed. Due to the single stream sequential playback of the Mark5 data, some ramp-up time is required before all nodes can have access to required scan data. Core functions of each processing step are accomplished using optimized C programs. The coordination and execution of these programs across the cluster is accomplished using Pearl scripts, PostgreSQL commands, and a handful of miscellaneous system utilities. Mark5 data modules are loaded on Mark5 Data systems playback units, one per station. Data processing is started when the operator scans the Mark5 systems and runs a script that reads various configuration files and then creates an experiment-dependent status database used to delegate parallel tasks between nodes and storage areas (see Figure 2). This script forks into three processes: extract, translate, and correlate. Each of these processes iterates on available scan data and updates the status database as the work for each scan is completed. The extract process coordinates and monitors the transfer of data from each of the Mark5s to the Beowulf RAID storage systems. The translate process monitors and executes the data conversion processes on available scan files, and writes the translated files to the slave nodes. The correlate process monitors the execution of SoftC correlation processes on the slave nodes for scans that have completed translation. A comparison of the JVC and the legacy Block II correlator outputs reveals they are well within a formal error, and that the data are comparable with respect to their use in flight navigation. The processing speed of the JVC is improved over the Block II correlator by a factor of 4, largely due to the elimination of the reel-to-reel tape drives used in the Block II correlator.

Rogstad, Stephen P.↗

Joint Factorization of QCD and QED Radiation in Lepton-Hadron Scattering

The factorization theorem plays an important role in the analysis of high energy quantum chromodynamic (QCD) processes, separating the nonperturbative hadronic interaction into the universal parton distribution functions (PDFs) and fragmentation functions (FFs) and the process-dependent interactions into short distance perturbative calculations, with any interference power suppressed. With a virtual photon exchange, lepton-hadron deep inelastic scattering (DIS) provides an electromagnetic hard probe for the partonic structure of colliding hadrons and has played an important role in the development of QCD factorization. However, the collision induced QED radiation can change the momentum of the exchanged but unobserved virtual photon, making the photon-hadron frame, where the factorization formalism for DIS and semi-inclusive DIS (SIDIS) was derived, ill defined. A new analogous factorization approach has been introduced to separate the leading power process-independent QED radiative contributions to the single photon exchange by introducing lepton distribution functions (LDFs) and lepton fragmentation functions (LFFs), while process-dependent effects are perturbatively calculated with large logarithms removed [J. High Energ. Phys. 2021, 157 (2021)]. These LDFs and LFFs are considered global, as they appear in many different interactions, such as e+e-, DIS and SIDIS, so data from experiments can be used to fit and describe these functions across a wide range of lepton scattering. In this work, I will apply this new hybrid factorization approach to lepton-hadron DIS and SIDIS. For DIS, I derive the NLO short distance perturbative contribution to the cross section and demonstrate the effects the QED radiation has on the cross section using this approach using the CTEQ parameterization for the QCD functions. As part of the SIDIS analysis, I study the cross-section in two different kinematic regions: (1) the scattered lepton and observed hadron are not near back-to-back, and (2) they are close to back-to-back, where collinear QCD factorization works for (1) and TMD QCD factorization for (2) while collinear QED factorization works for both. As part of this work, I show the effects on the SIDIS cross section using fixed order calculations for the unpolarized structure function by first showing the effect of the radiative corrections on the main kinematic variables, especially how the internal transverse momentum is significantly correlated to the external angular dependence, and then the unpolarized structure function (or cross section) with matching between the descriptions for low and high transverse momentum. This work will impact the calculations for predictions for data from COMPASS and various Jefferson Lab experiments.

Cammarota, Justin [Univ. of Kentucky, Lexington, K↗