Analysis of Direct Air Capture Integrated with Wind Energy and Enhanced Oil Recovery.

Direct air capture (DAC) is a decarbonization solution to remove carbon dioxide (CO2) from the atmosphere. The key challenges for accelerating DAC deployment are its energy requirements, high capital costs, and finding low-risk and low-cost sequestration or utilization pathways. Deploying DAC facilities proximal to sequestration or use sites and where the supply of low-cost renewable electricity is plentiful can minimize the energy, transportation, operational, and overall costs. Moreover, the increased 45Q tax credits in the Inflation Reduction Act of 2022 can further incentivize DAC deployment. This work provides a techno-economic assessment of two configurations: temperature swing adsorption-based DAC and membrane-based DAC integrated for operation with wind energy in West Texas to provide proximal access to enhanced oil recovery (EOR) operations. We evaluate the levelized cost of DAC and the cumulative cost of sequestering a ton of CO2 through EOR to identify opportunities for economic viability. Finally, we determine the profitability of CO2 sequestration under different EOR recovery factors and oil prices. We find that opportunities to reduce costs through proximal sequestration, integration with renewable energy, and the current level of policy support in the US can significantly incentivize and rapidly accelerate the deployment of DAC, especially for membrane-based technologies.

Technological Options for Direct Air Capture: A Comparative Process Engineering Review.

The direct capture of CO2 from ambient air presents a means of decelerating the growth of global atmospheric CO2 concentrations. Considerations relating to process engineering are the focus of this review and have received significantly less attention than those relating to the design of materials for direct air capture (DAC). We summarize minimum thermodynamic energy requirements, second law efficiencies, major unit operations and associated energy requirements, capital and operating expenses, and potential alternative process designs. We also highlight process designs applied toward more concentrated sources of CO2 that, if extended to lower concentrations, could help move DAC units closer to more economical continuous operation. Addressing shortcomings highlighted here could aid in the design of improved DAC processes that overcome trade-offs between capture performance and DAC cost.

Job Insecurity during an Economic Crisis: the Psychological Consequences of Widespread Corporate Cost-Cutting Announcements.

Economic crises, such as the one induced by the COVID-19 pandemic, and resulting widespread corporate cost-cutting, drastically alter the nature of work. Job insecurity represents a critical intermediate between the economic ramifications of an economic crisis and work and stress outcomes, however, the underlying cognitive consequences of job insecurity and how to buffer those effects are not well understood. We examine how corporate cost-cutting announcements indirectly relate to employees' attention through their relationship with employee job insecurity and investigate supervisor support as a potential buffer of these relationships. We used multi-source data to test our research model, combining data on cost-cutting announcements (budget cuts, layoffs, and furloughs) in news articles for 165 organizations with survey data from 421 full-time employees from these organizations between March 26, 2020 and April 8, 2020. Cost-cutting announcements are positively related to job insecurity, which is related to employee's attention with supervisor support mitigating the effects of job insecurity on attention. Grounded in self-regulation theories, we contribute to and extend the theoretical understanding of the organizational context for job insecurity and cognitive outcomes. We discuss the implications for organizations to manage and prepare for future economic crises, specifically on organizational communication and supervisor interventions.

I Don't Want to Go Back: Examining the Return to Physical Workspaces During COVID-19.

OBJECTIVE: We study employee perspectives on return to physical workspaces to ultimately inform employers' and policy makers' decision making around the return to work during COVID-19. METHODS: We tested the three-component conceptual model using survey data collected in the United States in May 2020 from samples of energy workers (N = 333). RESULTS: Women, non-Caucasians, and employees living in multi-generational households were less willing to return. Concerns about childcare were negatively related to willingness to return, whereas organizational strategies for mitigating COVID-19 transmission at work were positively related to willingness to return. COVID-19 infections in an employees' network were also negatively related to employees' willingness to return. CONCLUSIONS: Blanket policies may miss the nuanced needs of different employee groups. Employers and policy makers should adopt flexible approaches to ensure a return to workspaces that addresses employee concerns and needs.

Structure Dominates Localization of Tracers within Aging Nanoparticle Glasses.

We investigate the transport and localization of tracer probes in a glassy matrix as a function of relative size using dynamic X-ray scattering experiments and molecular dynamics simulations. The quiescent relaxations of tracer particles evolve with increasing waiting time, tw. The corresponding relaxation times increase exponentially at small tw and then transition to a power-law behavior at longer tw. As tracer size decreases, the aging behavior weakens and the particles become less localized within the matrix until they delocalize at a critical size ratio δ0 ≈ 0.38. Localization does not vary with sample age even as the relaxations slow by approximately an order of magnitude, suggesting that matrix structure controls tracer localization.

Soft Interactions Modify the Diffusive Dynamics of Polymer-Grafted Nanoparticles in Solutions of Free Polymer.

We examine the dynamics of silica particles grafted with high molecular weight polystyrene suspended in semidilute solutions of chemically similar linear polymer using X-ray photon correlation spectroscopy. The particle dynamics decouple from the bulk viscosity despite their large hydrodynamic size and instead experience an effective viscosity that depends on the molecular weight of the free polymer chains. Unlike for hard-sphere nanoparticles in semidilute polymer solutions, the diffusivities of the polymer-grafted nanoparticles do not collapse onto a master curve solely as a function of normalized length scales. Instead, the diffusivities can be collapsed across two orders of magnitude in free polymer molecular weight and concentration and one order of magnitude in grafted molecular weight by incorporating the ratio of free to grafted polymer molecular weights. These results suggest that the soft interaction potential between polymer-grafted nanoparticles and free polymer allows polymer-grafted nanoparticles to diffuse faster than predicted based on bulk rheology and modifies the coupling between grafted particle dynamics and the relaxations of the surrounding free polymer.

Conformational change and suppression of the Θ-temperature for solutions of polymer-grafted nanoparticles.

We determine the conformational change of polystyrene chains grafted to silica nanoparticles dispersed in deuterated cyclohexane using small-angle neutron scattering. The cyclohexane/polystyrene system exhibits an upper-critical solution temperature below which the system phase separates. By grafting the polystyrene chains to a nano-sized spherical silica particle, we observe a significant suppression in the Θ-temperature, decreasing from ≈38 °C for free polystyrene chains in d12-cyclohexane to ≈34 °C for the polystyrene-grafted nanoparticles. Above this temperature, the grafted chains are swollen and extended from the particle surface, resulting in well-dispersed grafted nanoparticles. Below this temperature, the grafted chains fully expel the solvent and collapse on the particle surface, destabilizing the nanoparticle suspension and leading to aggregation. We attribute the suppression of the Θ-temperature to a competition between entropic and enthalpic energies arising from the structure of the polymer-grafted nanoparticle in which the enthalpic terms appear to dominate.

Particle dispersion in porous media: Differentiating effects of geometry and fluid rheology.

We investigate the effects of geometric order and fluid rheology on the dispersion of micron-sized particles in two-dimensional microfluidic porous media. Particles suspended in a mixture of glycerol and water or in solutions of partially hydrolyzed polyacrylamide (HPAM) polymers were imaged as they flowed through arrays of microscale posts. From the trajectories of the particles, we calculated the velocity distributions and thereafter obtained the longitudinal and transverse dispersion coefficients. Particles flowed in the shear-thinning HPAM solution through periodic arrays of microposts were more likely to switch between streamlines, due to elastic instabilities. As a result, the distributions of particle velocity were broader in HPAM solutions than in glycerol-water mixtures for ordered geometries. In a disordered array of microposts, however, there was little difference between the velocity distributions obtained in glycerol-water and in HPAM solutions. Correspondingly, particles flowed through ordered post arrays in HPAM solutions exhibited enhanced transverse dispersion. This result suggests that periodic geometric order amplifies the effects of the elasticity-induced velocity fluctuations, whereas geometric disorder of barriers effectively averages out the fluctuations.

Nanoparticle diffusion in crowded and confined media.

We identify distinct mechanisms controlling slowing of nanoparticle diffusion through complex media featuring both rigid geometrical confinement and soft mobile crowders. Towards this end, we use confocal microscopy and single particle tracking to probe the diffusion of 400 nm nanoparticles suspended in Newtonian water, in a Newtonian glycerol/water mixture, or in a non-Newtonian polymer solution through a model porous medium, a packed bed of microscale glass beads. The mobility of nanoparticles, as quantified by the long-time diffusion coefficient extracted from the particle mean-squared displacement, slows as the average pore size of the packed bed media decreases for both Newtonian and non-Newtonian solutions. The distribution of particle displacements is non-Gaussian, consistent with the spatial heterogeneity of the geometrical confinement imposed by the packed bed. The slowing of nanoparticle mobility in all solutions follows the predictions of models that describe hydrodynamic interactions with the packed bed. In non-Newtonian solutions, depletion interactions due to the polymers near the glass beads result in temporary adsorption of particles onto the bead surface, as indicated by a stretched-exponential distribution of residence times. Our results therefore suggest that the confined diffusive dynamics of nanoparticles in polymer solutions is controlled by two competing mechanisms: hydrodynamic interactions between particles and spatial obstacles, which dictate the long-time slowing of diffusion, and depletion interactions between particles and confining walls due to the macromolecules, which control transient adsorption and hence alter the statistics of the short-time motion.

Nanoparticle dispersion in disordered porous media with and without polymer additives.

In purely viscous Newtonian fluids, mechanical mixing of the fluid stream as it moves through an unstructured porous medium controls the long-time dispersion of molecular tracers. In applications ranging from environmental remediation to materials processing, however, particles are transported through porous media in polymer solutions and melts, for which the fluid properties depend on the shear rate and extent of deformation. How the flow characteristics of polymer solutions affect the spreading of finite-sized particles remains poorly understood - both on the microscopic scale as local velocity profiles, and on the macroscale as dispersion. Here, we show across a range of flow rates and disordered porous media configurations that the long-time transport coefficients of particles flowed in water, in a viscous Newtonian fluid, and in a non-Newtonian shear-thinning polymer solution collapse onto scaling curves, independent of the fluid rheology. Thus the addition of polymer does not impact nanoparticle dispersion through disordered porous media.

Structural characterization of aqueous solution poly(oligo(ethylene oxide) monomethyl methacrylate)-grafted silica nanoparticles.

The structure of aqueous dispersions of poly(oligo(ethylene oxide) monomethyl methacrylate)-grafted silica nanoparticles was characterized using contrast variation small-angle neutron scattering studies. Modeling the low hybrid concentration dispersion scattering data using a fuzzy sphere and a polydisperse core-shell model, demonstrated that the polymer chains are highly swollen in the dispersions as compared to the dimensions of the free polymer chains in dilute solution. At higher hybrid concentrations, the dispersions were well described using a Percus-Yevick approximation to describe the structure factor. These structural characterization tools are excellent starting points for effective molecular level descriptors of dewetting and macroscopic phase transitions for polymer tethered hybrid nanoparticle systems.

Graphene Nanocomposites with High Molecular Weight Poly(ε-caprolactone) Grafts: Controlled Synthesis and Accelerated Crystallization.

Grafting of high molecular weight polymers to graphitic nanoplatelets is a critical step toward the development of high performance graphene nanocomposites. However, designing such a grafting route has remained a major impediment. Herein, we report a "grafting to" synthetic pathway by which high molecular weight polymer, poly(ε-caprolactone) (PCL), is tethered, at high grafting density, to highly anisotropic graphitic nanoplatelets. The efficacy of this tethering route and the resultant structural arrangements within the composite are confirmed by neutron and X-ray scattering measurements in the melt and solution phase. In the semicrystalline state, X-ray analysis indicates that chain tethering onto the graphitic nanoplatelets results in conformational changes of the polymer chains, which enhance the nucleation process and aid formation of PCL crystallites. This is corroborated by the superior thermal properties of the composite, manifested in accelerated crystallization kinetics and a significant increase in the thermal degradation temperature. In principle, this synthesis route can be extended to a variety of high molecular weight polymers, which can open new avenues to solution-based processing of graphitic nanomaterials and the fabrication of complex 3D patterned graphitic nanocomposites.

pH-Induced Re-entrant Microstructural Transitions in Cationic Surfactant-Hydrotrope Mixtures.

The structural transitions occurring with change in pH for aqueous mixtures of a cationic surfactant (cetyltrimethylammonium bromide, CTAB) and a hydrotrope (sodium salicylate, NaSal) were investigated at various temperatures using dynamic light scattering and small-angle neutron scattering. Direct structural studies show a transition from rigid cylindrical micelles at neutral pH to spherical micelles at ∼ pH 2 upon protonation of salicylate molecules; however, an unanticipated reversion to flexible cylindrical micelles with further decrease in pH was observed. We also observed these microstructure transitions from cylinders at high pH to spherical micelles at intermediate pH to flexible cylindrical micelles at low pH were highly sensitive to temperature. Our results suggest that, in addition to the well-described electrostatic and hydrophobic interactions in cationic surfactant-hydrotrope mixtures, the pH-induced microstructural changes are potentially governed by complementary cation-π and hydrogen bonding interactions.

Wetting-Dewetting and Dispersion-Aggregation Transitions Are Distinct for Polymer Grafted Nanoparticles in Chemically Dissimilar Polymer Matrix.

Simulations and experiments are conducted on mixtures containing polymer grafted nanoparticles in a chemically distinct polymer matrix, where the graft and matrix polymers exhibit attractive enthalpic interactions at low temperatures that become progressively repulsive as temperature is increased. Both coarse-grained molecular dynamics simulations, and X-ray scattering and neutron scattering experiments with deuterated polystyrene (dPS) grafted silica and poly(vinyl methyl ether) PVME matrix show that the sharp phase transition from (mixed) dispersed to (demixed) aggregated morphologies due to the increasingly repulsive effective interactions between the blend components is distinct from the continuous wetting-dewetting transition. Strikingly, this is unlike the extensively studied chemically identical graft-matrix composites, where the two transitions have been considered to be synonymous, and is also unlike the free (ungrafted) blends of the same graft and matrix homopolymers, where the wetting-dewetting is a sharp transition coinciding with the macrophase separation.

Diffusive dynamics of nanoparticles in ultra-confined media.

Differential dynamic microscopy (DDM) was used to investigate the diffusive dynamics of nanoparticles of diameter 200-400 nm that were strongly confined in a periodic square array of cylindrical nanoposts. The minimum distance between posts was 1.3-5 times the diameter of the nanoparticles. The image structure functions obtained from the DDM analysis were isotropic and could be fit by a stretched exponential function. The relaxation time scaled diffusively across the range of wave vectors studied, and the corresponding scalar diffusivities decreased monotonically with increased confinement. The decrease in diffusivity could be described by models for hindered diffusion that accounted for steric restrictions and hydrodynamic interactions. The stretching exponent decreased linearly as the nanoparticles were increasingly confined by the posts. Together, these results are consistent with a picture in which strongly confined nanoparticles experience a heterogeneous spatial environment arising from hydrodynamics and volume exclusion on time scales comparable to cage escape, leading to multiple relaxation processes and Fickian but non-Gaussian diffusive dynamics.

Size-Dependent Dynamics of Nanoparticles in Unentangled Polyelectrolyte Solutions.

The mobility of polystyrene nanoparticles ranging in diameter from 300 nm to 2 µm was measured in dilute and semidilute solutions of partially hydrolyzed polyacrylamide. In this model system, the ratio of particle to polymer size controls the long-time diffusivity of nanoparticles. The particle dynamics transition from subdiffusive on short time scales to Fickian on long time scales, qualitatively similar to predictions for polymer dynamics using a Rouse model. The diffusivities extracted from the long-time Fickian regime, however, are larger than those predicted by the Stokes-Einstein equation and the bulk zero-shear viscosity and moreover do not collapse according to hydrodynamic models. The size-dependent deviations of the long-time particle diffusivities derive instead from the coupling between the dynamics of the particle and the polymer over the length scale of the particle. Although the long-time diffusivities collapse according to predictions, deviations of the short-time scaling exponents and the crossover time between subdiffusive and Fickian dynamics indicate that the particles are only partially coupled to the relaxation modes of the polymer.

Conducting instant adhesives by grafting of silane polymer onto expanded graphite.

A "grafting to" methodology for the attachment of a silane based polymer (SG) onto functionalized graphitic platelets is demonstrated. The siloxy end groups of the modifier were further cross-linked without addition of any external curative. These sterically stabilized nanoplatelets with a high grafting density ensured complete screening of the attractive interparticle interactions. As a result, a better dispersion of platelets was observed compared to the physically mixed platelets in the polymer matrix (SUG). The larger size of the polymer tethered graphitic particles and the greater extent of heat liberated due to grafting resulted in a higher enthalpic contribution in the case of SG compared to SUG. This makes the formation of SG thermodynamically more favorable compared to SUG. Presence of a hierarchical spatial arrangement with a good dispersion of graphitic platelets was observed within the siloxane matrix in the case of SG compared to SUG. The nanoparticle tethered composite generated exhibited an "instant" conducting adhesive behavior. The adhesive properties of the SG were found to be increased due to grafting of graphitic platelets when compared with the neat polymer. Further, SG exhibited a conductive character whereas the neat polymer and SUG demonstrated an insulating character.

Mechanical reinforcement of epoxy with self-assembled synthetic clay in smectic order.

Epoxy films containing self-assembled 2D colloidal α-zirconium phosphate nanoplatelets (ZrP) in smectic order were prepared using a simple, energy-efficient fabrication process suitable to industrial processing. The ZrP nanoplatelets form a chiral smectic mesophase with simultaneous lamellar order and helical arrangements in epoxy. The epoxy nanocomposite films are transparent and flexible and exhibit exceptionally high tensile modulus and strength. The findings have broad implications for development of multifunctional materials for engineering applications.

Stress generation and tailoring of electronic properties of expanded graphite by click chemistry.

The generation of stress in expanded graphite (E-GPT) due to covalent attachment of bulky side groups connected via a hetero atom is reported. Specifically, E-GPT is modified at different levels of grafting using "click" chemistry to graft 1-ethynyl-4-fluoro benzene onto graphene sheets via a triazole ring. In the range of grafting densitites examined, Raman spectroscopy indicates that the stress generated in graphene is linearly dependent on the extent of grafting. The functionalized graphene platelets with 6% functionalization transform from semi-metal behavior of the pristine material to semi-conductor behavior and indicates the ability of functionalization to change optical and electronic properties of graphene platelets similar to the deposition of thin layers of top gate oxides onto graphene.