Phase field simulation of liquid filling on grooved surfaces for complete, partial, and pseudo-partial wetting cases.

We develop and harness a phase field simulation method to study liquid filling on grooved surfaces. We consider both short-range and long-range liquid-solid interactions, with the latter including purely attractive and repulsive interactions as well as those with short-range attraction and long-range repulsion. This allows us to capture complete, partial, and pseudo-partial wetting states, demonstrating complex disjoining pressure profiles over the full range of possible contact angles as previously proposed in the literature. Applying the simulation method to study liquid filling on grooved surfaces, we compare the filling transition for the three different classes of wetting states as we vary the pressure difference between the liquid and gas phases. The filling and emptying transitions are reversible for the complete wetting case, while significant hysteresis is observed for the partial and pseudo-partial cases. In agreement with previous studies, we also show that the critical pressure for the filling transition follows the Kelvin equation for the complete and partial wetting scenarios. Finally, we find the filling transition can display a number of distinct morphological pathways for the pseudo-partial wetting cases, as we demonstrate here for varying groove dimensions.

Predicting Hemiwicking Dynamics on Textured Substrates.

The ability to predict liquid transport rates on textured surfaces is key to the design and optimization of devices and processes such as oil recovery, coatings, reaction-separation, high-throughput screening, and thermal management. In this work we develop a fully analytical model to predict the propagation coefficients for liquids hemiwicking through micropillar arrays. This is carried out by balancing the capillary driving force and a viscous resistive force and solving the Navier-Stokes equation for representative channels. The model is validated against a large data set of experimental hemiwicking coefficients harvested from the literature and measured in-house using high-speed imaging. The theoretical predictions show excellent agreement with the measured values and improved accuracy compared to previously proposed models. Furthermore, using lattice Boltzmann (LB) simulations, we demonstrate that the present model is applicable over a broad range of geometries. The scaling of velocity with texture geometry, implicit in our model, is compared against experimental data, where good agreement is observed for most practical systems. The analytical expression presented here offers a tool for developing design guidelines for surface chemistry and microstructure selection for liquid propagation on textured surfaces.

Visualizing nanoparticle dissolution by imaging mass spectrometry.

We demonstrate the ability to visualize nanoparticle dissolution while simultaneously providing chemical signatures that differentiate between citrate-capped silver nanoparticles (AgNPs), AgNPs forced into dissolution via exposure to UV radiation, silver nitrate (AgNO3), and AgNO3/citrate deposited from aqueous solutions and suspensions. We utilize recently developed inkjet printing (IJP) protocols to deposit the different solutions/suspensions as NP aggregates and soluble species, which separate onto surfaces in situ, and collect mass spectral imaging data via time-of-flight secondary ion mass spectrometry (TOF-SIMS). Resulting 2D Ag(+) chemical images provide the ability to distinguish between the different Ag-containing starting materials and, when coupled with mass spectral peak ratios, provide information-rich data sets for quick and reproducible visualization of NP-based aqueous constituents. When compared to other measurements aimed at studying NP dissolution, the IJP-TOF-SIMS approach offers valuable information that can potentially help in understanding the complex equilibria in NP-containing solutions and suspensions, including NP dissolution kinetics and extent of overall dissolution.

Automated correlation and classification of secondary ion mass spectrometry images using a k-means cluster method.

We present a novel method for correlating and classifying ion-specific time-of-flight secondary ion mass spectrometry (ToF-SIMS) images within a multispectral dataset by grouping images with similar pixel intensity distributions. Binary centroid images are created by employing a k-means-based custom algorithm. Centroid images are compared to grayscale SIMS images using a newly developed correlation method that assigns the SIMS images to classes that have similar spatial (rather than spectral) patterns. Image features of both large and small spatial extent are identified without the need for image pre-processing, such as normalization or fixed-range mass-binning. A subsequent classification step tracks the class assignment of SIMS images over multiple iterations of increasing n classes per iteration, providing information about groups of images that have similar chemistry. Details are discussed while presenting data acquired with ToF-SIMS on a model sample of laser-printed inks. This approach can lead to the identification of distinct ion-specific chemistries for mass spectral imaging by ToF-SIMS, as well as matrix-assisted laser desorption ionization (MALDI), and desorption electrospray ionization (DESI).

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry.

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.

Solid with infused reactive liquid (SWIRL): A novel liquid-based separation approach for effective CO2 capture.

Economical CO2 capture demands low-energy separation strategies. We use a liquid-infused surface (LIS) approach to immobilize reactive liquids, such as amines, on a textured and thermally conductive solid substrate with high surface-area to volume ratio (A/V) continuum geometry. The infused, micrometer-thick liquid retains that high A/V and directly contacts the gas phase, alleviating mass transport resistance typically encountered in mesoporous solid adsorbents. We name this LIS class "solid with infused reactive liquid" (SWIRL). SWIRL-amine requires no water dilution or costly mixing unlike the current liquid-based commercial approach. SWIRL-tetraethylenepentamine (TEPA) shows stable, high capture capacities at power plant CO2 concentrations near flue gas temperatures, preventing energy-intensive temperature swings needed for other approaches. Water vapor increases CO2 capacity of SWIRL-TEPA without compromising stability.

Electron scattering cross section measurements in a variable pressure scanning electron microscope.

Scattering of the incident electron beam in the variable pressure scanning electron microscope (VPSEM) affects the ability to perform quantitative chemical measurements. However, the manner in which the sum of the elastic and inelastic scattering cross sections varies as a function of gas type and accelerating voltage in the VPSEM is not well understood. A dual Faraday cup was constructed to measure the scattered fraction of the primary beam as a function of gas pressure, working distance, and accelerating voltage in air, water vapor, and argon environments. Experimentally measured values of the scattering cross section agree with previous experimental work, and agree within a factor of two with those values calculated carefully from theory.