Christine Cardinal Roberts

Effect of soluble polymer binder on particle distribution in a drying particulate coating.

Soluble polymer is frequently added to inorganic particle suspensions to provide mechanical strength and adhesiveness to particulate coatings. To engineer coating microstructure, it is essential to understand how drying conditions and dispersion composition influence particle and polymer distribution in a drying coating. Here, a 1D model revealing the transient concentration profiles of particles and soluble polymer in a drying suspension is proposed. Sedimentation, evaporation and diffusion govern particle movement with the presence of soluble polymer influencing the evaporation rate and solution viscosity. Results are summarized in drying regime maps that predict particle accumulation at the free surface or near the substrate as conditions vary. Calculations and experiments based on a model system of poly(vinyl alcohol) (PVA), silica particles and water reveal that the addition of PVA slows the sedimentation and diffusion of the particles during drying such that accumulation of particles at the free surface is more likely.

Drying and cracking of soft latex coatings

The minimum film formation temperature (MFFT) is the minimum drying temperature needed for a latex coating to coalesce into an optically clear, dense crack-free film. To better understand the interplay of forces near this critical temperature, cryogenic scanning electron microscopy (cryoSEM) was used to track the latex particle deformation and water migration in coatings dried at temperatures just above and below the MFFT. Although the latex particles completely coalesced at both temperatures by the end of the drying process, it was discovered that particle deformation during the early drying stages was drastically different. Below the MFFT, cracks initiated just as menisci began to recede into the packing of consolidated particles, whereas above the MFFT, partial particle deformation occurred before menisci entered the coating and cracks were not observed. The spacing between cracks measured in coatings dried at varying temperatures decreased with decreasing drying temperature near the MFFT, whereas it was independent of temperature below a critical temperature. Finally, the addition of small amounts of silica aggregates was found to lessen the cracking of latex coatings near the MFFT without adversely affecting their optical clarity.

Circulation within confined droplets in Hele-Shaw channels

Liquid droplets flowing through a rectangular microfluidic channel develop a vortical flow field due to the presence of shear forces from the surrounding fluid. In this paper, we present an experimental and computational study of droplet velocities and internal flow patterns in a rectangular pressure-driven flow for droplet diameters ranging from 0.1 to 2 times the channel height. Our study shows excellent agreement with asymptotic predictions of droplet and interfacial velocities for infinitesimally small droplets. As the droplet diameter nears the size of the channel height, the droplet velocity slows significantly, and the changing external flow field causes a qualitative change in the location of internal vortices. This behavior is relevant for future studies of mass transfer in microfluidic devices.

Physical Properties of Low-Molecular Weight Polydimethylsiloxane Fluids

Physical property measurements including viscosity, density, thermal conductivity, and heat capacity of low-molecular weight polydimethylsiloxane (PDMS) fluids were measured over a wide temperature range (˗50 oC to 150 oC when possible). Properties of blends of 1 cSt and 20 cSt PDMS fluids were also investigated. Uncertainties in the measurements are cited. These measurements will provide greater fidelity predictions of environmental sensing device behavior in hot and cold environments.

Multiscale models of nuclear waste reprocessing : from the mesoscale to the plant-scale.

Nuclear waste reprocessing and nonproliferation models are needed to support the renaissance in nuclear energy. This report summarizes an LDRD project to develop predictive capabilities to aid the next-generation nuclear fuel reprocessing, in SIERRA Mechanics, Sandia’s high performance computing multiphysics code suite and Cantera, an open source software product for thermodynamics and kinetic modeling. Much of the focus of the project has been to develop a moving conformal decomposition finite element method (CDFEM) method applicable to mass transport at the water/oil droplet interface that occurs in the turbulent emulsion of droplets within the contactor. Contactor-scale models were developed using SIERRA Mechanics turbulence modeling capability. Unit operations occur at the column-scale where many contactors are connected in series. Population balance models

Criteria for drop generation in multiphase microfluidic devices

A theory is presented for the transition between the coflowing and the drop-generation regimes observed in microfluidic channels with a rectangular cross section. This transition is characterized by a critical ratio of the dispersed- to continuous-phase volume flow rates. At flow-rate ratios higher than this critical value, drop generation is suppressed. The critical ratio corresponds to the fluid cross section where the dispersed-phase fluid is just tangent to the channel walls. The transition criterion is a function of the ratio of the fluid viscosities, the three-phase contact angle formed between the fluid phases and the channel walls, and the aspect ratio of the channel cross section; the transition is independent of interfacial tension. Hysteretic behavior of drop generation with respect to the flow-rate ratio is predicted for partially wetting dispersed-phase fluids. Experimental data are consistent with this theory.

Modeling Manufacturing Impacts on Aging and Reliability of Polyurethane Foams

Polyurethane is a complex multiphase material that evolves from a viscous liquid to a system of percolating bubbles, which are created via a CO2 generating reaction. The continuous phase polymerizes to a solid during the foaming process generating heat. Foams introduced into a mold increase their volume up to tenfold, and the dynamics of the expansion process may lead to voids and will produce gradients in density and degree of polymerization. These inhomogeneities can lead to structural stability issues upon aging. For instance, structural components in weapon systems have been shown to change shape as they age depending on their molding history, which can threaten critical tolerances. The purpose of this project is to develop a Cradle-to-Grave multiphysics model, which allows us to predict the material properties of foam from its birth through aging in the stockpile, where its dimensional stability is important.

Dispersion and Solution Processes

This chapter explores processes that convert particle dispersions or suspensions, polymer solutions, and liquid monomers into coatings and 3D parts. The chapter begins with a section on the fundamentals that covers colloidal dispersions, polymer solutions, rheology, and drying. Then shape casting, namely slip casting, is discussed with an emphasis on understanding the effect of dispersion variables on the slip casting rate. A section on coating and tape casting processes follows. In this section, several common coating methods are introduced and applications in polymer and ceramic coatings are included. After a brief introduction to injection molding and extrusion processes that are based on dispersions, additive processes that employ curable monomers are discussed.

New composite separator pellet to increase power density and reduce size of thermal batteries.

We show that it is possible to manufacture strong macroporous ceramic films that can be backfilled with electrolyte to form rigid separator pellets suitable for use in thermal batteries. Several new ceramic manufacturing processes are developed to produce sintered magnesium oxide foams with connected porosities of over 80% by volume and with sufficient strength to withstand the battery manufacturing steps. The effects of processing parameters are quantified, and methods to imbibe electrolyte into the ceramic scaffold demonstrated. Preliminary single cell battery testing show that some of our first generation pellets exhibit longer voltage life with comparable resistance at the critical early times to that exhibited by a traditional pressed pellets. Although more development work is needed to optimize the processes to create these rigid separator pellets, the results indicate the potential of such ceramic separator pellets to be equal, if not superior to, current pressed pellets. Furthermore, they could be a replacement for critical material that is no longer available, as well as improving battery separator strength, decreasing production costs, and leading to shorter battery stacks for long-life batteries.