Monte Carlo Simulation Modeling of Nanoparticle-Polymer Cosuspensions.

Creation of high-quality and novel polymer-particle nanocomposites to a large extent depends on understanding the behaviors of individual polymer chains and particles, especially at the mixing state in a liquid solvent. Simulations can help identify critical parameters and equations that govern the suspension behaviors. This study is the first attempt to understand the agglomeration processes of ZnO nanoparticle and poly(methyl methacrylate) polymer cosuspensions through a constant number Monte Carlo simulation. A modified Derjaguin-Landau-Verwey-Overbeek theory is used to describe the particle-particle interactions that lead to agglomeration. The average agglomerate size and number are measured as a function of suspension resting time, particle to polymer volume ratio, polymer chain length, and suspension drying. The agglomerate size increases persistently with the resting time and particle content increase, ranging from 1.2 µm for the 1 vol % particle content suspension to 4.6 µm for the 20 vol % particle content suspension after 30 min of suspension resting. The agglomerate size distribution for all of the particle contents follows a lognormal distribution. As the polymer chain length increases, agglomeration also becomes more severe. If drying is accounted for and thus the solids loading continually increases, the suspension becomes much more stable because of increases in viscosity and depletion stabilization.

Suspension-based imprint lithography of ZnO-PMMA hybrids.

Imprint lithography has been explored as a method to transfer arrays of patterned features onto pure polymers and polymer/metallic nanoparticle composites. Despite the success of this method for those materials, it has never been achieved on the sub-micron scale with polymer-oxide particle hybrids. This study patterns ZnO-PMMA (poly(methyl methacrylate)) hybrids via imprint lithography from co-suspensions of PMMA and ZnO nanoparticles in anisole from 1 vol% to 20 vol% ZnO solids loading. ZnO nanoparticles are functionalized with nonanoic acid to disperse the nanoparticles in anisole with dissolved PMMA. The feature fidelity of the patterned arrays decreases with increasing ZnO content, indicating an increase in particle agglomeration as the ZnO particle content increases. Feature size, ZnO content, and ZnO nanoparticle agglomeration are critical factors influencing the photoluminescence (PL) intensity. The ZnO solids loading at a 500 nm feature size needs to be 10 vol% or higher for the enhanced PL response. When the ridge size increases to 1 µm, ZnO solids loading as low as 1 vol% is feasible. This method of lithographic patterning of nanoparticle-polymer suspensions can be applied to a wide variety of hybrid devices and has the potential to open many applications including optical devices and biomedical screening.

Experimental and Modeling Study of Solvent Diffusion in PDMS for Nanoparticle-Polymer Cosuspension Imprint Lithography.

This study is the first that focuses on solvent migration in a polydimethylsiloxane (PDMS) stamp during the imprint lithography of ZnO-poly(methyl methacrylate) (PMMA) hybrid suspensions. Using suspensions with varying solids loading levels and ZnO/PMMA ratios, the uptake of the anisole solvent in the stamp is evaluated as a function of time. Laser confocal microscopy is employed as a unique technique to measure the penetration depth of the solvent into the stamp. The suspension solids loading affects the anisole saturation depth in the PDMS stamp. For the suspensions with low solids loading, the experimental data agree with the model for non-Fickian diffusion through a rubbery-elastic polymer. For the suspensions with high solids loading, the data agree more with a sigmoidal diffusion curve, reflecting the rubbery-viscous behavior of a swelling polymer. This difference is due to the degree of swelling in the PDMS. Higher solids loadings induce more swelling because the rate of anisole diffusing into the stamp is increased, likely due to the less dense buildup of the solids as the suspension dries.

One-pot, bioinspired coatings to reduce the flammability of flexible polyurethane foams.

In this manuscript, natural materials were combined into a single "pot" to produce flexible, highly fire resistant, and bioinspired coatings on flexible polyurethane foam (PUF). In one step, PUF was coated with a fire protective layer constructed of a polysaccharide binder (starch or agar), a boron fire retardant (boric acid or derivative), and a dirt char former (montmorillonite clay). Nearly all coatings produced a 63% reduction in a critical flammability value, the peak heat release rate (PHRR). One formulation produced a 75% reduction in PHRR. This technology was validated in full-scale furniture fire tests, where a 75% reduction in PHRR was measured. At these PHRR values, this technology could reduce the fire threat of furniture from significant fire damage in and beyond the room of fire origin to being contained to the burning furniture. This flammability reduction was caused by three mechanisms-the gas-phase and condensed-phase processes of the boron fire retardant and the condensed-phase process of the clay. We describe the one-pot coating process and the impact of the coating composition on flammability.