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Creators/Authors contains: "Gramlich, William"

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  1. Abstract Micro-scale inorganic particles (d > 1 µm) have reduced surface area and higher density, making them negatively buoyant in most dip-coating mixtures. Their controlled delivery in hard-to-reach places through entrainment is possible but challenging due to the density mismatch between them and the liquid matrix called liquid carrier system (LCS). In this work, the particle transfer mechanism from the complex density mismatching mixture was investigated. The LCS solution was prepared and optimized using a polymer binder and an evaporating solvent. The inorganic particles were dispersed in the LCS by stirring at the just suspending speed to maintain the pseudo suspension characteristics for the heterogeneous mixture. The effect of solid loading and the binder volume fraction on solid transfer has been reported at room temperature. Two coating regimes are observed (i) heterogeneous coating where particle clusters are formed at a low capillary number and (ii) effective viscous regime, where full coverage can be observed on the substrate. ‘Zero’ particle entrainment was not observed even at a low capillary number of the mixture, which can be attributed to the presence of the binder and hydrodynamic flow of the particles due to the stirring of the mixture. The critical film thickness for particle entrainment is$${h}^{*}=0.16a$$ h = 0.16 a for 6.5% binder and$${h}^{*}=0.26a$$ h = 0.26 a for 10.5% binder, which are smaller than previously reported in literature. Furthermore, the transferred particle matrices closely follow the analytical expression (modified LLD) of density matching suspension which demonstrate that the density mismatch effect can be neutralized with the stirring energy. The findings of this research will help to understand this high-volume solid transfer technique and develop novel manufacturing processes. 
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  2. Abstract Cationic bottlebrush homopolymers are polymerized using a grafting‐through approach by ring‐opening metathesis polymerization (ROMP) to afford well‐defined polymers. Quaternary ammonium macromonomers (MMs) are prepared by quaternizing tertiary amine MMs synthesized by reversible addition‐fragmentation chain transfer (RAFT) polymerization. The quaternary ammonium MMs undergo ROMP to target molecular weights (Mn= 30 000–100 000 g mol−1) and a low dispersity (Đ= 1.10–1.30). Halide‐ligand exchange between the third generation Grubbs catalyst (G3) and halide counter ions (bromide and iodide ions) of MMs changes the catalyst activity throughout ROMP, causing it to deviate from pseudo‐first order kinetic behavior; however, the polymerization still follows controlled behavior without significant catalyst termination. Increasing steric bulk of the MMs decreases the polymerization rate as well. Amphiphilic block copolymers are synthesized by sequential polymerization of quaternary ammonium MMs and polystyrene (PS) MMs. Using a PS macroinitiator affords block copolymers with lowerĐvalues as compared to the less active cationic macroinitiator. 
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