Quantification of nanoparticle interactions in pure solvents and a concentrated PDMS solution as a function of...

Using turbidity measurements, we quantified the interactions between PDMS-grafted silica nanoparticles (PDMS-g-silica) in pure solvents and a concentrated polymer solution with a focus on detecting the impact of solvent quality on graft layer stretching. This work is an extension of our previous work where we showed that interfacial wetting of the grafted polymer leads to depletion restabilization in semidilute and concentrated polymer solutions in good solvents (Dutta, N.; Green, D. Langmuir 2008, 24, 5260-5269). Subsequently, we showed that the criterion for depletion restabilization holds for both good and marginally poor solvents (Dutta, N.; Green, D. Langmuir 2010, 26, 16737-16744). In this work, we quantified nanoparticle interactions in terms of the second virial coefficient (B2), which captures the stretching of the brush in a good solvent in comparison to compression in a poor solvent. The transition from stretching to compression of the graft layer as a function of solvent quality was also supported by self-consistent mean-field (SCF) calculations. The PDMS-g-silica nanoparticles in a concentrated polymer solution in a good solvent within the complete wetting region behaved as though they were in a good solvent rather than in a polymer melt where on the basis of the SCF calculations the graft layers were expected to behave ideally. Overall, our results indicate that turbidity measurements can be used to determine the second virial coefficients for polymer-grafted nanoparticles in solvents and concentrated polymer solutions, and the relative values of the coefficients correspond well to those from theoretical calculations.