Tunable Plasmonic Microcapsules with Embedded Noble Metal Nanoparticles for Optical Microsensing

We report a comprehensive investigation of the synthetic conditions leading to the formation of tunable plasmonic microcapsules (MCs) made of a hydrophobic liquid core encapsulated into a hard silica shell embedding plasmonic metallic nanoparticles (NPs). The distinctive and remarkable features of the prepared MCs are the inert nanometer-thin silica shell and the small plasmonic NPs embedded in it, which confer interesting optical absorbance properties. We tie the mechanical robustness of the MCs to the thickness of their silica shell. We show that several oils can be used for the synthesis of MCs and we evidence how the relative solubility of the silica precursor and the polarity of the oil phase influence the final MC characteristics. We also evidence the synthesis of “monoflavor” or “multiflavor” MCs with, respectively, a single type of NPs or a mixture of metallic NPs, respectively, embedded in the silica shell. Using experiments and simulations, we demonstrate that the optical response of the MCs can be finely tuned by choosing the right ratio between Ag and Au NPs initially suspended in the solution. Our heterogeneous hybrid MCs exhibit optical properties directly resulting from the choice of NP composition and shell thickness, making them of great interest not only for mechanical and chemical microsensing but also for applications in photothermal therapy, surface-enhanced Raman spectroscopy studies, microreactor vesicles for interfacial electrocatalysis, antimicrobial activity, and drug delivery. Our simple and versatile emulsion template method holds great promise for the tailored design of a generation of multifunctional MCs consisting of modular nanoscale building blocks

Temperature- and thickness-dependent elastic moduli of polymer thin films

The mechanical properties of polymer ultrathin films are usually different from those of their counterparts in bulk. Understanding the effect of thickness on the mechanical properties of these films is crucial for their applications. However, it is a great challenge to measure their elastic modulus experimentally with in situ heating. In this study, a thermodynamic model for temperature- (T) and thickness (h)-dependent elastic moduli of polymer thin films Ef(T,h) is developed with verification by the reported experimental data on polystyrene (PS) thin films. For the PS thin films on a passivated substrate, Ef(T,h) decreases with the decreasing film thickness, when h is less than 60 nm at ambient temperature. However, the onset thickness (h*), at which thickness Ef(T,h) deviates from the bulk value, can be modulated by T. h* becomes larger at higher T because of the depression of the quenching depth, which determines the thickness of the surface layer δ

Structure-property relationships from universal signatures of plasticity in disordered solids

When deformed beyond their elastic limits, crystalline solids flow plastically via particle rearrangements localized around structural defects. Disordered solids also flow, but without obvious structural defects. We link structure to plasticity in disordered solids via a microscopic structural quantity, “softness,” designed by machine learning to be maximally predictive of rearrangements. Experimental results and computations enabled us to measure the spatial correlations and strain response of softness, as well as two measures of plasticity: the size of rearrangements and the yield strain. All four quantities maintained remarkable commonality in their values for disordered packings of objects ranging from atoms to grains, spanning seven orders of magnitude in diameter and 13 orders of magnitude in elastic modulus. These commonalities link the spatial correlations and strain response of softness to rearrangement size and yield strain, respectively

C60: the first one-component gel?

Until now, gels have been formed of multicomponent soft matter systems, consisting of a solvent and one or more macromolecular or colloidal species. Here we show that, for sufficient quench rates, the Girifalco model of C60 can form gels which we identify by their slow dynamics and long-lived network structure. These gels are stable at room temperature, at least on the simulation timescale up to 100 ns. At moderate temperatures around 1000 K, below the bulk glass transition temperature, C60 exhibits crystallisation and phase separation proceeds without the dynamical arrest associated with gelation, in contrast to many colloidal systems.Comment: Accepted by J. Phys. Chem. C. special issue 'Clusters in complex fluids

Mechanical Properties of Glassy Polyethylene Nanofibers via Molecular Dynamics Simulations

The extent to which the intrinsic mechanical properties of polymer fibers depend on physical size has been a matter of dispute that is relevant to most nanofiber applications. Here, we report the elastic and plastic properties determined from molecular dynamics simulations of amorphous, glassy polymer nanofibers with diameter ranging from 3.7 to 17.7 nm. We find that, for a given temperature, the Young’s elastic modulus E decreases with fiber radius and can be as much as 52% lower than that of the corresponding bulk material. Poisson’s ratio ν of the polymer comprising these nanofibers was found to decrease from a value of 0.3 to 0.1 with decreasing fiber radius. Our findings also indicate that a small but finite stress exists on the simulated nanofibers prior to elongation, attributable to surface tension. When strained uniaxially up to a tensile strain of ε = 0.2 over the range of strain rates and temperatures considered, the nanofibers exhibit a yield stress σy between 40 and 72 MPa, which is not strongly dependent on fiber radius; this yield stress is approximately half that of the same polyethylene simulated in the amorphous bulk.DuPont MIT AllianceDuPont (Firm) (Young Professor Award

Qualitative discrepancy between different measures of dynamics in thin polymer films

We have used ellipsometry to measure the initial stages of interface healing in bilayer polystyrene films. We also used ellipsometry to measure the glass transition temperature Tg of the same or identically prepared samples. The results indicate that as the film thickness is decreased, the time constant for the interface healing process increases, while at the same time the measured glass transition temperature in the same samples decreases as the film thickness is decreased. This qualitative difference in the behavior indicates that it is not always possible to make inferences about one probe of polymer dynamics from measurements of another. We propose a reason for this discrepancy based on a previously discussed origin for reduction in the Tg value of thin films

Reply to comment on “The properties of free polymer surfaces and their effect upon the glass transition temperature of thin polystyrene films" by S.A. Hutcheson and G.B. McKenna

In this reply we address the comment by Hutcheson and McKenna regarding our recent manuscript [EPJE 15, 473 (2004)] which studies the embedding of gold (Au) nanoparticles into Polystyrene (PS) surfaces. In particular, we clarify comments concerning the force used to model the embedding process. We also repeat our simulations using correct values for the creep compliance J(t). We show that these new simulations more accurately describe the data presented in our original paper and reinforce our main conclusions regarding the nature of the properties of free polymer surfaces. Finally, we address their inability to reproduce our simulation results by showing that the use of their force [Phys. Rev. Lett. 94, 076103 (2005)] in our embedding simulations enables us to mimic their own simulation results