Particle localization and hyperuniformity of polymer‐grafted nanoparticle materials

Chremos, Alexandros; Douglas, Jack F.

doi:10.1002/andp.201600342

Cited by 50 publications

(53 citation statements)

References 77 publications

(100 reference statements)

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“…We suggest that the transition between the power law scalings observed by Antonetti et al 12 for all different polymer architectures can be rationalized as the emergent dynamical heterogeneity that is characteristic of strongly interacting soft particle systems. 60 …”

Section: Resultsmentioning

confidence: 99%

Influence of polymer architectures on diffusion in unentangled polymer melts

2017

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Recent simulations have indicated that the thermodynamic properties and the glassy dynamics of polymer melts are strongly influenced by average molecular shape, as quantified by the radius of gyration tensor of the polymer molecules, and that average molecular shape can be tuned by varying molecular topology (e.g., ring, star, linear chain, etc.). In the present work, we investigate if molecular shape is similarly a predominant factor in understanding the polymer center of mass diffusion D in the melt, as already established for polymer solutions. We find that all our D data for unentangled polymer melts having a range of topologies can be reasonably described as a power law of the polymer hydrodynamic radius Rh. In particular, this scaling is similar to the scaling of D for a tracer sphere having a radius on the order of the chain radius of gyration, Rg. We conclude that chain topology influences molecular dynamics in as much as the polymer topology influences average molecular shape. Experimental evidence seems to suggest that this situation is also true for entangled polymer melts.

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Section: Resultsmentioning

confidence: 99%

Influence of polymer architectures on diffusion in unentangled polymer melts

2017

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“…102–104 Similar trends have been observed in polymer-grafted nanoparticles having a moderate grafting density where this effect is especially large. 40 The dynamics of both polyelectrolyte stars having inter-mediate number of arms and moderately polymer-grafted nanoparticles show sharp slowing down with increasing concentration that is symptomatic of incipient solidification. Sciortino and coworkers 105 have recently shown that nanoparticles with a moderate number of grafted DNA chains can form an equilibrium amorphous state in which the crystalline state is metastable.…”

Section: Discussionmentioning

confidence: 99%

“…Stars having a moderate value of f can naturally be expected to behave as “soft” particles exhibiting significant fluctuations in size and shape as in case of flexible polymers. Simulation studies of other soft particle systems such as polymer-grafted nanoparticles 38–40 have indicated a tendency to form equilibrium disordered solids rather than crystalline materials because of the fluctuating effect of the conformational disorder packing having low compressibility as in the case of crystals. We may then expect polyelectrolytes stars having an intermediate number of arms to form soft amorphous solid.…”

Section: Introductionmentioning

confidence: 99%

Solution properties of star polyelectrolytes having a moderate number of arms

Chremos

Douglas

2017

The Journal of Chemical Physics

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We investigate polyelectrolyte stars having a moderate number of arms by molecular dynamics simulations of a coarse-grained model over a range of polyelectrolyte concentrations, where both the counter-ions and solvent are treated explicitly. This class of polymeric materials is found to exhibit rather distinct static and dynamic properties from linear and highly branched star polyelectrolyte solutions emphasized in past studies. Moderately branched polymers are particle-like in many of their properties, while at the same time they exhibit large fluctuations in size and shape as in the case of linear chain polymers. Correspondingly, these fluctuations suppress crystallization at high polymer concentrations, leading apparently to an amorphous rather than crystalline solid state at high polyelectrolyte concentrations. We quantify the onset of this transition by measuring the polymer size and shape fluctuations of our model star polyelectrolytes and the static and dynamic structure factor of these solutions over a wide range of polyelectrolyte concentration. Our findings for star polyelectrolytes are similar to those of polymer-grafted nanoparticles having a moderate grafting density, which is natural given the soft and highly deformable nature of both of these ‘particles’.

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“…The hyperuniformity concept has brought new attention to the importance of quantifying the large-scale structural correlations in amorphous systems, regardless of whether they are hyperuniform. This has been borne out in recent studies concerning molecular jamming processes that underlie glass-formation in polymeric materials [76,79], and quantifying the large-scale structure of amorphous ices and transitions between their different forms [80]. Understanding structural and physical properties of a system as it approaches a hyperuniform state or whether near hyperuniformity is signaling crucial large-scale structural changes in a system will be shown to be fundamentally important and is expected to lead to new insights about condensed phases of matter.…”

Section: Disordered Hyperuniform Systems Are Distinguishable States Omentioning

confidence: 99%

Hyperuniform states of matter

2018

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Hyperuniform states of matter are correlated systems that are characterized by an anomalous suppression of longwavelength (i.e., large-length-scale) density fluctuations compared to those found in garden-variety disordered systems, such as ordinary fluids and amorphous solids. All perfect crystals, perfect quasicrystals and special disordered systems are hyperuniform. Thus, the hyperuniformity concept enables a unified framework to classify and structurally characterize crystals, quasicrystals and the exotic disordered varieties. While disordered hyperuniform systems were largely unknown in the scientific community over a decade ago, now there is a realization that such systems arise in a host of contexts across the physical, materials, chemical, mathematical, engineering, and biological sciences, including disordered ground states, glass formation, jamming, Coulomb systems, spin systems, photonic and electronic band structure, localization of waves and excitations, self-organization, fluid dynamics, number theory, stochastic point processes, integral and stochastic geometry, the immune system, and photoreceptor cells. Such unusual amorphous states can be obtained via equilibrium or nonequilibrium routes, and come in both quantum-mechanical and classical varieties. The connections of hyperuniform states of matter to many different areas of fundamental science appear to be profound and yet our theoretical understanding of these unusual systems is only in its infancy. The purpose of this review article is to introduce the reader to the theoretical foundations of hyperuniform ordered and disordered systems. Special focus will be placed on fundamental and practical aspects of the disordered kinds, including our current state of knowledge of these exotic amorphous systems as well as their formation and novel physical properties.

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Particle localization and hyperuniformity of polymer‐grafted nanoparticle materials

Cited by 50 publications

References 77 publications

Influence of polymer architectures on diffusion in unentangled polymer melts

Influence of polymer architectures on diffusion in unentangled polymer melts

Solution properties of star polyelectrolytes having a moderate number of arms

Hyperuniform states of matter

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