The thermomechanical behavior of polymer nanocomposites is mostly governed by interfacial properties which rely on particle–polymer interactions, particle loading, and dispersion state. We recently showed that poly(methyl methacrylate) (PMMA) adsorbed nanoparticles in poly(ethylene oxide) (PEO) matrices displayed an unusual thermal stiffening response. The molecular origin of this unique stiffening behavior resulted from the enhanced PEO mobility within glassy PMMA chains adsorbed on nanoparticles. In addition, dynamic asymmetry and chemical heterogeneities existing in the interfacial layers around particles were shown to improve the reinforcement of composites as a result of good interchain mixing. Here, the role of chain rigidity in this interfacially controlled reinforcement in PEO composites is investigated. We show that particles adsorbed with less rigid polymers improve the mechanical properties of composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys.
Aggregation and gelation in a tunable aqueous colloid–polymer bridging system
We report a colloid–polymer model system with tunable bridging interactions for microscopic studies of structure and dynamics using confocal imaging. The interactions between trifluoroethyl methacrylate-co-tert-butyl methacrylate copolymer particles and poly(acrylic acid) (PAA) polymers were controllable via polymer concentration and pH. The strength of adsorption of PAA on the particles, driven by pH-dependent interactions with polymer brush stabilizers on the particle surfaces, was tuned via solution pH. Particle–polymer suspensions formulated at low pH, where polymers strongly adsorbed to the particles, contained clusters or weak gels at particle volume fractions of ϕ = 0.15 and ϕ = 0.40. At high pH, where the PAA only weakly adsorbed to the particle surface, particles largely remained dispersed, and the suspensions behaved as a dense fluid. The ability to visualize the suspension structure is likely to provide insight into the role of polymer-driven bridging interactions in the behavior of colloidal suspensions.
more » « less- Award ID(s):
- 1803728
- NSF-PAR ID:
- 10470598
- Publisher / Repository:
- AIP Publishing
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 11
- ISSN:
- 0021-9606
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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ABSTRACT 2019 ,57 , 9–14 -
We report a facile method to prepare polymer-grafted plasmonic metal nanoparticles (NPs) that exhibit pH-responsive surface-enhanced Raman scattering (SERS). The concept is based on the use of pH- responsive polymers, such as poly(acrylic acid) (PAA) and poly(allylamine hydrochloride) (PAH), as multi- dentate ligands to wrap around the surface of NPs instead of forming polymer brushes. Upon changing the solvent quality, the grafted pH-responsive polymers would drive reversible aggregation of NPs, leading to a decreased interparticle distance. This creates numerous hot spots, resulting in a secondary enhancement of SERS as compared to the SERS from discrete NPs. For negatively charged PAA-grafted NPs, the SERS response at pH 2.5 showed a secondary enhancement of up to 104-fold as compared to the response for discrete NPs at pH 12. Similarly, positively charged PAH-grafted AuNPs showed an oppo- site response to pH. We demonstrated that enhanced SERS with thiol-containing and charged molecular probes was indeed from the pH-driven solubility change of polymer ligands. Our method is different from the conventional SERS sensors in the solid state. With pH-responsive polymer-grafted NPs, SERS can be performed in solution with high reproducibility and sensitivity but without the need for sample pre-con- centration. These findings could pave the way for innovative designs of polymer ligands for metal NPs where polymer ligands do not compromise interparticle plasmon coupling.more » « less
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The rheology of suspensions of rings (tori) rotating in an unbounded low Reynolds number simple shear flow is calculated using numerical simulations at dilute particle number densities ( n ≪ 1 ). Suspensions of non-Brownian rings are studied by computing pair interactions that include hydrodynamic interactions modeled using slender body theory and particle collisions modeled using a short-range repulsive force. Particle contact and hydrodynamic interactions were found to have comparable influences on the steady-state Jeffery orbit distribution. The average tilt of the ring away from the flow-vorticity plane increased during pairwise interactions compared to the tilt associated with Jeffery rotation and the steady-state orbit distribution. Particle stresses associated with the increased tilt during the interaction were found to be comparable to the stresses induced directly by particle contact forces and the hydrodynamic velocity disturbances of other particles. The hydrodynamic diffusivity coefficients in the gradient and vorticity directions were also obtained and were found to be two orders of magnitude larger than the corresponding values in fiber suspensions at the same particle concentrations. Rotary Brownian dynamics simulations of isolated Brownian rings were used to understand the shear rate dependence of suspension rheology. The orbit distribution observed in the regime of weak Brownian motion, P e ≫ ϕ T − 3, was surprisingly similar to that obtained from pairwise interaction calculations of non-Brownian rings. Here, the Peclet number P e is the ratio of the shear rate and the rotary diffusivity of the particle and ϕ T is the effective inverse-aspect ratio of the particle (approximately equal to 2 π times the inverse of its non-dimensional Jeffery time period). Thus, the rheology results obtained from pairwise interactions should retain accuracy even for weakly Brownian rings ( n ≪ 1 and ϕ T − 3 ≪ P e ).more » « less
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It is well-known that particle–polymer interactions strongly control the adsorption and conformations of adsorbed chains. Interfacial layers around nanoparticles consisting of adsorbed and free matrix chains have been extensively studied to reveal their rheological contribution to the behavior of nanocomposites. This work focuses on how chemical heterogeneity of the interfacial layers around the particles governs the microscopic mechanical properties of polymer nanocomposites. Low glass-transition temperature composites consisting of poly(vinyl acetate) coated silica nanoparticles in poly(ethylene oxide) and poly(methyl acrylate) matrices, and of poly(methyl methacrylate) silica nanoparticles in a poly(methyl acrylate) matrix are examined using rheology and X-ray photon correlation spectroscopy. We demonstrate that miscibility between the adsorbed and matrix chains in the interfacial layers led to the observed unusual reinforcement. We suggest that packing of chains in the interfacial regions may also contribute to the reinforcement in the polymer nanocomposites. These features may be used in designing mechanically adaptive composites operating at varying temperature.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0101697
