skip to main content

Title: Poisson ratio mismatch drives low-strain reinforcement in elastomeric nanocomposites
Introduction of nanoparticulate additives can dramatically impact elastomer mechanical response, with large enhancements in modulus, toughness, and strength. Despite the societal importance of these effects, their mechanistic origin remains unsettled. Here, using a combination of theory and molecular dynamics simulation, we show that low-strain extensional reinforcement of elastomers is driven by a nanoparticulate-jamming-induced suppression in the composite Poisson ratio. This suppression forces an increase in rubber volume with extensional deformation, effectively converting a portion of the rubber's bulk modulus into an extensional modulus. A theory describing this effect is shown to interrelate the Poisson ratio and modulus across a matrix of simulated elastomeric nanocomposites of varying loading and nanoparticle structure. This model provides a design rule for structured nanoparticulates that maximizes elastomer mechanical response via suppression of the composite Poisson ratio. It also positions elastomeric nanocomposites as having a qualitatively different character than Poisson-ratio-matched plastic nanocomposites, where this mechanism is absent.
Authors:
;
Award ID(s):
1650460
Publication Date:
NSF-PAR ID:
10127595
Journal Name:
Soft Matter
Volume:
15
Issue:
4
Page Range or eLocation-ID:
656 to 670
ISSN:
1744-683X
Sponsoring Org:
National Science Foundation
More Like this
  1. Emulsion templates can produce a wide range of unique microstructures via solidification of the continuous phase. Some of these structures result in unique, fluid-filled composites reminiscent of biological tissue when the templating droplets develop into closed-cell structures. However, the state-of-the-art falls short in replicating the mechanical and functional response of biological structures due to stiff, fragile, and bio-incompatible materials while lacking systematic processing parameters. This article describes the synthesis of high internal phase, closed-cell, polydimethylsiloxane (PDMS) elastomeric foams which simultaneously achieve biocompatibility, mechanical robustness, flexibility, and selective permeability. Water-in-oil high internal phase emulsions (HIPEs) stabilized by silica nano-particles (SNPs) provide the microstructural template, resulting in a >74% by volume aqueous phase (up to 82%). To overcome the prohibitive barrier to HIPE formation when using a mechanically-superior, but highly viscous commercial PDMS kit, we produce HIPE templates via centrifugation of low internal phase emulsions (LIPEs, <30% by volume dispersed phase). This oil phase crosslinks into an aqueous-filled (water + glycerol + NaCl) elastomeric composite. The composite's microstructural dependence on viscosity ratio, mixing speed, emulsifier concentration, and centrifugal force are systematically characterized. The resulting microstructured, fluid-filled elastomer composites exhibit mechanically robust and highly flexible behavior due to the excellent properties of themore »PDMS continuous phase.« less
  2. Abstract

    In this study, we discuss the characterization and quantification of composite microstructures formed by the external field manipulation of high aspect ratio magnetic particles in an elastomeric matrix. In our prior work, we have demonstrated that the simultaneous application of electric and magnetic fields on hard magnetic particles with geometric anisotropy can create a hierarchy of structures at different length scales, which can be used to achieve a wide range of properties. We aim to characterize these hierarchical structures and relate them to final composite properties so we can achieve our ultimate goal of designing a material for a prescribed performance. The complex particle structures are formed during processing by using electric and magnetic fields, and they are then locked-in by curing the polymer matrix around the particles. The model materials used in the study are barium hexaferrite (BHF) particles and polydimethylsiloxane (PDMS) elastomer. BHF was selected for its hard magnetic properties and high geometric anisotropy. PDMS was selected for its good mechanical properties and its tunable curing kinetics. The resulting BHF-PDMS composites are magnetoactive, i.e., they will deform and actuate in response to magnetic fields. In order to investigate the resulting particle orientation, distribution and alignment and tomore »predict the composite’s macro scale properties, we developed techniques to quantify the particle structures.

    The general framework we developed allows us to quantify and directly compare the microstructures created within the composites. To identify structures at the different length scales, images of the composite are taken using both optical microscopy and scanning electron microscopy. We then use ImageJ to analyze them and gather data on particle size, location, and orientation angle. The data is then exported to MATLAB, and is used to run a Minimum Spanning Tree Algorithm to classify the particle structures, and von Mises Distributions to quantify the alignment of said structures.

    Important findings show 1) the ability to control structure using a combination of external electric, magnetic and thermal fields; 2) that electric fields promote long range order while magnetic fields promote short-range order; and 3) the resulting hierarchical structure greatly influence bulk material properties. Manipulating particles in a composite material is technologically important because changes in microstructure can alter the properties of the bulk material. The multifield processing we investigate here can form the basis for next generation additive manufacturing platforms where desired properties are tailored locally through in-situ hierarchical control of particle arrangements.

    « less
  3. Polymer nanocomposites exhibit unique effective properties that do not follow conventional effective media approaches. The nanoparticle-polymer interphase has been shown to strongly influence the nanocomposites behavior due o its significant volume when the particles are nano-sized, affording an opportunity to tune the dielectric response of the resulting nanocomposite. In this study, we investigate the effects of TiO2 nanoparticles on the electrical properties and the charges distribution and transport in polydimethylsiloxane (PDMS) nanocomposites. Impedance spectroscopy shows suppression of interfacial Maxwell-Wagner-Sillars (MWS) polarization accompanied by a reduction in the low frequency dielectric permittivity and loss at high temperatures in the presence of the TiO2 nanoparticles. Thermally stimulated discharge current measurements confirm that the suppression of the interfacial polarization relaxations happens by redistributing or depleting the charges through the composite and hindering their mobility, potentially resulting in lower electrical conduction and higher breakdown strength. Although the model materials investigated here are TiO2 nanoparticles and Sylgard 184 PDMS, our findings can be extended to other nanoparticulate-filled elastomer composites to design lightweight dielectrics, actuators and sensors with improved capabilities.
  4. Polymer nanocomposites have been sought after for their light weight, high performance (strength-to-mass ratio, renewability, etc.), and multi-functionality (actuation, sensing, protection against lightning strikes, etc.). Nano-/micro-engineering has achieved such advanced properties by controlling crystallinity, phases, and interfaces/interphases; hierarchical structuring, often bio-inspired, has been also implemented. While driven by the advanced properties of nanofillers, properties of polymer nanocomposites are critically affected by their structuring and interfaces/interphases due to their small size (< ~50 nm) and large surface area per volume. Measures of their property improvement by nanofiller addition are often smaller than theoretically predicted. Currently, application of these novel engineered materials is limited because these materials cannot often be made in large sizes without compromising nano-scale organization, and because their multi-scale structure-property relationships are not well understood. In this work, we study precise and fast nanofiller structuring with non-contact and energy-efficient application of oscillating magnetic fields. Magnetic assembly is a promising, scalable method to deliver bulk amount of nanocomposites while maintaining organized nanofiller structure throughout the composite volume. In the past, we have demonstrated controlled alignment of nanofillers with tunable inter-assembly distances with application of oscillating one-dimentional magnetic fields (~100s of G), by taking advantage of both magnetic attraction and repulsion.more »The low oscillation frequency (< 1 Hz) was tuned to achieve maghemite nanofiller alignment patterns, in an epoxy matrix, with different amount of inter-nanofiller contacts with the same nanofiller volume fraction (see Figure 1a). This work was recently expanded to three-dimensional assembly using a triaxial Helmholtz coil system (see Figure 1b); the system can apply the triaxial magnetic fields of varying magnitude (max. ±300G, ±250G, ±180G (x-y-z)) and frequency (0 to 1 Hz, ~0.1 Hz resolution) with controlled phase delay to the sample size of 1.5” x 2.5” x 3.5”(x-y-z). Two model systems are currently studied: maghemite nanofillers in an elastomer for magnetoactuation, and nickel-coated CNTs in an thermoset for mehcniacl and transport property reinforcement. The assembled nanofiller structures are currently characterized by microCT; microCT scan data (see Figure 1b) are segmented through a machine learning algorithm, and will be modeled for their transport properties using a Monte Carlo method. These estimated properties will be compared with the experimentally characterized mechanical, transport, and actuation properties, providing the structure-interphase-property relationships. In future, we plan to integrate these nanocomposites to CFRPs for interlaminar property reinforcement, possibly with an out-of-autoclave composite processing.« less
  5. Photo-induced thiol-ene crosslinking of allyl-functionalized cellulose nanocrystal (CNC)/polymer nanocomposites allows access to films that mimic the water-enhanced mechanical gradient characteristics of the squid beak. These films are prepared by mixing the functionalized CNCs and polymer in a solvent before solution casting and drying. The photocrosslinking agents are then imbibed into the film before UV exposure. Reported herein are studies aimed at better understanding the effect of the film preparation procedure, film thickness and the conditions under which the UV treatment is carried out. It was found that when the film is heated at a temperature higher than its glass transition temperature (Tg) during the UV irradiation step there is a greater enhancement in the mechanical properties of the films, presumably on account of more efficient crosslinking between the CNC fillers. Moreover, composite films that were compression molded (at 90°C) before the imbibing step displayed lower mechanical properties compared to the as-cast films, which is attributed to phase separation of the CNC fillers and polymer matrix during this additional processing step. Finally, the film thickness was also found to be a critical factor that affects the degree of crosslinking. For example, thinner films (50 µm) displayed a higher wet modulus ca.more »130 MPa compared to ca. 80 MPa for the thicker films (150 µm). Understanding the processing conditions allows access to a larger range of mechanical properties which is important for the design of new bio-inspired mechanical gradient nanocomposites.« less