Entropy-driven segregation of nanoparticles to cracks in multilayered composite polymer structures

Gupta, Suresh; Zhang, Qingling; Emrick, Todd; Balazs, Anna C.; Russell, Thomas P.

doi:10.1038/nmat1582

Cited by 341 publications

(274 citation statements)

References 18 publications

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“…S2) revealed AuNPs aggregates indicating a similar dispersion of the s-AZONPs and OPE-NPs in the blend (see Table 1 for the aggregates diameter). In a dry film, no morphological modification is expected to take place during the photoisomerization because of the lowest probability of percolation of 1 nm AuNP in a solid (26,27).…”

Section: Figurementioning

confidence: 99%

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Raimondo

Crivillers

Reinders

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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Interface tailoring represents a route for integrating complex functions in systems and materials. Although it is ubiquitous in biological systems-e.g., in membranes-synthetic attempts have not yet reached the same level of sophistication. Here, we report on the fabrication of an organic field-effect transistor featuring dualgate response. Alongside the electric control through the gate electrode, we incorporated photoresponsive nanostructures in the polymeric semiconductor via blending, thereby providing optical switching ability to the device. In particular, we mixed poly(3-hexylthiophene) with gold nanoparticles (AuNP) coated with a chemisorbed azobenzene-based self-assembled monolayer, acting as traps for the charges in the device. The light-induced isomerization between the trans and cis states of the azobenzene molecules coating the AuNP induces a variation of the tunneling barrier, which controls the efficiency of the charge trapping/detrapping process within the semiconducting film. Our approach offers unique solutions to digital commuting between optical and electric signals.O rganic field-effect transistors (OFETs) are basic building blocks for logic applications and for the development of electronic technologies based on soft matter (1-4). Currently, the greatest challenges in the field are the achievement of higher device performance and the development of devices featuring uncommon and multiple functionalities (5). In this regard, hybrid organic-inorganic materials are gaining much attention because, besides their easy processing, they can take advantage of the tunability of the chemical properties of the components, and thus of the material as a whole. Nanoparticles (NPs) of different materials (gold, silver, metal oxides, etc.) can be coated with selfassembled monolayers (SAMs) of a given molecular system, thereby providing them additional functions such as a specific surface energy or optoelectronic properties (6-8). These features can be optimized by achieving control over the packing of SAMs on the NPs (7). When NPs are integrated in a device, they can, for example, act as charge storage sites-i.e., trapping charges centers, allowing the system to act as a memory (9, 10).The incorporation of photochromic molecules into electronic devices to confer them a photoresponsive nature has been recently explored (11)(12)(13)(14). Among photochromic systems (15-18), azobenzene derivatives are known to undergo isomerization from trans to cis form, and vice versa, under illumination at a specific wavelength, as well as from cis to trans with temperature (15). In the last few years, we have extensively investigated the thiol-substituted azo-biphenyl (AZO, Fig. 1A) when chemisorbed on gold surfaces (19)(20)(21)(22). We demonstrated that such a SAM chemisorbed on the planar source and drain electrodes of an OFET can be used to modulate optically the charge injection at the metal-semiconductor interface because of the different tunneling barrier of the cis and trans SAMs (19). However, the observed light-modul...

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Section: Figurementioning

confidence: 99%

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Raimondo

Crivillers

Reinders

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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“…2D, tQD aggregates were more porous than the NR aggregates, due to their branched geometry inhibiting close packing (25,26) Multiple physical factors including nanoparticle−nanoparticle interactions, polymer−nanoparticle interactions, and variations in electric field in the electrospinning process play critical roles in determining the dispersion of nanoparticles in polymer nanocomposites (18,27).…”

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confidence: 99%

Influence of three-dimensional nanoparticle branching on the Young’s modulus of nanocomposites: Effect of interface orientation

Raja

Olson²,

Limaye³

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

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With the availability of nanoparticles with controlled size and shape, there has been renewed interest in the mechanical properties of polymer/nanoparticle blends. Despite the large number of theoretical studies, the effect of branching for nanofillers tens of nanometers in size on the elastic stiffness of these composite materials has received limited attention. Here, we examine the Young's modulus of nanocomposites based on a common block copolymer (BCP) blended with linear nanorods and nanoscale tetrapod Quantum Dots (tQDs), in electrospun fibers and thin films. We use a phenomenological lattice spring model (LSM) as a guide in understanding the changes in the Young's modulus of such composites as a function of filler shape. Reasonable agreement is achieved between the LSM and the experimental results for both nanoparticle shapes-with only a few key physical assumptions in both films and fibers-providing insight into the design of new nanocomposites and assisting in the development of a qualitative mechanistic understanding of their properties. The tQDs impart the greatest improvements, enhancing the Young's modulus by a factor of 2.5 at 20 wt.%. This is 1.5 times higher than identical composites containing nanorods. An unexpected finding from the simulations is that both the orientation of the nanoscale filler and the orientation of X-type covalent bonds at the nanoparticle-ligand interface are important for optimizing the mechanical properties of the nanocomposites. The tQD provides an orientational optimization of the interfacial and filler bonds arising from its three-dimensional branched shape unseen before in nanocomposites with inorganic nanofillers.three-dimensional nanoparticle branching | polymer fibers | nanocomposite films | lattice spring model | tetrapod quantum dot P olymer−nanoparticle composites have become a highly active topic of research with rapidly expanding applications (1), in part because of their high polymer−particle interfacial area and the unique shape-and size-dependent, tunable properties of nanoparticle reinforcements. For example, new polymer nanocomposites have been developed that can optically sense stress concentration (2), are responsive to magnetic, electrical, and thermal actuation (3, 4), and exhibit large changes in elastic modulus and glass transition temperature at low nanoparticle concentrations (5).While theoretical studies show that the Young's modulus of such polymer nanocomposites depends on nanoparticle shape (6), experimental studies are limited. Experimental studies on polymers (7) include the synergistic reinforcement effects of multiple nanocarbons (8) and the shape-dependent reinforcement effects of micrometer-sized tetrapods (9), microscale ceramic needles (10), carbon nanotubes (11), clay-based nanocomposites (12, 13), and others (14). Computational studies include the effects of nanoparticle packing and size on the nanocomposite Young's modulus (15-17). However, the effects of increasing nanoparticle branching on the mechanical behavior of nanocomposite...

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“…[240][241][242][243][244][245][246][247][248] Additionally, the burgeoning field of computational modelling of the different healing mechanisms is continually providing insights into ideal polymer and composite design parameters for, among other things, improved scalability and healing capabilities. [249][250][251][252][253][254][255][256][257][258][259][260][261][262][263][264][265][266][267] While future endeavours will undoubtedly improve current healing mechanisms towards efficient, fully autonomic and biomimetic healing materials, as well as yield other approaches to imparting autonomic repair, future research thrusts need to concentrate on issues related to employing self-healing materials in industrial applications. Several companies are beginning to lead the efforts to market and produce self-healing polymers (such as the company Autonomic Materials, which is developing microcapsule based self-healing elastomers, thermosets and powder coatings, 268 and Arkema Inc., which is currently producing polymers that heal via supramolecular assembly 269 ), but several issues that are rarely discussed in the literature, such as economic feasibility and long term 'healability' of the different healing mechanisms, need to be addressed before selfhealing materials can begin to replace current polymers and composites.…”

Section: Discussionmentioning

confidence: 99%

Self-healing polymers and composites

Mauldin¹,

Kessler²

2010

International Materials Reviews

235

136

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Inspired by the unique and efficient wound healing processes in biological systems, several approaches to develop synthetic polymers that can repair themselves with complete, or nearly complete, autonomy have recently been developed. This review aims to survey the rapidly expanding field of self-healing polymers by reviewing the major successful autonomic repairing mechanisms developed over the last decade. Additionally, we discuss several issues related to transferring these self-healing technologies from the laboratory to real applications, such as virgin polymer property changes as a result of the added healing functionality, healing in thin films v. bulk polymers, and healing in the presence of structural reinforcements.

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Entropy-driven segregation of nanoparticles to cracks in multilayered composite polymer structures

Cited by 341 publications

References 18 publications

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Optically switchable organic field-effect transistors based on photoresponsive gold nanoparticles blended with poly(3-hexylthiophene)

Influence of three-dimensional nanoparticle branching on the Young’s modulus of nanocomposites: Effect of interface orientation

Self-healing polymers and composites

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