. Here we show that model elastomeric artifi cial skins wrinkle in a hierarchical pattern consisting of self-similar buckles extending over fi ve orders of magnitude in length scale, ranging from a few nanometres to a few millimetres. We provide a mechanism for the formation of this hierarchical wrinkling pattern, and quantify our experimental fi ndings with both computations and a simple scaling theory. Th is allows us to harness the substrates for applications. In particular, we show how to use the multigeneration-wrinkled substrate for separating particles based on their size, while simultaneously forming linear chains of monodisperse particles.Wrinkling, buckling and other mechanical instabilities have been typically treated as a nuisance to be avoided rather than an exquisite pattern to be exploited. Although this view is changing with the growing understanding of how ubiquitous these phenomena are 9 , the utilization of wrinkling in applications has been hampered by the absence of a detailed understanding of the phenomena, as well as the ability to control it experimentally. Here we focus on the tunable hierarchical wrinkling of model stiff elastomeric artifi cial skins supported on a soft base. These wrinkles are fabricated by uniaxially stretching poly(dimethyl siloxane) (PDMS) network sheets (thickness ∼0.5 mm, Young modulus ∼1 MPa) 10 in a custom-designed stretching apparatus 11 and exposing them to ultraviolet/ozone (UVO) radiation for extended periods of time (30-60 minutes). Previous studies established that the UVO treatment of PDMS converts the fi rst ∼5 nm of the PDMS surface into a stiff 'skin' 12 , whose density is approximately a half of that of silica 13 . Optical microscopy and scanning force microscopy (SFM) experiments confi rm that the surfaces are originally fl at in the presence of strain.After the UVO treatment, the strain is removed from the specimen and, the skin buckles perpendicularly to the direction of the strain. The buckle morphology depends on the strain removal rate. Specifically, stretched and UVO-modified specimens released at a fast rate (strain removed abruptly)

The viscoelastic glass-to-rubber softening transition is analyzed for various cross-linked polymers reinforced with filler particles. We find that the loss modulus peak corresponding to the segmental relaxation process (glass transition) is not significantly affected by the particle surface area in carbon black-filled polybutadiene or by silane chemical coupling of poly(styrene-co-butadiene) to silica. Large differences in shape and magnitude of the peak in the loss tangent (tan δ) vs temperature are noted for these materials; however, this is due to variations in the storage modulus at small strains in the rubbery state, which is influenced by the nature of the jammed filler network. The use of a simple relaxation model demonstrates this feature of the viscoelastic glass transition in filled rubber. It is not necessary to invoke concepts involving a mobility-restricted polymer layer near the filler surfaces to explain the viscoelastic results. Atomic force microscopy conducted with an ultrasharp tungsten tip indicates that there may be some stiffening of the elastomer in the proximity of filler particles, but this does not translate into an appreciable effect on the segmental dynamics in these materials. IntroductionDespite significant research activity on the effect of nanoscale confinement on the glass transition temperature (T g ) of polymers, many controversial issues remain unresolved, as recently reviewed by Alcoutlabi and McKenna.1 Of particular relevance to the field of elastomers is the influence of reinforcing particles on the polymer T g . It is reasonable to expect that physical adsorption or chemical attachment of polymer chains to rigid particles can slow down the polymer dynamics, which might increase the glass transition of the polymer chains near particle surfaces. However, while some published studies show increases in T g upon the addition of carbon black, silica, or other fillers, others report no change in T g or even T g decreases.2-26 The nature of the interfacial interactions between the polymer and particles may account for some of the disparate results concerning the effect of fillers on T g .

Tsagaropoulos and Eisenberg [Macromolecules 1995, 28, 396; Macromolecules 1995, 28, 6067] reported a second loss tangent (tan δ) peak in temperature-dependent viscoelastic data for various un-cross-linked polymers filled with nanometer-sized silica particles. This peak, occurring at temperatures as much as 100 °C above the primary tan δ peak (glass-to-rubber softening transition), was ascribed to the glass transition of immobilized chains near the particles. This research is often cited as support for the existence of severely retarded segmental motion of polymer near the surfaces of small particles (glassy polymer shell). We offer a different interpretation of the results from Tsagaropoulos and Eisenberg, reinforced by our recent measurements on particle-filled polybutadiene and consideration of other literature data. Particles restrict the flow of some polymer chains, thus resulting in incomplete terminal relaxation, and partial cross-linking of unfilled polymers produces the same higher temperature tan δ peak. Polymer chains which are adsorbed onto filler surfaces are immobilized from a flow relaxation (chain diffusion/reptation) standpoint, but segmental relaxation (glass transition) is not substantially altered by small particles as a general rule.

We extended the self-assembly concepts of macromolecules in solutions to create a variety of unique nanosized polymeric core-shell nanoparticles by means which allow scale-up for industrial production. This paper describes the synthesis methods and the mechanisms governing the design of structural features required for a beneficial use as performance-enhancing additives in rubber vulcanizates as well as the performance of such rubber compositions. The nanoparticles were prepared by the polymerization of block copolymers and their self-assembly in solvents into micelles followed by a subsequent stabilization of their structure by core crosslinking. Depending on the type and macrostructure of the block copolymers, the solvent, the concentration, and other process parameters, a variety of core-shell nanoparticles of different shapes (spheres, hollow spheres, ellipsoids, linear and branched strings, etc.) and sizes have been reproducibly synthesized. Most of the nanoparticles were composed of a solid, highly cross-linked core and an elastomeric shell structure. The evolution and structure of the nanoparticles during the different process steps involved were examined and characterized. The unique performance of spherical nanoparticles as performance-enhancing additives and novel reinforcing agents was explored in rubber compounds. It was also shown that the basic spherical or string type nanoparticles can be used as templates for the design of composite structures comprising the basic polymeric nanoparticles and smaller organic, inorganic, or metallic substructures embedded in and attached to the elastomeric shell molecules.

The understanding of size-dependent properties is key to the implementation of nanotechnology. One controversial and unresolved topic is the influence of characteristic size on the glass transition temperature (T(g)) for ultrathin films and other nanoscale geometries. We show that T(g) does depend on size for polystyrene spherical domains with diameters from 20 to 70 nm which are formed from phase separation of diblock copolymers containing a poly(styrene-co-butadiene) soft block and a polystyrene hard block. A comparison of our data with published results on other block copolymer systems indicates that the size dependence of T(g) is a consequence of diffuse interfaces and does not reflect an intrinsic size effect. This is supported by our measurements on 27 nm polystyrene domains in a styrene-isobutylene-styrene triblock copolymer which indicate only a small T(g) depression (3 K) compared to bulk behavior. We expect no effect of size on T(g) in the limit as the solubility parameters of the hard and soft blocks diverge from each other. This strongly segregated limiting behavior agrees with published data for dry and aqueous suspensions of small polystyrene spheres but is in sharp contrast to the strong influence of film thickness on T(g) noted in the literature for free standing ultrathin polystyrene films.

The introduction of silanes to improve processability and properties of silica-reinforced rubber compounds is critical to the successful commercial use of silica as a filler in tires and other applications. The use of silanes to promote polymer-filler interactions is expected to limit the development of a percolated filler network and may also affect the mobility of polymer chains near the particles. Styrene-butadiene rubber (SBR) was reinforced with silica particles at a filler volume fraction of 0.19, and various levels of filler-filler shielding agent (n-octyltriethoxysilane) and polymerfiller coupling agent (3-mercaptopropyltrimethoxysilane) were incorporated. Both types of silane inhibited the filler flocculation process during annealing the uncured rubber materials, thus reducing the magnitude of the Payne effect. In contrast to the significant reinforcement effects noted in the strain-dependent shear modulus, the bulk modulus from hydrostatic compression was largely unaltered by the silanes. Addition of polymer-filler linkages using the coupling agent yielded bound rubber values up to 71%; however, this bound rubber exhibited glass transition behavior which was similar to the bulk SBR response, as determined by calorimetry and viscoelastic testing. Modifying the polymer-filler interface had a strong effect on the nature of the filler network, but it had very little influence on the segmental dynamics of polymer chains proximate to filler particles.

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