Andrew B. Croll

Looking Beyond Fibrillar Features to Scale Gecko‐Like Adhesion

Hand-sized gecko-inspired adhesives with reversible force capacities as high as 2950 N (29.5 N cm(-2) ) are designed without the use of fibrillar features through a simple scaling theory. The scaling theory describes both natural and synthetic gecko-inspired adhesives, over 14 orders of magnitude in adhesive force capacity, from nanoscopic to macroscopic length scales.

Wrinkling and strain localizations in polymer thin films

Wrinkles and strain localized features are observed in many natural systems and are useful surface patterns for a wide range of applications, including optical gratings and microfluidic devices. However, the transition from sinusoidal wrinkles to more complex strain localized features, such as delaminations or folds, is not well understood. In this paper, we investigate the onset of wrinkling and strain localizations in a model system of a glassy polymer film attached to a surface of an elastomeric substrate. We show that careful measurement of feature amplitude as a function of applied strain allows not only the determination of wrinkle, fold, or delamination onset but also allows clear distinction between each type of feature. We observe that amplitude increases discontinuously as delamination occurs; whereas, the amplitude for a fold deviates gradually compared to the amplitude for a nearby wrinkle as a function of applied strain. The folds observed in these experiments have an outward morphology from the surface, in contrast to folds that form into the plane for a film floating on a liquid substrate. A deformation mode map is presented, where the measured critical strain for localization is compared for films with thickness ranging from 5 nm to 180 nm.

Contact-line mechanics for pattern control

Wrinkled surfaces are ubiquitous in Nature and can be used in a large range of applications such as improved adhesives, microfluidic patterns, or as metrology instruments. Despite wide-ranging applications, existing methods do not permit local pattern control since all existing methods impose extensive compressive strains. In this article, we describe a new process that exploits the local deformation of a soft substrate as it stretches to form an adhesive interface with a thin polymer film. The wrinkle pattern is effectively a measurement of the strain-field created during the adhesion process, which shows a strong dependence on the speed of attachment. We develop simple scaling arguments to describe this velocity dependence and a critical velocity above which wrinkles do not form. Notably, our approach allows us to define the surface pattern “wrinkle-by-wrinkle”, thus permitting the creation of single wrinkles. Intricate patterns on laterally extensive length scales can also be produced by exploiting the shape of the contact line between the film and the substrate. This level of control—the placement of single features of prescribed trajectory—which is not present in any other method of thin film wrinkling, is absolutely necessary for any realistic, scalable application.

Onset of Plasticity in Thin Polystyrene Films

Polymer glasses have numerous advantageous mechanical properties in comparison to other materials. One of the most useful is the high degree of toughness that can be achieved due to significant yield occurring in the material. Remarkably, the onset of plasticity in polymeric materials is very poorly quantified, despite its importance as the ultimate limit of purely elastic behavior. Here, we report the results of a novel experiment which is extremely sensitive to the onset of yield and discuss its impact on measurement and elastic theory. In particular, we use an elastic instability to locally bend and impart a local tensile stress in a thin, glassy polystyrene film, and directly measure the resulting residual stress caused by the bending. We show that plastic failure is initiated at extremely low strains, of the order 10(-3) for polystyrene. Not only is this critical strain found to be small in comparison to bulk measurement, we show that it is influenced by thin film confinement--leading to an increase in the critical strain for plastic failure as film thickness approaches zero.

Kinetics of layer hopping in a diblock copolymer lamellar phase

In the ordered state, symmetric diblock copolymers self-assemble into an anisotropic lamellar morphology. The equilibrium thickness of the lamellae is the result of a delicate balance between enthalpic and entropic energies, which can be tuned by controlling the temperature. Here we devise a simple yet powerful method of detecting tiny changes in the lamellar thickness using optical microscopy. From such measurements we characterize the enthalpic interaction as well as the kinetics of molecules as they hop from one layer to the next in order to adjust the lamellar thickness in response to a temperature jump. The resolution of the measurements facilitate a direct comparison to predictions from self-consistent field theory.

Influence of Thin Film Confinement on Surface Plasticity in Polystyrene and Poly(2-vinylpyridine) Homopolymer and Block Copolymer Films

Delamination is used to impart a quantifiable local stain on thin films of homopolymer polystyrene and poly(2-vinylpyridine), as well as block copolymers made of styrene and 2-vinylpyridine. Direct observation of the damage caused by bending with atomic force microscopy and laser scanning confocal microscopy leads to the identification of a critical strain for the onset of plasticity. Moving beyond our initial scaling analysis, delamination shapes are fit to two model functions and a more precise value for curvature is used in the calculation of surface strain. The analysis presented here shows strain levels in thick films to be comparable to bulk measurements. Monitoring the critical strain leads to several observations: (1) as-cast PS-P2VP has a low critical strain, (2) annealing slowly increases critical strain as microstructural ordering takes place, and (3) similar to the homopolymer, both as-cast and ordered films both show increasing critical strain under thin-film confinement.

Hole nucleation in free-standing polymer membranes: the effects of varying molecular architecture

Free-standing liquid films are generally unstable, failing whenever a hole or pore is created. The same is true of a polymer melt, although the details of the instability can be more complex and dependent on molecular architecture. Here, we compare the nucleation of holes in homopolymer films and films made from diblock co-polymers that can order into a cylindrical or lamellar phase. The different degrees of internal order (no long-range order, lamellar order, cylindrical order) has significant effects on the rate of hole formation. We find that lamellar order decreases the rate of film rupture by at least two orders of magnitude when compared to isotropic films. The hole formation is well described by a classical nucleation process. Notably, we find that the barrier to hole formation is identical for all samples studied here, favouring a simple capillary model. The vast differences in stability between films of differing internal structure is entirely quantified by the “attempt frequency” of barrier penetration and not the free energy barrier itself.

Spreading of diblock copolymer droplets: A probe of polymer micro-rheology

We present an experimental study of the spreading dynamics of symmetric diblock copolymer droplets above and below the order-disorder transition. Disordered diblock droplets are found to spread as a homopolymer and follow Tanner’s law (the radius grows as R ∼ tm , where t is time and m = 1/10 . However, droplets that are in the ordered phase are found to be frustrated by the imposed lamellar microstructure. This frustration is likely at the root of the observed deviation from Tanner’s law: droplet spreading has a much slower power law ( m ∼ 0.05±0.01 . We show that the different spreading dynamics can be reconciled with conventional theory if a strain-rate-dependent viscosity is taken into account.

Late stage drainage of block copolymer stabilized emulsion drops

Polymer covered emulsion droplets have a considerable number of applications ranging from active cosmetics to advance drug delivery systems. In many of these systems the emulsion droplets do not exist in isolation but interact with other drops, surfaces and particles. In a step towards understanding how these complex mechanical interactions take place, we examine the interaction between a block copolymer covered emulsion droplet (polystyrene-b-poly(ethylene oxide) (PS-PEO) covered toluene) and a flat mica interface. As buoyancy pushes the droplet upwards, it buckles in as it nears the mica and traps a droplet of the surrounding fluid. The trapped outer fluid (water/glycerine in our experiment) drains out through an annular region of PEO brush. This study focuses on the late stage drainage, unique to large molecule surfactants, and examines the effects of the polymer and droplet size on the drainage rate. We introduce a scaling model of the drainage which highlights the importance of three lengthscales in the problem - the brush height, the slip length along the emulsion drop interface and the width of the annular contact region.

Using the sessile drop geometry to measure fluid and elastic block copolymer interfaces.

There is considerable interest in the fabrication and mechanics of soft spheres and capsules because of their use in a large number of applications ranging from targeted drug delivery to cosmetically active agents. Many systems, such as lipid and block copolymer vesicles, are already finding considerable industrial use where the performance of soft spheres depends intimately on their mechanics. New advanced features such as fast cargo delivery can be realized only if they fit into the existing mechanical niche of the system in question. Here we present a model system to demonstrate how a capsule structure can be fundamentally changed while maintaining its overall mechanical response as well as a simple, universal method to measure the resulting capsule material properties. Specifically, we use confocal microscopy to adapt the sessile drop geometry to a measurement of the static properties of an ensemble of polystyrene-b-poly(ethylene oxide) (PS-PEO)-stabilized oil droplets. We then synthesize a polystyrene-b-poly(acrylic acid)-b-polystyrene (PS-PAA-PS) elastic-shell-coated emulsion drop that shows an identical deformation to the fluidlike PS-PEO droplets. Both systems, in sessile geometry, can be related to their basic material properties through appropriate modeling. We find that the elastic shell is dominated by its surface tension, easily enabling it to match the static response of a purely fluid drop.