Jan Genzer

Recent developments in superhydrophobic surfaces and their relevance to marine fouling: a review

Abstract In this review, a brief synopsis of superhydrophobicity (i.e. extreme non-wettability) and its implications on marine fouling are presented. A short overview of wettability and recent experimental developments aimed at fabricating superhydrophobic surfaces by tailoring their chemical nature and physical appearance (i.e. substratum texture) are reviewed. The formation of responsive/“smart” surfaces, which adjust their physico-chemical properties to variations in some outside physical stimulus, including light, temperature, electric field, or solvent, is also described. Finally, implications of tailoring the surface chemistry, texture, and responsiveness of surfaces on the design of effective marine fouling coatings are considered and discussed.

Self-folding of polymer sheets using local light absorption

This paper demonstrates experimentally and models computationally a novel and simple approach for self-folding of thin sheets of polymer using unfocused light. The sheets are made of optically transparent, pre-strained polystyrene (also known as Shrinky-Dinks) that shrink in-plane if heated uniformly. Black ink patterned on either side of the polymer sheet provides localized absorption of light, which heats the underlying polymer to temperatures above its glass transition. At these temperatures, the predefined inked regions (i.e., hinges) relax and shrink, and thereby cause the planar sheet to fold into a three-dimensional object. Self-folding is therefore achieved in a simple manner without the use of multiple fabrication steps and converts a uniform external stimulus (i.e., unfocused light) on an otherwise compositionally homogenous substrate into a hinging response. Modeling captures effectively the experimental folding trends as a function of the hinge width and support temperature and suggests that the hinged region must exceed the glass transition temperature of the sheet for folding to occur.

Development and Testing of Hierarchically Wrinkled Coatings for Marine Antifouling

We report on the formation and testing of novel marine coatings comprising hierarchically wrinkled surface topographies (HWTS) having wrinkles of different length scales (generations) ranging from tens of nanometers to a fraction of a millimeter. The individual wrinkle generations are arranged in nested patterns, where each larger wrinkle resides underneath and represents a scaled-up version of the smaller wrinkle. We present and discuss results from field tests in seawater and laboratory experiments. The results of our field tests reveal that while coatings with flat topographies foul after relatively short time periods (4-15 weeks), the HWST coatings with the same chemistries as flat coatings remain relatively free of biofouling even after prolonged exposure to seawater (18 months). In contrast to flat coatings, the HWST substrates are not colonized by barnacles. These observations suggest that surface topography plays a dominant role in governing the coating defense against barnacle fouling even without fine-tuning the chemical composition of the overcoat. Laboratory experiments indicate that settlement of zoospores of the green alga Ulva and the strength of attachment of sporelings (young plants) depend on the chemical composition of the coating as well as surface topography.

Controlling the assembly of nanoparticles using surface grafted molecular and macromolecular gradients

We report on the generation of assemblies comprising number density gradients of nanoparticles in two (2D) and three (3D) dimensions. These structures are fabricated by creating a surface-bound organic template which directs the spatial arrangement of gold nanoparticles. The 2D template is made of amine-terminated organosilane with a concentration gradient along the solid substrate. The 3D matrix comprises surface-anchored poly(acryl amide), whose molecular weight changes gradually on the specimen. In both cases, the composite is assembled at low pH, where the positively charged –NH3+ groups within the organic scaffold attract negatively charged gold nanoparticles. We use a battery of experimental tools to determine the number density of particles along the gradient substrate and in the case of 3D structures also their spatial distribution. For 2D gradient assemblies, we show that gold nanoparticle coverage on the surface decreases gradually as the concentration of substrate-bound aminosilane decreases. The number of particles in the polymer brush/particle hybrid is found to increase with increasing polymer molecular weight. We show that for a given grafting density of polymer brush, larger particles predominantly stay near the brush–air interface. In contrast, smaller nanoparticles penetrate deeper into the polymer brush, thus forming a 3D structure. Finally, we discuss possible applications of these nanoparticle gradient assemblies.

Simultaneous bulk- and surface-initiated controlled radical polymerization from planar substrates.

We employ Monte Carlo computer simulations to investigate the simultaneous controlled radical polymerization in solution and from a flat surface. The bulk polymers grow at faster rates and possess narrower molecular weight distribution than polymers initiated from flat, impenetrable surfaces. The rate of surface-initiated polymerization depends on the density of initiator sites. Our results provide evidence that the assumption that the molecular weight of surface-initiated polymers is equal to that of polymers grown in bulk, invoked often in determining the grafting density of surface-bound polymers, is generally invalid.

Application of ion scattering techniques to characterize polymer surfaces and interfaces

Ion beam analysis techniques, particularly elastic recoil detection (ERD) also known as forward recoil spectrometry (Frcs) has proven to be a value tool to investigate polymer surfaces and interfaces. A review of ERD, related techniques and their impact on the field of polymer science is presented. The physics of the technique is described as well as the underlying principles of the interaction of ions with matter. Methods for optimization of ERD for polymer systems are also introduced, specifically techniques to improve the depth resolution and sensitivity. Details of the experimental setup and requirements are also laid out. After a discussion of ERD, strategies for the subsequent data analysis are described. The review ends with the breakthroughs in polymer science that ERD enabled in polymer diffusion, surfaces, interfaces, critical phenomena, and polymer modification.

Adsorption of a Nonionic Symmetric Triblock Copolymer on Surfaces with Different Hydrophobicity

This study investigates the adsorption of a symmetric triblock nonionic polymer comprising ethylene oxide (EO) and propylene oxide (PO) blocks (Pluronic P-105, EO(37)PO(56)EO(37)) on a range of substrates including hydrophobic, i.e., polypropylene (PP), poly(ethylene terephthalate) (PET), nylon, and graphite, and hydrophilic, i.e., cellulose and silica. The adsorption process and the structure of the hydrated adsorbed layers are followed by quartz crystal microgravimetry (QCM), surface plasmon resonance (SPR), and atomic force microscopy. The unhydrated surfaces are characterized by ellipsometry and contact angle techniques. The adsorption kinetics and the extent of adsorption are determined by monitoring the changes in resonance frequency and refractive index of sensors coated with ultrathin films of the various substrates. Langmuirian-type adsorption kinetics is observed in all cases studied. The amount of adsorbed Pluronic on hydrophobic polymer surfaces (PP, PET, and nylon) exceeds that on the hydrophilic cellulose. The hydrophobic (graphite) mineral surface adsorbs relatively low polymer mass, typical of a monolayer, while micellar structures are observed on the hydrophilic silica surface. The amount of water coupled to the adsorbed polymer layers is quantified by combining data from QCM, and SPR are found to increase with increasing polarity of the substrate. On the basis of contact angle data, the nonhydrated adsorbed structures produce modest increases in hydrophilicity of all the substrates investigated. Overall, insights are provided into the structure and stability of both hydrated and nonhydrated adsorbed triblock copolymer.

Elastomeric microparticles for acoustic mediated bioseparations.

BackgroundAcoustophoresis has been utilized successfully in applications including cell trapping, focusing, and purification. One current limitation of acoustophoresis for cell sorting is the reliance on the inherent physical properties of cells (e.g., compressibility, density) instead of selecting cells based upon biologically relevant surface-presenting antigens. Introducing an acoustophoretic cell sorting approach that allows biochemical specificity may overcome this limitation, thus advancing the value of acoustophoresis approaches for both the basic research and clinical fields.ResultsThe results presented herein demonstrate the ability for negative acoustic contrast particles (NACPs) to specifically capture and transport positive acoustic contrast particles (PACPs) to the antinode of an ultrasound standing wave. Emulsification and post curing of pre-polymers, either polydimethylsiloxane (PDMS) or polyvinylmethylsiloxane (PVMS), within aqueous surfactant solution results in the formation of stable NACPs that focus onto pressure antinodes. We used either photochemical reactions with biotin-tetrafluorophenyl azide (biotin-TFPA) or end-functionalization of Pluronic F108 surfactant to biofunctionalize NACPs. These biotinylated NACPs bind specifically to streptavidin polystyrene microparticles (as cell surrogates) and transport them to the pressure antinode within an acoustofluidic chip.ConclusionTo the best of our knowledge, this is the first demonstration of using NACPs as carriers for transport of PACPs in an ultrasound standing wave. By using different silicones (i.e., PDMS, PVMS) and curing chemistries, we demonstrate versatility of silicone materials for NACPs and advance the understanding of useful approaches for preparing NACPs. This bioseparation scheme holds potential for applications requiring rapid, continuous separations such as sorting and analysis of cells and biomolecules.

Determination of the Electron Escape Depth for NEXAFS Spectroscopy

A novel method was developed to determine carbon atom density as a function of depth by analyzing the postedge signal in near-edge X-ray absorption fine structure (NEXAFS) spectra. We show that the common assumption in the analysis of NEXAFS data from polymer films, namely, that the carbon atom density is constant as a function of depth, is not valid. This analysis method is then used to calculate the electron escape depth (EED) for NEXAFS in a model bilayer system that contains a perfluorinated polyether (PFPE) on top of a highly oriented pyrolitic graphite (HOPG) sample. Because the carbon atom densitites of both layers are known, in addition to the PFPE surface layer thickness, the EED is determined to be 1.95 nm. This EED is then used to measure the thickness of the perfluorinated surface layer of poly(4-(1H,1H,2H,2H-perfluorodecyl)oxymethylstyrene) (PFPS).

Computer simulation of copolymer phase behavior

Discontinuous molecular dynamics simulation is used to study the phase behavior of diblock copolymers modeled as chains of tangent hard spheres with square shoulder repulsions between unlike species as a function of chain length, volume fraction and interaction strength (χ). The location of the order–disorder transition for a symmetric copolymer is close to the predictions of Fredrickson and Helfand. Our simulation results for packing fractions of 0.35, 0.40, and 0.45 and chain lengths 10 and 20 are summarized in phase diagrams which display disordered, lamellae, perforated lamellae (PL), cylindrical, and BCC spherical (S) phases in the χN versus f plane. These phase diagrams are consistent with phase diagrams from other simulation studies. Contrary to theoretical predictions we observe the PL phase near regions of predicted gyroid stability, and the S phase only in the systems with high packing fraction and long chain length. These discrepancies may be due to the short chain lengths considered, as they a...