arXiv subjects

Joshua D. McGraw

Publications and source records attributed to Joshua D. McGraw.

At least 19 recordsLinked to original sources

arXiv2026

Microfluidic Oscillatory Rheology of Transported Soft Particles

Microfluidic channels have emerged as useful tools to control dynamic forcing on transported microscale objects, as encountered in emulsions, biological flows, and other soft matter systems. Tailored channel designs enable precise interfacial and bulk rheological measurements of complex materials over a wide range of forcing timescales. After a brief overview of recent experiments illustrating these techniques, we discuss perspectives for future research in this direction, including the study of lubrication films in highly confined droplets, the measurement of fast relaxation dynamics of complex interfaces, and the high-throughput rheological characterization of microscopic soft matter systems ranging from single macromolecules to cells.

cond-mat.soft↗

arXiv2023

Nanoparticle Taylor dispersion near charged surfaces with an open boundary

The dispersive spreading of microscopic particles in shear flows is influenced both by advection and thermal motion. At the nanoscale, interactions between such particles and their confining boundaries become unavoidable. We address the roles of electrostatic repulsion and absorption on the spatial distribution and dispersion of charged nanoparticles in near-surface shear flows, observed under evanescent illumination. The electrostatic repulsion between particles and the lower charged surface is tuned by varying electrolyte concentrations. Particles leaving the field of vision can be neglected from further analysis, such that the experimental ensemble is equivalent to that of Taylor dispersion with absorption. These two ingredients modify the particle distribution, deviating strongly from the Gibbs-Boltzmann one at the nanoscale studied here. The overall effect is to restrain the accessible space available to particles, leading to a striking, ten-fold reduction in the spreading dynamics as compared to the non-interacting case.

cond-mat.soft↗

arXiv2019

Interface-Sensitive Raman Microspectroscopy of Water via Confinement with a Multimodal Miniature Surface Forces Apparatus

Modern interfacial science is increasingly multi-disciplinary. Unique insight into interfacial interactions requires new multimodal techniques for interrogating surfaces with simultaneous complementary physical and chemical measurements. We describe here the design and testing of a microscope that incorporates a miniature Surface Forces Apparatus (μSFA) in sphere vs. flat mode for force-distance measurements, while simultaneously acquiring Raman spectra of the confined zone. The microscope uses a simple optical setup that isolates independent optical paths for (i) the illumination and imaging of Newton's Rings and (ii) Raman-mode excitation and efficient signal collection. We benchmark the methodology by examining Teflon thin films in asymmetric (Teflon-water-glass) and symmetric (Teflon-water-Teflon) configurations. Water is observed near the Teflon-glass interface with nanometer-scale sensitivity in both the distance and Raman signals. We perform chemically-resolved, label-free imaging of confined contact regions between Teflon and glass surfaces immersed in water. Remarkably, we estimate that the combined approach enables vibrational spectroscopy with single water monolayer sensitivity within minutes. Altogether, the Raman-μSFA allows exploration of molecular confinement between surfaces with chemical selectivity and correlation with interaction forces.

physics.ins-det↗

arXiv2019

A Multi-Modal Miniature Surface Forces Apparatus (uSFA) for Interfacial Science Measurements

Advances in the research of intermolecular and surface interactions result from the development of new and improved measurement techniques and combinations of existing techniques. Here, we present a new miniature version of the Surface Force Apparatus (the uSFA) that has been designed for ease of use and multi-modal capabilities with retention of the capabilities of other SFA models including accurate measurement of surface separation distance and physical characterization of dynamic and static physical forces (i.e., normal, shear, and friction) and interactions (e.g., van der Waals, electrostatic, hydrophobic, steric, biospecific). The small physical size of the uSFA, compared to previous SFA models, makes it portable and suitable for integration into commercially available optical and fluorescence light microscopes, as demonstrated here. The large optical path entry and exit ports make it ideal for concurrent force measurements and spectroscopy studies. Examples of the use of the uSFA in combination with surface plasmon resonance (SPR) and Raman spectroscopy measurements are presented. Due to the short working distance constraints associated with Raman spectroscopy, an interferometric technique was developed and applied for calculating the inter-surface separation distance based on Newtons rings. The introduction of the \muSFA will mark a transition in SFA usage from primarily physical characterization to concurrent physical characterization with in situ chemical and biological characterization to study interfacial phenomena, including (but not limited to) molecular adsorption, fluid flow dynamics, determination of surface species and morphology, and (bio) molecular binding kinetics.

physics.ins-det↗

arXiv2018

Influence of outer-layer finite-size effects on the rupture kinetics of a thin polymer film embedded in an immiscible matrix

In capillary-driven fluid dynamics, simple departures from equilibrium offer the chance to quantitatively model the resulting relaxations. These dynamics in turn provide insight on both practical and fundamental aspects of thin-film hydrodynamics. In this work, we describe a model trilayer dewetting experiment elucidating the effect of solid, no-slip confining boundaries on the bursting of a liquid film in a viscous environment. This experiment was inspired by an industrial polymer processing technique, multilayer coextrusion, in which thousands of alternating layers are stacked atop one another. When pushed to the nanoscale limit, the individual layers are found to break up on time scales shorter than the processing time. To gain insight on this dynamic problem, we here directly observe the growth rate of holes in the middle layer of the trilayer films described above, wherein the distance between the inner film and solid boundary can be orders of magnitude larger than its thickness. In otherwise identical experimental conditions, thinner films break up faster than thicker ones. This observation is found to agree with a scaling model that balances capillary driving power and viscous dissipation with, crucially, a no-slip boundary condition at the solid substrate/viscous environment boundary. In particular, even for the thinnest middle-layers, no finite-size effect is needed to explain the data. The dynamics of hole growth is captured by a single master curve over four orders of magnitude in the dimensionless hole radius and time, and is found to agree well with predictions including analytic expressions for the dissipation.

cond-mat.soft↗

arXiv2017

Adsorption-Induced Slip Inhibition for Polymer Melts on Ideal Substrates

Hydrodynamic slip of a liquid at a solid surface represents a fundamental phenomenon in fluid dynamics that governs liquid transport at small scales. For polymeric liquids, de Gennes predicted that the Navier boundary condition together with the theory of polymer dynamics imply extraordinarily large interfacial slip for entangled polymer melts on ideal surfaces; this Navier-de Gennes model was confirmed using dewetting experiments on ultra-smooth, low-energy substrates. Here, we use capillary leveling - surface tension driven flow of films with initially non-uniform thickness - of polymeric films on these same substrates. Measurement of the slip length from a robust one-parameter fit to a lubrication model is achieved. We show that at the lower shear rates involved in leveling experiments as compared to dewetting ones, the employed substrates can no longer be considered ideal. The data is instead consistent with physical adsorption of polymer chains at the solid/liquid interface. We extend the Navier-de Gennes description using one additional parameter, namely the density of physically adsorbed chains per unit surface. The resulting formulation is found to be in excellent agreement with the experimental observations.

cond-mat.soft↗

arXiv2017

Nucleated dewetting in supported ultra-thin liquid films with hydrodynamic slip

This study reveals the influence of the surface energy and solid/liquid boundary condition on the breakup mechanism of dewetting ultra-thin polymer films. Using silane self-assembled monolayers, SiO$_2$ substrates are rendered hydrophobic and provide a strong slip rather than a no-slip solid/liquid boundary condition. On undergoing these changes, the thin-film breakup morphology changes dramatically -- from a spinodal mechanism to a breakup which is governed by nucleation and growth. The experiments reveal a dependence of the hole density on film thickness and temperature. The combination of lowered surface energy and hydrodynamic slip brings the studied system closer to the conditions encountered in bursting unsupported films. As for unsupported polymer films, a critical nucleus size is inferred from a free energy model. This critical nucleus size is supported by the film breakup observed in the experiments using high speed \emph{in situ} atomic force microscopy.

cond-mat.soft↗

arXiv2016

Effects of slippage on the dewetting of a droplet

In many macroscopic dynamic wetting problems, it is assumed that the macroscopic interface is quasistatic, and the dissipation appears only in the region close to the contact line. When approaching the moving contact line, a microscopic mechanism is required to regularize the singularity of viscous dissipation. On the other hand, if the characteristic size of a fluidic system is reduced to a range comparable to the microscopic regularization length scale, the assumption that viscous effects are localized near the contact line is no longer justified. In the present work, such microscopic length is the slip length. We investigate the dewetting of a droplet using the boundary element method. Specifically, we solve for the axisymmetric Stokes flow with i) the Navier-slip boundary condition at the solid/liquid boundary, and ii) a time-independent microscopic contact angle at the contact line. The profile evolution is computed for different slip lengths and equilibrium contact angles. When decreasing the slip length, the typical nonsphericity first increases, reaches a maximum at a characteristic slip length $\tilde{b}_m$, and then decreases. Regarding different equilibrium contact angles, two universal rescalings are proposed to describe the behavior for slip lengths larger or smaller than $\tilde{b}_m$. Around $\tilde{b}_m$, the early time evolution of the profiles at the rim can be described by similarity solutions. The results are explained in terms of the structure of the flow field governed by different dissipation channels: viscous elongational flows for large slip lengths, friction at the substrate for intermediate slip lengths, and viscous shear flows for small slip lengths. Following the transitions between these dominant dissipation mechanisms, our study indicates a crossover to the quasistatic regime when the slip length is small compared to the droplet size.

physics.flu-dyn↗

arXiv2016

Influence of bidisperse self-assembled monolayer structure on the slip boundary condition of thin polymer films

Alkylsilane self-assembled monolayers (SAMs) are often used as model substrates for their ease of preparation and hydrophobic properties. We have observed that these atomically smooth monolayers also provide a slip boundary condition for dewetting films composed of unentangled polymers. This slip length, an indirect measure of the friction between a given liquid and different solids, is switchable and can be increased [Fetzer et al., Phys. Rev. Lett. 2005; Bäumchen et al. J. Phys.: Cond. Matt. 2012] if the alkyl chain length is changed from 18 to 12 backbone carbons, for example. Typically, this change in boundary condition is affected in a quantized way, using one or the other alkyl chain length, thus obtaining one or the other slip length. Here, we present results in which this SAM structure is changed in a continuous way. We prepare SAMs containing bidisperse mixed SAMs of alkyl silanes, with the composition as a control parameter. We find that all the mixed SAMs we investigated show an enhanced slip boundary condition as compared to the single-component SAMs. The slip boundary condition is accessed using optical and atomic force microscopy, and we describe these observations in the context of X-ray reflectivity measurements. The slip length, varying over nearly two orders of magnitude, of identical polymer melts on chemically similar SAMs is found to correlate with the density of exposed alkyl chains. Our results demonstrate the importance of a well characterized solid/liquid pair, down to the angstrom level, when discussing friction between a liquid and a solid.

cond-mat.soft↗

arXiv2016

Controlling Marangoni induced instabilities in spin-cast polymer films: how to prepare uniform films

In both research and industrial settings spin coating is extensively used to prepare highly uniform thin polymer films. However, under certain conditions, spin coating results in films with non-uniform surface morphologies. Although the spin coating process has been extensively studied, the origin of these morphologies is not fully understood and the formation of non-uniform spincast films remains a practical problem. Here we report on experiments demonstrating that the formation of surface instabilities during spin coating is dependent on temperature. Our results suggest that non-uniform spincast films form as a result of the Marangoni effect, which describes flow due to surface tension gradients. We find that both the wavelength and amplitude of the pattern increase with temperature. Finally, and most important from a practical viewpoint, the non-uniformities in the film thickness can be entirely avoided simply by lowering the spin coating temperature.

cond-mat.soft↗

arXiv2016

Slip-Mediated Dewetting of Polymer Microdroplets

Classical hydrodynamic models predict that infinite work is required to move a three-phase contact line, defined here as the line where a liquid/vapor interface intersects a solid surface. Assuming a slip boundary condition, in which the liquid slides against the solid, such an unphysical prediction is avoided. In this article, we present the results of experiments in which a contact line moves and where slip is a dominating and controllable factor. Spherical cap shaped polystyrene microdroplets, with non-equilibrium contact angle, are placed on solid self-assembled monolayer coatings from which they dewet. The relaxation is monitored using \textit{in situ} atomic force microscopy. We find that slip has a strong influence on the droplet evolutions, both on the transient non-spherical shapes and contact line dynamics. The observations are in agreement with scaling analysis and boundary element numerical integration of the governing Stokes equations, including a Navier slip boundary condition.

cond-mat.soft↗

arXiv2016

Short Chains Enhance Slip of Highly Entangled Polystyrenes during Thin Film Dewetting

We investigate the effect of short chains on slip of highly entangled polystyrenes (PS) during thin film dewetting from non-wetting fluorinated surfaces. Binary and ternary mixtures were prepared from monodisperse PS with weight average molecular weights $5 < M_\textrm{w} < 490$ kg/mol. Flow dynamics and rim morphology of dewetting holes were captured using optical and atomic force microscopy. Slip properties are assessed in the framework of hydrodynamic models describing the rim height profile of dewetting holes. We show that short chains with $M_\textrm{w}$ below the polymer critical molecular weight for entanglements, $M_\textrm{c}$, can play an important role in slip of highly entangled polymers. Among mixtures of the same $M_\textrm{w}$, those containing chains with $M<M_\textrm{c}$ exhibit larger slip lengths as the number average molecular weight, $M_\textrm{n}$, decreases. The slip enhancement effect is only applicable when chains with $M<M_\textrm{c}$ are mixed with highly entangled chains such that the content of the long chain component, $ϕ_\textrm{L}$, is dominant ($ϕ_\textrm{L}<0.5$). These results suggest that short chains affect slip of highly entangled polymers on non-wetting surfaces due to the physical or chemical disparities of end groups, and any associated dynamical effect their presence may have, as compared to the backbone units. The enhanced slip in this regard is attributed to the impact of chain end groups or short chain enrichment on the effective interfacial friction coefficient. Accordingly, for entangled PS, a higher concentration of end groups or short chains at the interface results in a lower effective friction coefficient which consequently enhances the slip length.

cond-mat.soft↗

arXiv2015

A direct quantitative measure of surface mobility in a glassy polymer

Thin polymer films have striking dynamical properties that differ from their bulk counterparts. With the simple geometry of a stepped polymer film on a substrate, we probe mobility above and below the glass transition temperature $T_{\textrm{g}}$. Above $T_{\textrm{g}}$ the entire film flows, while below $T_{\textrm{g}}$ only the near surface region responds to the excess interfacial energy. An analytical thin film model for flow limited to the free surface region shows excellent agreement with sub-$T_{\textrm{g}}$ data. The system transitions from whole film flow to surface localized flow over a narrow temperature region near the bulk $T_{\textrm{g}}$. The experiments and model provide a measure of surface mobility in a sample geometry where confinement and substrate effects are negligible. This fine control of the glassy rheology is of key interest to nanolithography among numerous other applications.

cond-mat.soft↗

arXiv2015

Influence of Slip on the Plateau-Rayleigh Instability on a Fibre

The Plateau-Rayleigh instability of a liquid column underlies a variety of fascinating phenomena that can be observed in everyday life. In contrast to the case of a free liquid cylinder, describing the evolution of a liquid layer on a solid fibre requires consideration of the solid-liquid interface. In this article, we revisit the Plateau-Rayleigh Instability of a liquid coating a fibre by varying the hydrodynamic boundary condition at the fibre-liquid interface, from no-slip to slip. While the wavelength is not sensitive to the solid-liquid interface, we find that the growth rate of the undulations strongly depends on the hydrodynamic boundary condition. The experiments are in excellent agreement with a new thin film theory incorporating slip, thus providing an original, quantitative and robust tool to measure slip lengths.

physics.flu-dyn↗

arXiv2013

Relaxation and Intermediate Asymptotics of a Rectangular Trench in a Viscous Film

The surface of a thin liquid film with nonconstant curvature flattens as a result of capillary forces. While this leveling is driven by local curvature gradients, the global boundary conditions greatly influence the dynamics. Here, we study the evolution of rectangular trenches in a polystyrene nanofilm. Initially, when the two sides of a trench are well separated, the asymmetric boundary condition given by the step height controls the dynamics. In this case, the evolution results from the leveling of two noninteracting steps. As the steps broaden further and start to interact, the global symmetric boundary condition alters the leveling dynamics. We report on full agreement between theory and experiments for: the capillary-driven flow and resulting time dependent height profiles; a crossover in the power-law dependence of the viscous energy dissipation as a function of time as the trench evolution transitions from two noninteracting to interacting steps; and the convergence of the profiles to a universal self-similar attractor that is given by the Green's function of the linear operator describing the dimensionless linearized thin film equation.

cond-mat.soft↗

arXiv2013

Numerical solutions of thin film equations for polymer flows

We report on the numerical implementation of thin film equations that describe the capillary-driven evolution of viscous films, in two-dimensional configurations. After recalling the general forms and features of these equations, we focus on two particular cases inspired by experiments: the leveling of a step at the free surface of a polymer film, and the leveling of a polymer droplet over an identical film. In each case, we first discuss the long-term self-similar regime reached by the numerical solution before comparing it to the experimental profile. The agreement between theory and experiment is excellent, thus providing a versatile probe for nanorheology of viscous liquids in thin film geometries.

cond-mat.soft↗

arXiv2013

Capillary leveling of stepped films with inhomogeneous molecular mobility

A homogeneous thin polymer film with a stepped height profile levels due to the presence of Laplace pressure gradients. Here we report on studies of polymeric samples with precisely controlled, spatially inhomogeneous molecular weight distributions. The viscosity of a polymer melt strongly depends on the chain length distribution; thus, we learn about thin-film hydrodynamics with viscosity gradients. These gradients are achieved by stacking two films with different molecular weights atop one another. After a sufficient time these samples can be well described as having one dimensional viscosity gradients in the plane of the film, with a uniform viscosity normal to the film. We develop a hydrodynamic model that accurately predicts the shape of the experimentally observed self-similar profiles. The model allows for the extraction of a capillary velocity, the ratio of the surface tension and the viscosity, in the system. The results are in excellent agreement with capillary velocity measurements of uniform mono- and bi-disperse stepped films and are consistent with bulk polymer rheology.

cond-mat.soft↗

arXiv2012

Capillary-driven flow induced by a stepped perturbation atop a viscous film

Thin viscous liquid films driven by capillarity are well described in the lubrication theory through the thin film equation. In this article, we present an analytical solution of this equation for a particular initial profile: a stepped perturbation. This initial condition allows a linearization of the problem making it amenable to Fourier analysis. The solution is obtained and characterized. As for a temperature step in the heat equation, self-similarity of the first kind of the full evolution is demonstrated and a long-term expression for the excess free energy is derived. In addition, hydrodynamical fields are described. The solution is then compared to experimental profiles from a model system: a polystyrene nanostep above the glass transition temperature which flows due to capillarity. The excellent agreement enables a precise measurement of the capillary velocity for this polymeric liquid, without involving any numerical simulation. More generally, as these results hold for any viscous system driven by capillarity, the present solution may provide a useful tool in hydrodynamics of thin viscous films.

cond-mat.soft↗