Kelvin equation for bridging transitions.

We study bridging transitions between a pair of nonplanar surfaces. We show that the transition can be described using a generalized Kelvin equation by mapping the system to a slit of finite length. The proposed equation is applied to analyze the asymptotic behavior of the growth of the bridging film, which occurs when the confining walls are gradually flattened. This phenomenon is characterized by a power-law divergence with geometry-dependent critical exponents that we determine for a wide class of walls' geometries. In particular, for a linear-wedge model, a covariance law revealing a relation between a geometric and Young's contact angle is presented. These predictions are shown to be fully in line with the numerical results obtained from a microscopic (classical) density functional theory.

Critical effects and scaling at meniscus osculation transitions.

We propose a simple scaling theory describing critical effects at rounded meniscus osculation transitions which occur when the Laplace radius of a condensed macroscopic drop of liquid coincides with the local radius of curvature R_{w} in a confining parabolic geometry. We argue that the exponent ß_{osc} characterizing the scale of the interfacial height ℓ_{0}∝R_{w}^{ß_{osc}} at osculation, for large R_{w}, falls into two regimes representing fluctuation-dominated and mean-field-like behavior, respectively. These two regimes are separated by an upper critical dimension, which is determined here explicitly and depends on the range of the intermolecular forces. In the fluctuation-dominated regime, representing the universality class of systems with short-range forces, the exponent is related to the value of the interfacial wandering exponent ζ by ß_{osc}=3ζ/(4-ζ). In contrast, in the mean-field regime, which was not previously identified and which occurs for systems with longer-range forces (and higher dimensions), the exponent ß_{osc} takes the same value as the exponent ß_{s}^{co} for complete wetting, which is determined directly by the intermolecular forces. The prediction ß_{osc}=3/7 in d=2 for systems with short-range forces (corresponding to ζ=1/2) is confirmed using an interfacial Hamiltonian model which determines the exact scaling form for the decay of the interfacial height probability distribution function. A numerical study in d=3, based on a microscopic model density-functional theory, determines that ß_{osc}≈ß_{s}^{co}≈0.326 close to the predicted value of 1/3 appropriate to the mean-field regime for dispersion forces.

Phase behavior of fluids in undulated nanopores.

The geometry of walls forming a narrow pore may qualitatively affect the phase behavior of the confined fluid. Specifically, the nature of condensation in nanopores formed of sinusoidally shaped walls (with amplitude A and period P) is governed by the wall mean separation L as follows. For L>L_{t}, where L_{t} increases with A, the pores exhibit standard capillary condensation similar to planar slits. In contrast, for L

Meniscus osculation and adsorption on geometrically structured walls.

We study the adsorption of simple fluids at smoothly structured, completely wet walls and show that a meniscus osculation transition occurs when the Laplace and geometrical radii of curvature of locally parabolic regions coincide. Macroscopically, the osculation transition is of fractional, 7/2, order and separates regimes in which the adsorption is microscopic, containing only a thin wetting layer, and mesoscopic, in which a meniscus exists. We develop a scaling theory for the rounding of the transition due to thin wetting layers and derive critical exponent relations that determine how the interfacial height scales with the geometrical radius of curvature. Connection with the general geometric construction proposed by Rascón and Parry is made. Our predictions are supported by a microscopic model density functional theory for drying at a sinusoidally shaped hard wall where we confirm the order of the transition and also an exact sum rule for the generalized contact theorem due to Upton. We show that as bulk coexistence is approached the adsorption isotherm separates into three regimes: A preosculation regime where it is microscopic, containing only a thin wetting layer; a mesoscopic regime, in which a meniscus sits within the troughs; and finally another microscopic regime where the liquid-gas interface unbinds from the crests of the substrate.

Digitally-Compensated Wideband 60 GHz Test-Bed for Power Amplifier Predistortion Experiments.

Millimeter waves will play an important role in communication systems in the near future. On the one hand, the bandwidths available at millimeter-wave frequencies allow for elevated data rates, but on the other hand, the wide bandwidth accentuates the effects of wireless front-end impairments on transmitted waveforms and makes their compensation more difficult. Research into front-end impairment compensation in millimeter-wave frequency bands is currently being carried out, mainly using expensive laboratory setups consisting of universal signal generators, spectral analyzers and high-speed oscilloscopes. This paper presents a detailed description of an in-house built MATLAB-controlled 60 GHz measurement test-bed developed using relatively inexpensive hardware components that are available on the market and equipped with digital compensation for the most critical front-end impairments, including the digital predistortion of the power amplifier. It also demonstrates the potential of digital predistortion linearization on two distinct 60 GHz power amplifiers: one integrated in a direct-conversion transceiver and an external one with 24 dBm output power.

Chiral Structure Formation during Casting of Cellulose Nanocrystalline Films.

A Landau-de Gennes formulation coupled with a mass-transfer equation was used to track the evaporation front and the development of chiral microstructures during the casting of sulfuric acid-hydrolyzed cellulose nanocrystal (CNC) films. These simulations are compared to thin-film casting experiments that used analogous processing parameters and environments. The results show that the initial concentration, chiral strength, surface anchoring, speed of drying, and the influence of initial shear alignment all affect the uniformity of the microstructure and the orientation of the chiral director. In this report, we aim to show that under optimal casting conditions, the lateral size of planar microstructural domains that exhibit uniform selective reflection can be achieved on the order of millimeters.

Dielectric Barrier Discharge Applicator for Heating Carbon Nanotube-Loaded Interfaces and Enhancing 3D-Printed Bond Strength.

Material extrusion (ME) 3D printing is a revolutionary technique for manufacturing thermoplastic parts; however, the printed parts typically suffer from poor interlayer bonding, which causes weak tensile strength in the build direction. Many methods have been proposed to address the mechanical deficiencies of 3D-printed parts, but most fall short of a production-ready solution. Here we report the use of a dielectric barrier discharge (DBD) plasma electrode mounted concentrically around the nozzle of an ME 3D printer for in situ welding of thermoplastic parts. This is the first report of a DBD being used as a non-contact means to induce Joule heating in resistive composite materials. The polymer welding process is accomplished by coupling the DBD with the carbon nanotube-loaded interfaces between the 3D-printed layers. The current passing through the part results in rapid resistive heating of the nanotubes and thermal welding of the interfaces. We show that parts printed with this method have isotropic strength and are equivalent to their injection-molded counterparts.

Scaling of wetting and prewetting transitions on nanopatterned walls.

We consider a nanopatterned planar wall consisting of a periodic array of stripes of width L, which are completely wet by liquid (contact angle θ=0), separated by regions of width D which are completely dry (contact angle θ=π). Using microscopic density functional theory, we show that, in the presence of long-ranged dispersion forces, the wall-gas interface undergoes a first-order wetting transition, at bulk coexistence as the separation D is reduced to a value D_{w}∝lnL, induced by the bridging between neighboring liquid droplets. Associated with this is a line of prewetting transitions occurring off coexistence. By varying the stripe width L, we show that the prewetting line shows universal scaling behavior and data collapse. This verifies predictions based on mesoscopic models for the scaling properties associated with finite-size effects at complete wetting including the logarithmic singular contribution to the surface free energy.

Bridging of liquid drops at chemically structured walls.

Using mesoscopic interfacial models and microscopic density functional theory we study fluid adsorption at a dry wall decorated with three completely wet stripes of width L separated by distances D_{1} and D_{2}. The stripes interact with the fluid with long-range forces inducing a large finite-size contribution to the surface free energy. We show that this nonextensive free-energy contribution scales with lnL and drives different types of bridging transition corresponding to the merging of liquid drops adsorbed at neighboring wetting stripes when the separation between them is molecularly small. We determine the surface phase diagram and show that this exhibits two triple points, where isolated drops, double drops, and triple drops coexist. For the symmetric case, D_{1}=D_{2}≡D, our results also confirm that the equilibrium droplet configuration always has the symmetry of the substrate corresponding to either three isolated drops when D is large or a single triple drop when D is small; however, symmetry-broken configurations do occur in a metastable part of the phase diagram which lies very close to the equilibrium-bridging phase boundary. Implications for phase transitions on other types of patterned surface are considered.

Symmetry-breaking morphological transitions at chemically nanopatterned walls.

We study the structure and morphological changes of fluids that are in contact with solid composites formed by alternating and microscopically wide stripes of two different materials. One type of the stripes interacts with the fluid via long-ranged Lennard-Jones-like potential and tends to be completely wet, while the other type is purely repulsive and thus tends to be completely dry. We consider closed systems with a fixed number of particles that allows for stabilization of fluid configurations breaking the lateral symmetry of the wall potential. These include liquid morphologies corresponding to a sessile drop that is formed by a sequence of bridging transitions that connect neighboring wet regions adsorbed at the attractive stripes. We study the character of the transitions depending on the wall composition, stripes width, and system size. Using a (classical) nonlocal density functional theory (DFT), we show that the transitions between different liquid morphologies are typically weakly first-order but become rounded if the wavelength of the system is lower than a certain critical value L_{c}. We also argue that in the thermodynamic limit, i.e., for macroscopically large systems, the wall becomes wet via an infinite sequence of first-order bridging transitions that are, however, getting rapidly weaker and weaker and eventually become indistinguishable from a continuous process as the size of the bridging drop increases. Finally, we construct the global phase diagram and study the density dependence of the contact angle of the bridging drops using DFT density profiles and a simple macroscopic theory.

Orientation Relaxation Dynamics in Cellulose Nanocrystal Dispersions in the Chiral Liquid Crystalline Phase.

A Landau-de Gennes formulation was implemented in dynamic finite element simulations to compare with postshear relaxation experiments that were conducted on cholesteric cellulose nanocrystal (CNC) dispersions. Our study focused on the microstructural reassembly of CNCs in lyotropic dispersions as parameters such as chiral strength and gap confinement were varied. Our simulation results show that homeotropic and/or more complicated three-dimensional helical configurations are possible, depending on the choice of these parameters. We also observed how dynamic banding patterns develop into the hierarchical microstructures that are characterized by an equilibrium pitch length in both the experiments and simulations. This work has immediate relevance for cellulose nanocrystal dispersion processing and provides new insight into fluid phase ordering for tailorable optical properties.

Radio Frequency Heating of Carbon Nanotube Composite Materials.

Here, we give the first-ever report of radio frequency (RF) electromagnetic heating of polymer nanocomposite materials via direct-contact and capacitively coupled electric field applicators. Notably, RF heating allows nanocomposite materials to be resistively heated with electric fields. We highlight our novel RF heating technique for multiwalled carbon nanotube (MWCNT) thermoplastic composites and measure their broadband dielectric properties. We also demonstrate three different electric field applicator configurations and discuss their practical use in an industrial setting. We demonstrate the use of RF heating to cure an automotive-grade epoxy loaded with MWCNTs. Our results show that lap shear joints cured faster with the RF method compared with control samples cured in an oven because of the heat-transfer advantages of directly heating the epoxy composite. Finally, we implement our RF curing technique to assemble an automotive structure by locally curing an epoxy adhesive applied to a truck chassis.

Edge contact angle and modified Kelvin equation for condensation in open pores.

We consider capillary condensation transitions occurring in open slits of width L and finite height H immersed in a reservoir of vapor. In this case the pressure at which condensation occurs is closer to saturation compared to that occurring in an infinite slit (H=∞) due to the presence of two menisci that are pinned near the open ends. Using macroscopic arguments, we derive a modified Kelvin equation for the pressure p_{cc}(L;H) at which condensation occurs and show that the two menisci are characterized by an edge contact angle θ_{e} that is always larger than the equilibrium contact angle θ, only equal to it in the limit of macroscopic H. For walls that are completely wet (θ=0) the edge contact angle depends only on the aspect ratio of the capillary and is well described by θ_{e}≈sqrt[πL/2H] for large H. Similar results apply for condensation in cylindrical pores of finite length. We test these predictions against numerical results obtained using a microscopic density-functional model where the presence of an edge contact angle characterizing the shape of the menisci is clearly visible from the density profiles. Below the wetting temperature T_{w} we find very good agreement for slit pores of widths of just a few tens of molecular diameters, while above T_{w} the modified Kelvin equation only becomes accurate for much larger systems.

Welding of 3D-printed carbon nanotube-polymer composites by locally induced microwave heating.

Additive manufacturing through material extrusion, often termed three-dimensional (3D) printing, is a burgeoning method for manufacturing thermoplastic components. However, a key obstacle facing 3D-printed plastic parts in engineering applications is the weak weld between successive filament traces, which often leads to delamination and mechanical failure. This is the chief obstacle to the use of thermoplastic additive manufacturing. We report a novel concept for welding 3D-printed thermoplastic interfaces using intense localized heating of carbon nanotubes (CNTs) by microwave irradiation. The microwave heating of the CNT-polymer composites is a function of CNT percolation, as shown through in situ infrared imaging and simulation. We apply CNT-loaded coatings to a 3D printer filament; after printing, microwave irradiation is shown to improve the weld fracture strength by 275%. These remarkable results open up entirely new design spaces for additive manufacturing and also yield new insight into the coupling between dielectric properties and radio frequency field response for nanomaterial networks.

Scaling behavior of thin films on chemically heterogeneous walls.

We study the adsorption of a fluid in the grand canonical ensemble occurring at a planar heterogeneous wall which is decorated with a chemical stripe of width L. We suppose that the material of the stripe strongly preferentially adsorbs the liquid in contrast to the outer material which is only partially wet. This competition leads to the nucleation of a droplet of liquid on the stripe, the height h_{m} and shape of which (at bulk two-phase coexistence) has been predicted previously using mesoscopic interfacial Hamiltonian theory. We test these predictions using a microscopic Fundamental Measure Density Functional Theory which incorporates short-ranged fluid-fluid and fully long-ranged wall-fluid interactions. Our model functional accurately describes packing effects not captured by the interfacial Hamiltonian but still we show that there is excellent agreement with the predictions h_{m}≈L^{1/2} and for the scaled circular shape of the drop even for L as small as 50 molecular diameters. For smaller stripes the droplet height is considerably lower than that predicted by the mesoscopic interfacial theory. Phase transitions for droplet configurations occurring on substrates with multiple stripes are also discussed.

The effect of bending stiffness on scaling laws for the size of colloidal nanosheets.

Using coarse-grained Brownian dynamics simulations, we study the relationship between hydrodynamic radius ([Formula: see text] and the lateral size ([Formula: see text] of dispersed nanosheets. Our simulation results show that the bending modulus of the nanosheets has a significant impact on the exponent of this power-law relationship between the radius of gyration (and thus [Formula: see text] and [Formula: see text] The exponent can vary from 0.17 to 1. This sheds light on the interpretation of dynamic light scattering (DLS) measurements, such that DLS data can capture both nanosheet lateral size and modulus (which is, in turn, affected by nanosheet thickness).

Synthesis and characterization of styrene oxide adducts with cysteine, histidine, and lysine in human globin.

Styrene 7,8-oxide (SO), a reactive metabolic intermediate of the industrial chemical styrene, binds covalently at nucleophilic amino acid residues of blood proteins in vivo and in vitro. In this study, SO adducts with cysteine, lysine, and histidine were synthesized, characterized, and then used as authentic standards to assign and quantitate the SO adducts in globin incubated with SO. S-(2-Hydroxy-1-phenylethyl)cysteine and S-(2-hydroxy-2-phenylethyl)cysteine were prepared by direct alkylation of cysteine with (R)-SO or (S)-SO. To prepare the SO adducts with lysine and histidine, Nalpha-Boc-protected amino acids were alkylated with (R)-SO or (S)-SO followed by deprotection of the Boc group to obtain Nepsilon-(2-hydroxy-1-phenylethyl)lysine and Nepsilon-(2-hydroxy-2-phenylethyl)lysine as well as Npi-(2-hydroxy-1-phenylethyl)histidine, Npi-(2-hydroxy-2-phenylethyl)histidine, Ntau-(2-hydroxy-1-phenylethyl)histidine, and Ntau-(2-hydroxy-2-phenylethyl)histidine. The individual regioisomers were isolated from their mixtures by semipreparative HPLC, and their structure was assigned using NMR techniques. The SO-modified globin, isolated from human hemoglobin incubated in vitro with racemic SO at a molar ratio SO/globin of 100:1 or 10:1, was digested with pronase and subjected to LC/MS and GC/MS analysis. All known regioisomers of the SO adducts were detected, with S-(2-hydroxy-1-phenylethyl)cysteine, Nepsilon-(2-hydroxy-1-phenylethyl)lysine, and Ntau-(2-hydroxy-2-phenylethyl)histidine being the most abundant in the modified globin. Deuterated analogues of the SO adducts were employed as internal standards. The SO-amino acid adducts described here appear to be suitable biomarkers for long-term exposures to styrene or SO.