PAA/PEO Comb Polymer Effects on Rheological Properties and Inter-particle Forces in Aqueous Silica Suspensions

Journal of Colloid and Interface Science. Jun, 2003  |  Pubmed ID: 16256604

The effects of a poly(acrylic acid) (PAA)-poly(ethylene) (PEO) comb polymer dispersant on the rheological properties and inter-particle forces in aqueous silica suspensions have been studied under varying pH conditions. The comb polymer was found to adsorb more strongly under acidic than basic conditions, indicating that the PAA backbone of the copolymer preferentially adsorbs onto silica surfaces with the PEO "teeth" extending out from the surface into the solution. In the presence of low concentrations of copolymer, the silica suspensions were stable due to electrostatic repulsions between the silica surfaces. At higher copolymer concentrations and under neutral and basic conditions, where the copolymer interacted only weakly with silica, the suspensions showed a transition from a dispersed to weakly flocculated state and attractive forces were measured between silica surfaces. Under acidic conditions, the silica dispersion also destabilized at intermediate copolymer adsorbed density and then was re-stabilized at higher adsorbed coverage. The silica suspensions were stable at high copolymer coverage due to steric repulsions between the particles. The destabilization at intermediate coverage is thought to be due to polymer bridging between particles or possibly depletion forces.

Chaotic Mixing in Three-dimensional Microvascular Networks Fabricated by Direct-write Assembly

Nature Materials. Apr, 2003  |  Pubmed ID: 12690401

The creation of geometrically complex fluidic devices is a subject of broad fundamental and technological interest. Here, we demonstrate the fabrication of three-dimensional (3D) microvascular networks through direct-write assembly of a fugitive organic ink. This approach yields a pervasive network of smooth cylindrical channels (approximately 10-300 microm) with defined connectivity. Square-spiral towers, isolated within this vascular network, promote fluid mixing through chaotic advection. These vertical towers give rise to dramatic improvements in mixing relative to simple straight (1D) and square-wave (2D) channels while significantly reducing the device planar footprint. We envisage that 3D microvascular networks will provide an enabling platform for a wide array of fluidic-based applications.

Stress Development During Drying of Calcium Carbonate Suspensions Containing Carboxymethylcellulose and Latex Particles

Journal of Colloid and Interface Science. Apr, 2004  |  Pubmed ID: 14985016

Stress development during drying of coatings produced from aqueous dispersions of calcium carbonate particles in the presence and absence of organic binders was studied using a controlled-environment stress apparatus that simultaneously monitored drying stress, weight loss, and relative humidity. Specifically, the influence of two organic binders on drying stress evolution was investigated: (1) carboxymethylcellulose, a water-soluble viscosifying aid, and (2) a styrene-butadiene latex emulsion of varying glass transition temperature. The stress histories exhibited three distinct regions. First, a period of stress rise was observed, which reflected the capillary tension exerted by the liquid on the particle network. Second, a maximum stress was observed. Third, it was followed by a period of either stress decay or rise depending on the organic species present. Significant differences in stress histories were observed between coatings containing soluble and nonsoluble binders. Maximum drying stresses (sigmamax) of 0.2-0.5 MPa were observed for coatings produced from pure calcium carbonate or calcium carbonate-latex suspensions, whereas coatings with carboxymethylcellulose exhibited substantially higher sigmamax values of 1-2 MPa. Upon drying, these coatings were quite hygroscopic, such that cyclic variations in relative humidity induced large cyclic changes in residual stress.

Microperiodic Structures: Direct Writing of Three-dimensional Webs

Nature. Mar, 2004  |  Pubmed ID: 15042080

Applications are emerging that require the creation of fine-scale structures in three dimensions--examples include scaffolds for tissue engineering, micro-fluidic devices and photonic materials that control light propagation over a range of frequencies. But writing methods such as dip-pen nanolithography and ink-jet printing are either confined to two dimensions or beset by wetting and spreading problems. Here we use concentrated polyelectrolyte inks to write three-dimensional microperiodic structures directly without using masks. Our technique enables us to write arbitrary three-dimensional patterns whose features are nearly two orders of magnitude smaller than those attained with other multilayer printing techniques.

Structural Evolution of Colloidal Crystals with Increasing Ionic Strength

Langmuir : the ACS Journal of Surfaces and Colloids. Aug, 2004  |  Pubmed ID: 15301486

We have directly observed the structural evolution of colloidal crystals as a function of increasing ionic strength using confocal scanning laser microscopy. Silica colloids were sedimented onto a glass substrate in deionized water to create large, single domain crystals. The solution ionic strength was then increased by one of three methods of controlled electrolyte addition: (1) direct injection of electrolyte solutions, (2) single step diffusion of electrolyte solutions through a dialysis membrane, and (3) multiple step diffusion of electrolyte solutions of increasing ionic strength through a dialysis membrane. During direct injection of electrolyte solutions, initially large, single domain colloidal crystals were shear melted and then evolved into polycrystalline structures at low ionic strengths and gels at higher ionic strengths. Diffusion of electrolyte solutions though dialysis membranes in a single step produced gradient-driven transport that also melted initial single domain crystals to yield polycrystalline and gel structures similar to the injection approach. Interestingly, the multistep diffusion of several electrolyte solutions through dialysis membranes facilitated retention of large, single domain crystals even as particles came into adhesive contact. This was achieved by reducing the contraction rate of the crystalline lattice to allow sufficient time for diffusion-limited configurational rearrangements to occur within the evolving structure. These mechanically robust, single domain colloidal crystals may find important applications as templates for photonic materials and sensors.

Nanoparticle-mediated Epitaxial Assembly of Colloidal Crystals on Patterned Substrates

Langmuir : the ACS Journal of Surfaces and Colloids. Jun, 2004  |  Pubmed ID: 15986661

We have studied the assembly of 3-D colloidal crystals from binary mixtures of colloidal microspheres and highly charged nanoparticles on flat and epitaxially patterned substrates created by focused ion beam milling. The microspheres were settled onto these substrates from dilute binary mixtures. Laser scanning confocal microscopy was used to directly observe microsphere structural evolution during sedimentation, nanoparticle gelation, and subsequent drying. After microsphere settling, the nanoparticle solution surrounding the colloidal crystal was gelled in situ by introducing ammonia vapor, which increased the pH and enabled drying with minimal microsphere rearrangement. By infilling the dried colloidal crystals with an index-matched fluorescent dye solution, we generated full 3-D reconstructions of their structure including defects as a function of initial suspension composition and pitch of the patterned features. Through proper control over these important parameters, 3-D colloidal crystals were created with low defect densities suitable for use as templates for photonic crystals and photonic band gap materials.

Soluble Organic Additive Effects on Stress Development During Drying of Calcium Carbonate Suspensions

Journal of Colloid and Interface Science. Oct, 2005  |  Pubmed ID: 16122547

The effect of polymer, plasticizer, and surfactant additives on stress development during drying of calcium carbonate particulate coatings was studied using a controlled-environment apparatus that simultaneously monitors drying stress, weight loss, and relative humidity. We found that the calcium carbonate coatings display a drying stress evolution typical of granular films, which is characterized by a sharp capillary-induced stress rise followed by a rapid stress relaxation. The addition of a soluble polymer to the CaCO3 suspension resulted in a two-stage stress evolution process. The initial stress rise stems from capillary-pressure-induced stresses within the film, while the second, larger stress rise occurs due to solidification and shrinkage of the polymeric species. Measurements on the corresponding pure polymer solutions established a clear correlation between the magnitude of residual stress in both the polymer and CaCO3-polymer films to the physical properties of the polymer phase, i.e. its glass transition temperature, T(g), and Young's modulus. The addition of small organic molecules can reduce the residual stress observed in the CaCO3-polymer films; e.g., glycerol, which acts as a plasticizer, reduces the drying stress by lowering T(g), while surfactant additions reduce the surface tension of the liquid phase, and, hence, the magnitude of the capillary pressure within the film.

Electrostatically Tuned Interactions in Silica Microsphere-polystyrene Nanoparticle Mixtures

Langmuir : the ACS Journal of Surfaces and Colloids. Sep, 2005  |  Pubmed ID: 16142928

We explore the generality of nanoparticle haloing as a novel colloidal stabilization mechanism in binary mixtures of silica microspheres and polystyrene nanoparticles. By selectively tuning their electrostatic interactions, both the initial microsphere stability and the role of nanoparticle additions are varied. Adsorption isotherm and zeta potential measurements indicate that highly charged nanoparticles exhibit a weak (haloing) association with negligibly charged microspheres, whereas they either strongly adsorb onto oppositely charged or are repelled by like-charged microsphere surfaces, respectively. Bulk sedimentation and confocal scanning fluorescence microscopy reveal that important differences in system stability emerge depending on whether the added nanoparticles serve as haloing, bridging, or depletant species.

Interparticle Interactions and Direct Imaging of Colloidal Phases Assembled from Microsphere-nanoparticle Mixtures

Langmuir : the ACS Journal of Surfaces and Colloids. Oct, 2005  |  Pubmed ID: 16229517

We investigate the interparticle interactions, phase behavior, and structure of microsphere-nanoparticle mixtures that possess high size and charge asymmetry. We employ a novel Monte Carlo simulation scheme to calculate the effective microsphere interactions in suspension, yielding new insight into the origin of the experimentally observed behavior. The initial settling velocity, final sediment density, and three-dimensional structure of colloidal phases assembled from these binary mixtures via gravitational settling of silica microspheres in water and index-matched solutions exhibit a strong compositional dependence. Confocal laser scanning microscopy is used to directly image and quantify their structural evolution during assembly. Below a lower critical nanoparticle volume fraction (phi(nano) < phi(L,C)), the intrinsic van der Waals attraction between microspheres leads to the formation of colloidal gels. These gels exhibit enhanced consolidation as phi(nano) approaches phi(L,C). When phi(nano) exceeds phi(L,C), an effective repulsion arises between microspheres due to the formation of a dynamic nanoparticle halo around the colloids. From this stable fluid phase, the microspheres settle into a crystalline array. Finally, above an upper critical nanoparticle volume fraction (phi(nano) > phi(U,C)), colloidal gels form whose structure becomes more open with increasing nanoparticle concentration due to the emergence of an effective microsphere attraction, whose magnitude exhibits a superlinear dependence on phi(nano).

Light-regulated Electrostatic Interactions in Colloidal Suspensions

Journal of the American Chemical Society. Oct, 2005  |  Pubmed ID: 16231901

The net charge of a colloidal particle was controlled using light and a new photocleavable self-assembled monolayer (SAM). The SAM contained a terminal ammonium group and a centrally located carboxylic acid group that was masked with an ortho-nitrobenzyl functionality. Once exposed to UV light, the 2-nitrobenzyl group was cleaved, therefore transforming the colloidal particle from a net positive (silica-SAM-NH3+) to a net negative (silica-SAM-COO-) charge. By varying the UV exposure time, their zeta potential could be tailored between +26 and -60 mV at neutral pH. To demonstrate a photoinduced gel-to-fluid phase transition, a binary colloidal suspension composed of silica-SAM-NH3+ and negatively charged, rhodamine-labeled silica particles was mixed to form a gel. Exposure to UV light rendered all of the particles negative and therefore converted the system into a colloidal fluid that settles to form a dense sediment.

Phase Behavior and Rheological Properties of Polyelectrolyte Inks for Direct-write Assembly

Langmuir : the ACS Journal of Surfaces and Colloids. Jan, 2005  |  Pubmed ID: 15620339

Three-dimensional (3-D) structures with micron-sized features have been fabricated via the direct-write assembly of polyelectrolyte inks. By mixing oppositely charged species under solution conditions that promote polyelectrolyte exchange reactions, we have created concentrated fluids capable of flowing through microscale deposition nozzles. Ink deposition into an alcohol/water coagulation reservoir yielded polyelectrolyte filaments that rapidly solidify to enable three-dimensional patterning of microperiodic structures with self-supporting features. The influence of ink and reservoir chemistry on the phase behavior, rheological properties, and assembly of concentrated polyelectrolyte complexes is reported with an emphasis on the optimal conditions for 3-D writing.

Concentrated Hydroxyapatite Inks for Direct-write Assembly of 3-D Periodic Scaffolds

Biomaterials. Oct, 2005  |  Pubmed ID: 15878368

Hydroxyapatite (HA) scaffolds with a 3-D periodic architecture and multiscale porosity have been fabricated by direct-write assembly. Concentrated HA inks with tailored viscoelastic properties were developed to enable the construction of complex 3-D architectures comprised of self-supporting cylindrical rods in a layer-by-layer patterning sequence. By controlling their lattice constant and sintering conditions, 3-D periodic HA scaffolds were produced with a bimodal pore size distribution. Mercury intrusion porosimetry (MIP) was used to determine the characteristic pore size and volume associated with the interconnected pore channels between HA rods and the finer pores within the partially sintered HA rods.

Phase Behavior and 3D Structure of Strongly Attractive Microsphere-nanoparticle Mixtures

Langmuir : the ACS Journal of Surfaces and Colloids. Nov, 2005  |  Pubmed ID: 16285769

We investigate the phase behavior and 3D structure of strongly attractive mixtures of silica microspheres and polystyrene nanoparticles. These binary mixtures are electrostatically tuned to promote a repulsion between like-charged (microsphere-microsphere and nanoparticle-nanoparticle) species and a strong attraction between oppositely charged (microsphere-nanoparticle) species. Using confocal fluorescence scanning microscopy, we directly observe the 3D structure of colloidal phases assembled from these mixtures as a function of varying composition. In the absence of nanoparticle additions, the charged-stabilized microspheres assemble into a polycrystalline array upon sedimentation. With increasing nanoparticle volume fraction, nanoparticle bridges form between microspheres, inducing their flocculation. At even higher nanoparticle volume fractions, the microspheres become well coated with nanoparticles, leading to their charge reversal and subsequent restabilization. We demonstrate how this fluid-gel-fluid transition can be utilized to control the morphology of the colloidal phases formed under gravity-driven sedimentation.

Nonlinear Elasticity and Yielding of Nanoparticle Glasses

Langmuir : the ACS Journal of Surfaces and Colloids. Mar, 2006  |  Pubmed ID: 16519437

We employ experiment and theory to explore the nonlinear elasticity and yielding of concentrated suspensions of nanoparticles which interact via purely repulsive forces. These glassy suspensions are found to exhibit high exponent power law or simple exponential dependences of the shear elastic modulus and perturbative yield stress on nanoparticle volume fraction, as well as a monotonic decrease of the perturbative yield strain with increasing concentration. Our experimental observations are in good agreement with the predictions of a recently developed microscopic statistical mechanical theory, which describes glassy dynamics based on a nonequilibrium free energy that incorporates local cage correlations and activated barrier hopping processes [(1) Schweizer, K. S.; Saltzman, E. J. J. Chem. Phys. 2003, 119, 1181. (2) Saltzman, E. J.; Schweizer, K. S. J. Chem. Phys. 2003, 119, 1197. (3) Kobelev, V.; Schweizer, K. S. Phy. Rev. E 2005, 71, 021401].

Microfluidic Assembly of Homogeneous and Janus Colloid-filled Hydrogel Granules

Langmuir : the ACS Journal of Surfaces and Colloids. Oct, 2006  |  Pubmed ID: 17014093

The microfluidic assembly of colloid-filled hydrogel granules of varying shape and composition is described. First, drops are formed by shearing a concentrated colloidal microsphere-acrylamide suspension in a continuous oil phase using a sheath-flow device. Both homogeneous and Janus (hemispherically distinct) spheres and disks are produced by confining the assembled drops in microchannels of varying geometry. Next, photopolymerization is carried out shortly after drop breakup to preserve their morphology. Representative wet and dried granules are characterized using fluorescence and scanning electron microscopy, respectively. Our approach offers a facile route for assembling colloid-filled hydrogel granules with controlled shape and composition.

Patterning Colloidal Films Via Evaporative Lithography

Physical Review Letters. Apr, 2007  |  Pubmed ID: 17501317

We investigate evaporative lithography as a route for patterning colloidal films. Films are dried beneath a mask that induces periodic variations between regions of free and hindered evaporation. Direct imaging reveals that particles segregate laterally within the film, as fluid and entrained particles migrate towards regions of higher evaporative flux. The films exhibit remarkable pattern formation that can be regulated by tuning the initial suspension composition, separation distance between the mask and underlying film, and mask geometry.

Self-healing Materials with Microvascular Networks

Nature Materials. Aug, 2007  |  Pubmed ID: 17558429

Self-healing polymers composed of microencapsulated healing agents exhibit remarkable mechanical performance and regenerative ability, but are limited to autonomic repair of a single damage event in a given location. Self-healing is triggered by crack-induced rupture of the embedded capsules; thus, once a localized region is depleted of healing agent, further repair is precluded. Re-mendable polymers can achieve multiple healing cycles, but require external intervention in the form of heat treatment and applied pressure. Here, we report a self-healing system capable of autonomously repairing repeated damage events. Our bio-inspired coating-substrate design delivers healing agent to cracks in a polymer coating via a three-dimensional microvascular network embedded in the substrate. Crack damage in the epoxy coating is healed repeatedly. This approach opens new avenues for continuous delivery of healing agents for self-repair as well as other active species for additional functionality.

In Vivo Bone Response to 3D Periodic Hydroxyapatite Scaffolds Assembled by Direct Ink Writing

Journal of Biomedical Materials Research. Part A. Dec, 2007  |  Pubmed ID: 17559109

The in vivo bone response of 3D periodic hydroxyapatite (HA) scaffolds is investigated. Two groups of HA scaffolds (11 mm diameter x 3.5 mm thick) are fabricated by direct-write assembly of a concentrated HA ink. The scaffolds consist of cylindrical rods periodically arranged into four quadrants with varying separation distances between rods. In the first group, HA rods (250 microm in diameter) are patterned to create pore channels, whose areal dimensions are 250 x 250 microm(2) in quadrant 1, 250 x 500 microm(2) in quadrants 2 and 4, and 500 x 500 microm(2) in quadrant 3. In the second group, HA rods (400 microm in diameter) are patterned to create pore channels, whose areal dimensions of 500 x 500 microm(2) in quadrant 1, 500 x 750 microm(2) in quadrants 2 and 4, and 750 x 750 microm(2) in quadrant 3. Each group of scaffolds is partially densified by sintering at 1200 degrees C prior to being implanted bilaterally in trephine defects of skeletally mature New Zealand White rabbits. Their tissue response is evaluated at 8 and 16 weeks using micro-computed tomography, histology, and scanning electron microscopy. New trabecular bone is conducted rapidly and efficiently across substantial distances within these patterned 3D HA scaffolds. Our observations suggest that HA rods are first coated with a layer of new bone followed by subsequent scaffold infilling via outward and inward radial growth of the coated regions. Direct-write assembly of 3D periodic scaffolds composed of micro-porous HA rods arrayed to produce macro-pores that are size-matched to trabecular bone may represent an optimal strategy for bone repair and replacement structures.

Direct Flow Visualization of Colloidal Gels in Microfluidic Channels

Langmuir : the ACS Journal of Surfaces and Colloids. Aug, 2007  |  Pubmed ID: 17629305

The behavior of colloidal gels under pressure-driven flow in square microchannels is quantified by microscopic particle image velocimetry (muPIV) and compared to predictions of available rheological models. The gels consist of hydrophobically modified silica microspheres (phi = 0.15-0.33) suspended in a refractive index-matched fluid along with fluorescent tracers to aid visualization. Measured velocity flow profiles show a transition from plug flow to more fluid-like behavior with increasing volumetric flow rate (Q) at all phi. This transition is not captured by theoretical predictions of the flow profile based on the Herschel-Bulkley model. Rather, a model that accounts for gel breakup into a suspension of clusters at elevated shear rates by assuming a finite viscosity at infinite shear is needed to accurately predict the flow behavior of colloidal gels at large Q.

Phase Behavior and Rheological Properties of Polyamine-rich Complexes for Direct-write Assembly

Langmuir : the ACS Journal of Surfaces and Colloids. Dec, 2007  |  Pubmed ID: 17973413

Polyamine-rich complexes are developed for microscale patterning of planar and 3-D structures by direct ink writing. The complexes are formed by mixing poly(allylamine) hydrochloride and poly(acrylic acid) sodium salt in water in a nonstoichiometric ratio. Their phase behavior, rheological properties, and coagulation behavior in alcohol-water reservoirs are characterized. Direct comparisons are made between these complexes, which are based on mixtures of linear polyelectrolytes, and prior observations of complexes composed of linear and highly branched chains. [Gratson, G. M.; Xu, M.; Lewis, J. A. Nature 2004, 428, 386. Gratson, G. M.; Lewis, J. A. Langmuir 2005, 21, 457-464.] The optimal polyamine-rich ink and reservoir compositions are identified for direct-write assembly of wavy, gradient, and 3-D microperiodic architectures.

Marangoni Effects on Evaporative Lithographic Patterning of Colloidal Films

Langmuir : the ACS Journal of Surfaces and Colloids. Apr, 2008  |  Pubmed ID: 18315026

We investigate the effects of Marangoni stresses on the evaporative lithographic patterning of colloidal films (Harris, D. J.; Hu, H.; Conrad, J. C.; Lewis, J. A. Phys. Rev. Lett. 2007, 98 (14), 148301). Films are dried beneath a mask that induces periodically varying regions of free and hindered evaporation. Direct imaging reveals that silica microspheres suspended within an organic solvent exhibit recirculating flows induced by temperature and surface tension gradients that arise during drying. The films display remarkable pattern formation with a majority of the particles deposited in the masked regions. Above a critical colloid volume fraction, recirculating flows are suppressed, leading to particle deposition in unmasked regions of high evaporative flux.

Quantitative Measurement of Nanoparticle Halo Formation Around Colloidal Microspheres in Binary Mixtures

Langmuir : the ACS Journal of Surfaces and Colloids. Jun, 2008  |  Pubmed ID: 18507406

A new colloidal stabilization mechanism, known as nanoparticle "haloing" (Tohver, V.; Smay, J. E.; Braem, A.; Braun, P. V.; Lewis, J. A. Proc. Natl. Acad. Sci. U.S.A. 2001, 98, (16), 8950-8954), has been predicted theoretically and inferred experimentally in microsphere-nanoparticle mixtures that possess high charge and size asymmetry. The term "halo" implies the existence of a nonzero separation distance between the highly charged nanoparticles and the negligibly charged microspheres that they surround. By means of ultrasmall-angle X-ray scattering, we have quantified the microsphere-nanoparticle separation distance as well as the number of nanoparticles and their lateral separation distance within the self-organized halos that form in these binary mixtures.

Structure of Colloidal Gels During Microchannel Flow

Langmuir : the ACS Journal of Surfaces and Colloids. Aug, 2008  |  Pubmed ID: 18582141

We investigate the structure and flow behavior of colloidal gels in microchannels using confocal microscopy. Silica particles are first coated with a cationic polyelectrolyte and then flocculated by the addition of an anionic polyelectrolyte. In the quiescent state, the suspension is an isotropic and homogeneous gel. Under shear flow, the suspension contains dense clusters that yield at intercluster boundaries, resulting in network breakup at high shear rates. These structural changes coincide with a transition from pluglike flow at low pressures to fluidlike flow at high pressures.

Structure and Dynamics of Biphasic Colloidal Mixtures

Physical Review. E, Statistical, Nonlinear, and Soft Matter Physics. Jun, 2008  |  Pubmed ID: 18643205

We investigate the structure and dynamics of biphasic colloidal mixtures composed of coexisting attractive and repulsive microspheres by confocal microscopy. Attractive gels formed in the presence of repulsive microspheres are more spatially homogeneous and, on average, are both more locally tenuous and have fewer large voids than their unary counterparts. The repulsive microspheres within these mixtures display heterogeneous dynamics, with some species exhibiting freely diffusive Brownian motion while others are trapped within the gel network during aggregation.

Size Ratio Effects on Interparticle Interactions and Phase Behavior of Microsphere-nanoparticle Mixtures

Langmuir : the ACS Journal of Surfaces and Colloids. Oct, 2008  |  Pubmed ID: 18816017

We investigate the interparticle interactions and phase behavior of microsphere-nanoparticle mixtures of high charge asymmetry and varying size ratio. In the absence of nanoparticles, negligibly charged microspheres flocculate as a result of van der Waals interactions. Upon addition of a lower critical nanoparticle volume fraction, the microspheres are stabilized by the formation of nanoparticle halos around each microsphere. , A weak attraction between the two species leads to a pronounced enhancement of the effective nanoparticle concentration near the microsphere surface relative to the bulk solution. Above an upper critical nanoparticle volume fraction, the microspheres undergo reentrant gelation. Binary mixtures, in which the effective nanoparticle size is reduced at a fixed microsphere diameter, exhibit a narrow window of stability that ultimately disappears with increasing ionic strength. By contrast, binary mixtures of varying microsphere diameter are stabilized at similar nanoparticle volume fractions and exhibit a broader window of stability with decreasing size ratio. This unexpected observation may arise from the reduced attraction between smaller microspheres because negligible differences in nanoparticle halo formation are observed in these mixtures.

Ultrathin Silicon Solar Microcells for Semitransparent, Mechanically Flexible and Microconcentrator Module Designs

Nature Materials. Nov, 2008  |  Pubmed ID: 18836435

The high natural abundance of silicon, together with its excellent reliability and good efficiency in solar cells, suggest its continued use in production of solar energy, on massive scales, for the foreseeable future. Although organics, nanocrystals, nanowires and other new materials hold significant promise, many opportunities continue to exist for research into unconventional means of exploiting silicon in advanced photovoltaic systems. Here, we describe modules that use large-scale arrays of silicon solar microcells created from bulk wafers and integrated in diverse spatial layouts on foreign substrates by transfer printing. The resulting devices can offer useful features, including high degrees of mechanical flexibility, user-definable transparency and ultrathin-form-factor microconcentrator designs. Detailed studies of the processes for creating and manipulating such microcells, together with theoretical and experimental investigations of the electrical, mechanical and optical characteristics of several types of module that incorporate them, illuminate the key aspects.

Omnidirectional Printing of Flexible, Stretchable, and Spanning Silver Microelectrodes

Science (New York, N.Y.). Mar, 2009  |  Pubmed ID: 19213878

Flexible, stretchable, and spanning microelectrodes that carry signals from one circuit element to another are needed for many emerging forms of electronic and optoelectronic devices. We have patterned silver microelectrodes by omnidirectional printing of concentrated nanoparticle inks in both uniform and high-aspect ratio motifs with minimum widths of approximately 2 micrometers onto semiconductor, plastic, and glass substrates. The patterned microelectrodes can withstand repeated bending and stretching to large levels of strain with minimal degradation of their electrical properties. With this approach, wire bonding to fragile three-dimensional devices and spanning interconnects for solar cell and light-emitting diode arrays are demonstrated.

Cationic Comb Polymer Superdispersants for Colloidal Silica Suspensions

Langmuir : the ACS Journal of Surfaces and Colloids. Jun, 2009  |  Pubmed ID: 19400573

We investigate the ability of a cationic comb polymer composed of a poly(trimethylammonium iodide ethyl methacrylate) (PTMAM) backbone and uncharged poly(ethylene glycol) (PEG) teeth to stabilize aqueous silica suspensions of varying ionic strength and pH. Both PTMAM-g-PEG and its homopolymer backbone, PTMAM, are synthesized via reversible addition-fragmentation chain transfer followed by quaternization of the pendant amine groups with methyl iodide. Through a combination of polymer adsorption, zeta potential, and sedimentation measurements as well as confocal imaging of sediment structures, we find that PTMAM-g-PEG imparts stability over a broad range of solution conditions, where pure PTMAM fails.

Evaporative Lithographic Patterning of Binary Colloidal Films

Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences. Dec, 2009  |  Pubmed ID: 19933133

Evaporative lithography offers a promising new route for patterning a broad array of soft materials. In this approach, a mask is placed above a drying film to create regions of free and hindered evaporation, which drive fluid convection and entrained particles to regions of highest evaporative flux. We show that binary colloidal films exhibit remarkable pattern formation when subjected to a periodic evaporative landscape during drying.

Two- and Three-dimensional Folding of Thin Film Single-crystalline Silicon for Photovoltaic Power Applications

Proceedings of the National Academy of Sciences of the United States of America. Dec, 2009  |  Pubmed ID: 19934059

Fabrication of 3D electronic structures in the micrometer-to-millimeter range is extremely challenging due to the inherently 2D nature of most conventional wafer-based fabrication methods. Self-assembly, and the related method of self-folding of planar patterned membranes, provide a promising means to solve this problem. Here, we investigate self-assembly processes driven by wetting interactions to shape the contour of a functional, nonplanar photovoltaic (PV) device. A mechanics model based on the theory of thin plates is developed to identify the critical conditions for self-folding of different 2D geometrical shapes. This strategy is demonstrated for specifically designed millimeter-scale silicon objects, which are self-assembled into spherical, and other 3D shapes and integrated into fully functional light-trapping PV devices. The resulting 3D devices offer a promising way to efficiently harvest solar energy in thin cells using concentrator microarrays that function without active light tracking systems.

Structural Evolution of Colloidal Gels During Constricted Microchannel Flow

Langmuir : the ACS Journal of Surfaces and Colloids. May, 2010  |  Pubmed ID: 20369847

We investigate the structure of colloidal gels flowing through constrictions in microchannels using confocal microscopy. As the gel traverses the constricted region, both the average velocity and particle density increase downstream. While the average flow profile is smoothly varying, stagnation zones develop at the constriction entry, leading to markedly nonuniform local flow profiles. Dense clusters undergo shear-induced yielding at intercluster boundaries, which enhances the structural heterogeneity of the suspension at the constriction outlet.

Printed Origami Structures

Advanced Materials (Deerfield Beach, Fla.). May, 2010  |  Pubmed ID: 20397151

Multidimensional Architectures for Functional Optical Devices

Advanced Materials (Deerfield Beach, Fla.). Mar, 2010  |  Pubmed ID: 20401933

Materials exhibiting multidimensional structure with characteristic lengths ranging from the nanometer to the micrometer scale have extraordinary potential for emerging optical applications based on the regulation of light-matter interactions via the mesoscale organization of matter. As the structural dimensionality increases, the opportunities for controlling light-matter interactions become increasingly diverse and powerful. Recent advances in multidimensional structures have been demonstrated that serve as the basis for three-dimensional photonic-bandgap materials, metamaterials, optical cloaks, highly efficient low-cost solar cells, and chemical and biological sensors. In this Review, the state-of-the-art design and fabrication of multidimensional architectures for functional optical devices are covered and the next steps for this important field are described.

Printed Origami Structures (Adv. Mater. 20/2010)

Advanced Materials (Deerfield Beach, Fla.). May, 2010  |  Pubmed ID: 20503211

Direct-write Assembly of Microperiodic Planar and Spanning ITO Microelectrodes

Chemical Communications (Cambridge, England). Oct, 2010  |  Pubmed ID: 20820510

Printed Sn-doped In(2)O(3) (ITO) microelectrodes are fabricated by direct-write assembly of sol-gel inks with varying concentration. This maskless, non-lithographic approach provides a facile route to patterning transparent conductive features in planar arrays and spanning architectures.

Genotyping by Alkaline Dehybridization Using Graphically Encoded Particles

Chemistry (Weinheim an Der Bergstrasse, Germany). Mar, 2011  |  Pubmed ID: 21305624

This work describes a nonenzymatic, isothermal genotyping method based on the kinetic differences exhibited in the dehybridization of perfectly matched (PM) and single-base mismatched (MM) DNA duplexes in an alkaline solution. Multifunctional encoded hydrogel particles incorporating allele-specific oligonucleotide (ASO) probes in two distinct regions were fabricated by using microfluidic-based stop-flow lithography. Each particle contained two distinct ASO probe sequences differing at a single base position, and thus each particle was capable of simultaneously probing two distinct target alleles. Fluorescently labeled target alleles were annealed to both probe regions of a particle, and the rate of duplex dehybridization was monitored by using fluorescence microscopy. Duplex dehybridization was achieved through an alkaline stimulus using either a pH step function or a temporal pH gradient. When a single target probe sequence was used, the rate of mismatch duplex dehybridization could be discriminated from the rate of perfect match duplex dehybridization. In a more demanding application in which two distinct probe sequences were used, we found that the rate profiles provided a means to discriminate probe dehybridizations from both of the two mismatched duplexes as well as to distinguish at high certainty the dehybridization of the two perfectly matched duplexes. These results demonstrate an ability of alkaline dehybridization to correctly discriminate the rank hierarchy of thermodynamic stability among four sets of perfect match and single-base mismatch duplexes. We further demonstrate that these rate profiles are strongly temperature dependent and illustrate how the sensitivity can be compensated beneficially by the use of an actuating gradient pH field.

Conformal Printing of Electrically Small Antennas on Three-dimensional Surfaces

Advanced Materials (Deerfield Beach, Fla.). Mar, 2011  |  Pubmed ID: 21400592

Omnidirectional Printing of 3D Microvascular Networks

Advanced Materials (Deerfield Beach, Fla.). Jun, 2011  |  Pubmed ID: 21438034

Transparent Conductive Grids Via Direct Writing of Silver Nanoparticle Inks

Nanoscale. Jul, 2011  |  Pubmed ID: 21491039

Transparent conductive grids are patterned by direct writing of concentrated silver nanoparticle inks. This maskless, etch-free patterning approach is used to produce well-defined, two-dimensional periodic arrays composed of conductive features with center-to-center separation distances of up to 400 µm and an optical transmittance as high as 94.1%.

Pen-on-paper Flexible Electronics

Advanced Materials (Deerfield Beach, Fla.). Aug, 2011  |  Pubmed ID: 21688330

3D Microperiodic Hydrogel Scaffolds for Robust Neuronal Cultures

Advanced Functional Materials. Jan, 2011  |  Pubmed ID: 21709750

Three-dimensional (3D) microperiodic scaffolds of poly(2-hydroxyethyl methacrylate) (pHEMA) have been fabricated by direct-write assembly of a photopolymerizable hydrogel ink. The ink is initially composed of physically entangled pHEMA chains dissolved in a solution of HEMA monomer, comonomer, photoinitiator and water. Upon printing 3D scaffolds of varying architecture, the ink filaments are exposed to UV light, where they are transformed into an interpenetrating hydrogel network of chemically cross-linked and physically entangled pHEMA chains. These 3D microperiodic scaffolds are rendered growth compliant for primary rat hippocampal neurons by absorption of polylysine. Neuronal cells thrive on these scaffolds, forming differentiated, intricately branched networks. Confocal laser scanning microscopy reveals that both cell distribution and extent of neuronal process alignment depend upon scaffold architecture. This work provides an important step forward in the creation of suitable platforms for in vitro study of sensitive cell types.

Photocurable Liquid Core-fugitive Shell Printing of Optical Waveguides

Advanced Materials (Deerfield Beach, Fla.). Nov, 2011  |  Pubmed ID: 21989713

Reactive Silver Inks for Patterning High-conductivity Features at Mild Temperatures

Journal of the American Chemical Society. Jan, 2012  |  Pubmed ID: 22220580

Reactive silver inks for printing highly conductive features (>10(4) S/cm) at room temperature have been created. These inks are stable, particle-free, and suitable for a wide range of patterning techniques. Upon annealing at 90 °C, the printed electrodes exhibit an electrical conductivity equivalent to that of bulk silver.

Impact of Text and Email Messaging on the Sexual Health of Young People: a Randomised Controlled Trial

Journal of Epidemiology and Community Health. Jan, 2012  |  Pubmed ID: 21415232

To carry out a randomised controlled trial on the effect of a new method of health promotion-email and mobile phone text messages (short messaging service (SMS))-on young people's sexual health.